Greenhouse gases in Earth's atmosphereIn order, Earth's most abundant greenhouse gases are: When these gases are ranked by their contribution to the greenhouse effect, the most important are:
The major non-gas contributor Earth's greenhouse effect, clouds, also absorb and emit infrared radiation and thus have an effect on radiative properties of the greenhouse gases.45 The contribution to the greenhouse effect by a gas is affected by both the characteristics of the gas and its abundance. For example, on a molecule-for-molecule basis methane is a much stronger greenhouse gas than carbon dioxide, but it is present in much smaller concentrations so that its total contribution is smaller. It is not possible to state that a certain gas causes an exact percentage of the greenhouse effect, because the influences of the various gases are not additive. The higher ends of the ranges quoted are for the gas alone; the lower ends, for the gas counting overlaps.54 Other greenhouse gases include, but are not limited to, 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.6 Although contributing to many other physical and chemical reactions, the major atmospheric constituents, nitrogen (N2), oxygen (O2), and argon (Ar), are not greenhouse gases. This is because homonuclear diatomic molecules such as N2 and O2 and monatomic molecules such as Ar have no net change in their dipole moment when they vibrate and hence are almost totally unaffected by infrared light. Although heteronuclear diatomics such as carbon monoxide (CO) or hydrogen chloride (HCl) absorb IR, these molecules are short-lived in the atmosphere owing to their reactivity and solubility. As a consequence they do not contribute significantly to the greenhouse effect and are not often included when discussing greenhouse gases. Late 19th century scientists experimentally discovered that N2 and O2 did not absorb infrared radiation (called, at that time, "dark radiation") and that CO2 and many other gases did absorb such radiation. It was recognized in the early 20th century that the greenhouse gases in the atmosphere caused the Earth's overall temperature to be higher than it would be without them. Natural and anthropogenic
Top: Increasing atmospheric CO2 levels as measured in the atmosphere and ice cores. Bottom: The amount of net carbon increase in the atmosphere, compared to carbon emissions from burning fossil fuel.
Aside from purely human-produced synthetic halocarbons, most greenhouse gases have sources from both the ecosystem in general (natural) and from human activities specifically (anthropogenic). During the pre-industrial holocene, concentrations of existing gases were roughly constant. In the industrial era, human activities have added greenhouse gases to the atmosphere, mainly through the burning of fossil fuels and clearing of forests.78
Ice cores provide evidence for variation in greenhouse gas concentrations over the past 800,000 years. Both CO2 and CH4 vary between glacial and interglacial phases, and concentrations of these gases correlate strongly with temperature. Before the ice core record, direct measurements do not exist. Various proxies and modelling suggests large variations; 500 Myr ago CO2 levels were likely 10 times higher than now.9 Indeed higher CO2 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 Mya.101112 The spread of land plants is thought to have reduced CO2 concentrations during the late Devonian, and plant activities as both sources and sinks of CO2 have since been important in providing stabilising feedbacks.13 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 Mya, by a colossal volcanic outgassing which raised the CO2 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 1mm per day.14 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 only about 1% of emissions from human sources.1415 Anthropogenic greenhouse gases
The projected temperature increase for a range of greenhouse gas stabilization scenarios (the coloured bands). The black line in middle of the shaded area indicates 'best estimates'; the red and the blue lines the likely limits. From the work of IPCC AR4, 2007.
