The Keeling curve is what is used to track how many parts per million (ppm) of CO2 is in the atmosphere. This goes back 800,000 years, using ice core data. After 1958, it uses sensors and measurements directly from Mauna Loa in Hawaii. Check it out.
To learn why scientists know the rise is definitely caused by human activities, see Ralph Keeling's explanation. An independent way to know CO2 concentrations is by measuring the ratio of Carbon-13 to Carbon-12. To scientists, climate change is undoubtedly due to human burning of fossil fuels - there is no legitimate scientific debate about this any more, it is clear from multiple streams of data and analysis.
To get a history of how science has studied climate change and for dozens of references to numerous aspects of this complex science topic, go here - it is extensive and is updated regularly.
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