The earth is strongly heated every day by incoming radiation from the sun. This heating is offset by an equally strong infrared radiation leaving the planet. Interestingly, if Earth were without any atmosphere, and if its surface reflectivity did not change, global-mean surface temperature would be roughly 33°C colder than it is today. This large difference is due to the strong atmospheric absorption of infrared radiation leaving the earth's surface. The major atmospheric infrared absorbers are clouds, water vapor, and CO2. This strong infrared absorption (and strong reemission) effect is extremely robust: It is readily measured in the laboratory and is straightforwardly measured from earth-orbiting satellites. Simply put, adding CO2 to the atmosphere adds another "blanket" to the planet and, thus, directly changes the heat balance of the earth's atmosphere.
Individuals skeptical about the reality of global warming have correctly noted that, in terms of direct trapping of outgoing infrared radiation, water vapor is by far the dominant greenhouse gas on earth. Since water vapor dominates the current radiative balance, how can it be that CO2 is anything other than a minor contributor to earth's absorption of infrared radiation? Part of the answer comes from the well-known modeling result from infrared spectroscopy that net planetary radiative forcing changes roughly linearly in response to logarithmic changes in CO2 . Thus, a quadrupling of CO2 gives another roughly 1°C direct warming over the direct 1°C warming for a CO2 doubling, valid for the extreme assumption that water vapor mixing ratios and clouds do not change. Interestingly, this approximate relationship also holds for a large extended range as CO2 is decreased (see footnote 3).
It is thus hard to escape the conclusion that CO2 provides a measurable direct addition to the atmospheric trapping of infrared radiation leaving the surface of our planet.