Since about 1750 human activity has increased the concentration of carbon dioxide and other greenhouse gases.16 Natural sources of carbon dioxide are more than 20 times greater than sources due to human activity,17 but over periods longer than a few years natural sources are closely balanced by natural sinks such as weathering of continental rocks and photosynthesis of carbon compounds by plants and marine plankton. As a result of this balance, the atmospheric concentration of carbon dioxide remained between 260 and 280 parts per million for the 10,000 years between the end of the last glacial maximum and the start of the industrial era.18 Some of the main sources of greenhouse gases due to human activity include:
The seven sources of CO2 from fossil fuel combustion are (with percentage contributions for 2000–2004):20
The U.S. EPA ranks the major greenhouse gas contributing end-user sectors in the following order: industrial, transportation, residential, commercial and agricultural.21 Major sources of an individual's GHG include home heating and cooling, electricity consumption, and transportation. Corresponding conservation measures are improving home building insulation, compact fluorescent lamps and choosing energy-efficient vehicles. Carbon dioxide, methane, nitrous oxide and three groups of fluorinated gases (sulfur hexafluoride, HFCs, and PFCs) are the major greenhouse gases and the subject of the Kyoto Protocol, which came into force in 2005.22 Although CFCs are greenhouse gases, they are regulated by the Montreal Protocol, which was motivated by CFCs' contribution to ozone depletion rather than by their contribution to global warming. Note that ozone depletion has only a minor role in greenhouse warming though the two processes often are confused in the media. Nitrogen trifluoride (NF3) is used in the manufacture of microelectronics. It is a strong greenhouse gas, but presently its concentration is very low and it is not subject to greenhouse gas treaties. Role of water vaporWater vapor is a naturally occurring greenhouse gas and accounts for the largest percentage of the greenhouse effect, between 36% and 66% for water vapor alone, and between 66% and 85% when in factoring clouds.5 Water vapor concentrations fluctuate regionally, but human activity does not directly affect water vapor concentrations except at local scales (for example, near irrigated fields). The Clausius-Clapeyron relation establishes that air can hold more water vapor per unit volume when it warms. This and other basic principles indicate that increasing water vapor concentrations in warmer air will amplify the greenhouse effect created by anthropogenic greenhouse gases while maintaining nearly constant relative humidity. Thus water vapor acts as a positive feedback to the forcing provided by greenhouse gases such as CO2. This feedback effect is reproduced in current state-of-the-art climate models.2324 Greenhouse gas emissionsMeasurements from Antarctic ice cores show that just before industrial emissions started, atmospheric CO2 levels were about 280 parts per million by volume (ppm; the units µL/L are occasionally used and are identical to parts per million by volume). From the same ice cores it appears that CO2 concentrations stayed between 260 and 280 ppm during the preceding 10,000 years. Because of the way air is trapped in ice and the time period represented in each ice sample analyzed, figures for times several thousand years ago are averages over a few centuries and not annual levels.25 One study using evidence from stomata of fossilized leaves suggests greater variability, with CO2 levels above 300 ppm during the period 7,000–10,000 years ago,26 though others have argued that these findings more likely reflect calibration/contamination problems rather than actual CO2 variability.2728 Since the beginning of the Industrial Revolution, the concentrations of many of the greenhouse gases have increased. The concentration of CO2 has increased by about 100 ppm (i.e., from 280 ppm to 380 ppm). The first 50 ppm increase took place in about 200 years, from the start of the Industrial Revolution to around 1973; the next 50 ppm increase took place in about 33 years, from 1973 to 2006.29 Many observations are available online in a variety of Atmospheric Chemistry Observational Databases. The greenhouse gases with the largest radiative forcing are:
Global anthropogenic Carbon emissions 1751–2004.
(Source: IPCC radiative forcing report 1994 updated (to 1998) by IPCC TAR table 6.13031 ). Recent rates of change and emissionThe sharp acceleration in CO2 emissions since 2000 of >3% y−1 (>2 ppm y−1) from 1.1% y−1 during the 1990s is attributable to the lapse of formerly declining trends in carbon intensity of both developing and developed nations. Although over 3/4 of cumulative anthropogenic CO2 is still attributable to the developed world, China was responsible for most of global growth in emissions during this period. Localised plummeting emissions associated with the collapse of the Soviet Union have been followed by slow emissions growth in this region due to more efficient energy use, made necessary by the increasing proportion of it that is exported.20 In comparison, methane has not increased appreciably, and N2O by 0.25% y−1.32 The direct emissions from industry have declined due to a constant improvement in energy efficiency, but also to a high penetration of electricity. If one includes indirect emissions, related to the production of electricity, CO2 emissions from industry in Europe are roughly stabilized since 1994.33 AsiaAtmospheric levels of CO2 continue to rise, partly a sign of the industrial rise of Asian economies led by China.34 Over the 2000-2010 interval China is expected to increase its carbon dioxide emissions by 600 Mt, largely because of the rapid construction of old-fashioned power plants in poorer internal provinces.35 See also: Asian brown cloud United KingdomThe UK set itself a target of reducing carbon dioxide emissions by 20% from 1990 levels by 2010, but according to its own figures it will fall short of this target by almost 4%.36 United StatesThe United States emitted 16.3% more GHG in 2005 than it did in 1990.37 According to a preliminary estimate by the Netherlands Environmental Assessment Agency, the largest national producer of CO2 emissions since 2006 has been China with an estimated annual production of about 6200 megatonnes. China is followed by the United States with about 5,800 megatonnes. However the per capita emission figures of China are still about one quarter of those of the US population. Relative to 2005, China's fossil CO2 emissions increased in 2006 by 8.7%, while in the USA, comparable CO2 emissions decreased in 2006 by 1.4%. The agency notes that its estimates do not include some CO2 sources of uncertain magnitude.38 These figures rely on national CO2 data that do not include aviation. Although these tonnages are small compared to the CO2 in the Earth's atmosphere, they are significantly larger than pre-industrial levels.
