Of the greenhouse gases, carbon dioxide (CO₂) is the most significant. Natural sources of atmospheric CO₂ include outgassing from volcanoes, the combustion and natural decay of organic matter, and respiration by aerobic (oxygen-using) organisms. These sources are balanced, on average, by a set of physical, chemical, or biological processes, called “sinks,” that tend to remove CO₂ from the atmosphere. Significant natural sinks include terrestrial vegetation, which takes up CO₂ during the process of photosynthesis.

A number of oceanic processes also act as carbon sinks. One such process, called the “solubility pump,” involves the descent of surface seawater containing dissolved CO₂. Another process, the “biological pump,” involves the uptake of dissolved CO₂ by marine vegetation and phytoplankton (small free-floating photosynthetic organisms) living in the upper ocean or by other marine organisms that use CO₂ to build skeletons and other structures made of calcium carbonate (CaCO₃). As these organisms expire and fall to the ocean floor, the carbon they contain is transported downward and eventually buried at depth. A long-term balance between these natural sources and sinks leads to the background, or natural, level of CO₂ in the atmosphere.

In contrast, human activities increase atmospheric CO₂ levels primarily through the burning of fossil fuels—principally oil and coal and secondarily natural gas, for use in transportation, heating, and the generation of electrical power—and through the production of cement. Other anthropogenic sources include the burning of forests and the clearing of land. Anthropogenic emissions currently account for the annual release of about 7 gigatons (7 billion tons) of carbon into the atmosphere. Anthropogenic emissions are equal to approximately 3 percent of the total emissions of CO₂ by natural sources, and this amplified carbon load from human activities far exceeds the offsetting capacity of natural sinks (by perhaps as much as 2–3 gigatons per year).

CO₂ consequently accumulated in the atmosphere at an average rate of 1.4 ppm per year between 1959 and 2006 and roughly 2.0 ppm per year between 2006 and 2018. Overall, this rate of accumulation has been linear (that is, uniform over time). However, certain current sinks, such as the oceans, could become sources in the future (see Carbon cycle feedbacks). This may lead to a situation in which the concentration of atmospheric CO₂ builds at an exponential rate (that is, its rate of increase is also increasing).

The natural background level of carbon dioxide varies on timescales of millions of years because of slow changes in outgassing through volcanic activity. For example, roughly 100 million years ago, during the Cretaceous Period (145 million to 66 million years ago), CO₂ concentrations appear to have been several times higher than they are today (perhaps close to 2,000 ppm). Over the past 700,000 years, CO₂ concentrations have varied over a far smaller range (between roughly 180 and 300 ppm) in association with the same Earth orbital effects linked to the coming and going of the Pleistocene ice ages (see below Natural influences on climate). By the early 21st century CO₂ levels had reached 384 ppm, which is approximately 37 percent above the natural background level of roughly 280 ppm that existed at the beginning of the Industrial Revolution. Atmospheric CO₂ levels continued to increase, and by 2022 they had reached 419 ppm. Such levels are believed to be the highest in at least 800,000 years according to ice core measurements and may be the highest in at least 5 million years according to other lines of evidence.

Radiative forcing caused by carbon dioxide varies in an approximately logarithmic fashion with the concentration of that gas in the atmosphere. The logarithmic relationship occurs as the result of a saturation effect wherein it becomes increasingly difficult, as CO₂ concentrations increase, for additional CO₂ molecules to further influence the “infrared window” (a certain narrow band of wavelengths in the infrared region that is not absorbed by atmospheric gases). The logarithmic relationship predicts that the surface warming potential will rise by roughly the same amount for each doubling of CO₂ concentration. At current rates of fossil fuel use, a doubling of CO₂ concentrations over preindustrial levels is expected to take place by the middle of the 21st century (when CO₂ concentrations are projected to reach 560 ppm). A doubling of CO₂ concentrations would represent an increase of roughly 4 watts per square metre of radiative forcing. Given typical estimates of “climate sensitivity” in the absence of any offsetting factors, this energy increase would lead to a warming of 2 to 5 °C (3.6 to 9 °F) over preindustrial times (see Feedback mechanisms and climate sensitivity). The total radiative forcing by anthropogenic CO₂ emissions since the beginning of the industrial age is approximately 1.66 watts per square metre.

Methane

Methane (CH₄) is the second most important greenhouse gas. CH₄ is more potent than CO₂ because the radiative forcing produced per molecule is greater. In addition, the infrared window is less saturated in the range of wavelengths of radiation absorbed by CH₄, so more molecules may fill in the region. However, CH₄ exists in far lower concentrations than CO₂ in the atmosphere, and its concentrations by volume in the atmosphere are generally measured in parts per billion (ppb) rather than ppm. CH₄ also has a considerably shorter residence time in the atmosphere than CO₂ (the residence time for CH₄ is roughly 10 years, compared with hundreds of years for CO₂).

Natural sources of methane include tropical and northern wetlands, methane-oxidizing bacteria that feed on organic material consumed by termites, volcanoes, seepage vents of the seafloor in regions rich with organic sediment, and methane hydrates trapped along the continental shelves of the oceans and in polar permafrost. The primary natural sink for methane is the atmosphere itself, as methane reacts readily with the hydroxyl radical (∙OH) within the troposphere to form CO₂ and water vapour (H₂O). When CH₄ reaches the stratosphere, it is destroyed. Another natural sink is soil, where methane is oxidized by bacteria.

As with CO₂, human activity is increasing the CH₄ concentration faster than it can be offset by natural sinks. Anthropogenic sources currently account for approximately 70 percent of total annual emissions, leading to substantial increases in concentration over time. The major anthropogenic sources of atmospheric CH₄ are rice cultivation, livestock farming, the burning of coal and natural gas, the combustion of biomass, and the decomposition of organic matter in landfills. Future trends are particularly difficult to anticipate. This is in part due to an incomplete understanding of the climate feedbacks associated with CH₄ emissions. In addition it is difficult to predict how, as human populations grow, possible changes in livestock raising, rice cultivation, and energy utilization will influence CH₄ emissions.

It is believed that a sudden increase in the concentration of methane in the atmosphere was responsible for a warming event that raised average global temperatures by 4–8 °C (7.2–14.4 °F) over a few thousand years during the so-called Paleocene-Eocene Thermal Maximum, or PETM. This episode took place roughly 55 million years ago, and the rise in CH₄ appears to have been related to a massive volcanic eruption that interacted with methane-containing flood deposits. As a result, large amounts of gaseous CH₄ were injected into the atmosphere. It is difficult to know precisely how high these concentrations were or how long they persisted. At very high concentrations, residence times of CH₄ in the atmosphere can become much greater than the nominal 10-year residence time that applies today. Nevertheless, it is likely that these concentrations reached several ppm during the PETM.

Methane concentrations have also varied over a smaller range (between roughly 350 and 800 ppb) in association with the Pleistocene ice age cycles (see Natural influences on climate). Preindustrial levels of CH₄ in the atmosphere were approximately 700 ppb, whereas levels exceeded 1,915 ppb in the fall of 2022. (These concentrations are well above the natural levels observed for at least the past 650,000 years.) The net radiative forcing by anthropogenic CH₄ emissions is approximately 0.5 watt per square metre—or roughly one-third the radiative forcing of CO₂.