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Appendix 2





        Isotopes of Carbon






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        Both  C and  C are stable (nonradioactive) isotopes of  waters in some regions. For carbon that forms in the
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        carbon that occur naturally in Earth’s vegetation, water,  absence of oxygen (in “reducing conditions”), δ C val-
        and air. The  C isotope accounts for more than 99% of  ues can be far more negative, around –50 to –60‰.
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        all the carbon present on Earth, and  C accounts for   Carbon samples with relatively large amounts of  C
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        most of the rest. A small amount exists as radioactive  compared with  C have more positive δ C values and
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        14 C. Geochemists who analyze material for its carbon  are referred to as  C-enriched or  C-depleted. Sam-
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        isotope composition measure small variations around  ples with relatively small amounts of  C compared with
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        the average  C/ C ratio of less than 0.01.          12 C have more negative δ C values and are referred to
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           Similar to the convention used for oxygen isotopes,  as  C-depleted or  C-enriched.
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        measurements of  C/ C ratios are reported as depar-    Fractionation during photosynthesis causes changes
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        tures in parts per thousand (‰) from a laboratory   in δ C values (Figure 1). As the plants take inorganic
        standard:                                           carbon and turn it into organic carbon, they incorpo-
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                                                            rate the  C isotope into their living tissue more easily
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                   ( C/ C) sample  – ( C/ C) standard       than the  C isotope. This discrimination in favor of  C
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            δ C = –––––––––––––––––––––––––––––– × 1000               13
             13
            (‰)          ( C/ C)                            shifts the  δ C of organic matter toward values that
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                                 standard
                                                            are more negative than the initial inorganic carbon
           All measurements are referenced to standards sup-  source.
        plied by the National Bureau of Standards for use as a  For example, plant plankton in the ocean take inor-
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        common reference point. Like the oxygen isotope     ganic carbon from seawater with a δ C value near 0‰
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        ratios, carbon isotope ratios are multiplied by 1000 to  and convert it to organic carbon with a δ C value near
        convert the very small measured variations in an already  –22‰. Some of the organic carbon is sent to the deep
        small ratio to a more handy numerical form. As a result,  ocean, but most is oxidized back to inorganic form and
        δ C values for carbon that occurs in oxygen-rich con-  recycled within the ocean or sent back to the surface
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        ditions fall between –25‰ for some kinds of vegetation  waters. The net export of a small fraction of  C-rich
        on land to +2‰ for carbon dissolved in ocean surface  organic carbon to the deep ocean leaves the remaining
             Carbon source:  CO 2
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                 δ C = –7‰
           Fractionation     Fractionation
              –18‰               –6‰
         Trees and        Summer
          shrubs           grasses                      Carbon source:
           (C3)             (C4)                      Dissolved inorganic C
           –25‰                                         in surface ocean
                            –13‰                      (δ C initially = 0 ‰)
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                                              (Remaining inorganic C = +1‰)
                                                                              FIGURE 1 Photosynthesis and
                                                             Fractionation    carbon isotope fractionation
                                                                –22‰
                                                                              Photosynthesis on land and in the
                                                      Dead organic C          surface ocean converts inorganic
                                                         –22‰                 carbon to organic form and causes
                                                                              large negative shifts in δ C values of
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                                                                              the organic carbon produced.
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