Long-term trendAtmospheric carbon dioxide concentration is increasing at an increasing rate. In the 1960s, the average annual increase was only 37% of what it was in 2000 through 2007.39 Removal from the atmosphere and global warming potentialThis section deals with natural processes. For projects to deliberately remove greenhouses gases from the atmosphere, see geoengineering, carbon dioxide scrubbing and greenhouse gas remediation Aside from water vapor, which has a residence time of about nine days, most greenhouse gases 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. Greenhouse gases can be removed from the atmosphere by various processes:
In addition, the amount of Carbon dioxide and Methane entering the atmosphere can be reduced
However, ozone, a greenhouse gas, is formed:
Atmospheric lifetimeJacob (1999)40 defines the lifetime τ of an atmospheric species X in a one-box model as the average time that a molecule of X remains in the box. Mathematically τ 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 (Fout), chemical loss of X (L), and deposition of X (D) (all in kg/sec): The atmospheric lifetime of a species therefore measures the time required to restore equilibrium following an increase 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. The atmospheric lifetime of CO2 is often incorrectly stated to be only a few years because that is the average time for any CO2 molecule to stay in the atmosphere before being removed by mixing into the ocean, photosynthesis, or other processes. However, this ignores the balancing fluxes of CO2 into the atmosphere from the other reservoirs. It is the net concentration changes of the various greenhouse gases by all sources and sinks that determines atmospheric lifetime, not just the removal processes.citation needed Global warming potentialThe global warming potential (GWP) depends on both the efficiency of the molecule as a greenhouse gas and its atmospheric lifetime. GWP is measured relative to the same mass of CO2 and evaluated for a specific timescale. Thus, if a molecule has a high GWP on a short time scale (say 20 years) but has only a short lifetime, it will have a large GWP on a 20 year scale but a small one on a 100 year scale. Conversely, if a molecule has a longer atmospheric lifetime than CO2 its GWP will increase with time. Examples of the atmospheric lifetime and GWP for several greenhouse gases include:
Source: IPCC Fourth Assessment Report, Table 2.14. The use of CFC-12 (except some essential uses) has been phased out due to its ozone depleting properties.44 The phasing-out of less active HCFC-compounds will be completed in 2030.45 Airborne fractionAirborne fraction (AF) is the proportion of a emission (e.g. CO2) remaining in the atmosphere after a specified time. Canadell (2007)46 define the annual AF as the ratio of the atmospheric CO2 increase in a given year to that year’s total emissions, and calculate that of the average 9.1 PgC y-1 of total anthropogenic emissions from 2000 to 2006, the AF was 0.45. For CO2 the AF over the last 50 years (1956-2006) has been increasing at 0.25±0.21%/year.46 Related effectsCarbon monoxide has an indirect radiative effect by elevating concentrations of methane and tropospheric ozone through scavenging of atmospheric constituents (e.g., the hydroxyl radical, OH) that would otherwise destroy them. Carbon monoxide is created when carbon-containing fuels are burned incompletely. Through natural processes in the atmosphere, it is eventually oxidized to carbon dioxide. Carbon monoxide has an atmospheric lifetime of only a few months47 and as a consequence is spatially more variable than longer-lived gases. Another potentially important indirect effect comes from methane, which in addition to its direct radiative impact also contributes to ozone formation. Shindell et al (2005)48 argue that the contribution to climate change from methane is at least double previous estimates as a result of this effect.49 See also
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