• Delta13C;
  • F-F event;
  • atmospheric CO2 level;
  • south China


  1. Top of page
  2. Abstract
  3. 1. Introduction
  4. 2. Sampling and Methodology
  5. 3. Results
  6. 4. Discussion
  7. 5. Conclusions
  8. Acknowledgments
  9. References
  10. Supporting Information

[1] A perturbation of the global carbon cycle has often been used for interpreting the Frasnian-Famennian (F-F) mass extinction. However, the changes of atmospheric CO2 level (pCO2) during this interval are much debatable. To illustrate the carbon cycle during F-F transition, paired inorganic (δ13Ccarb) and organic (δ13Corg) carbon isotope analyses were carried out on two late Devonian carbonate sequences (Dongcun and Yangdi) from south China. The larger amplitude shift of δ13Corg compared to δ13Ccarb and its resultant Δ13C (Δ13C = δ13Ccarbδ13Corg) decrease indicate decreased atmospheric CO2level around the F-F boundary. The onset ofpCO2 level decrease predates that of marine regressions, which coincide with the beginning of conodont extinctions, suggesting that temperature decrease induced by decreased greenhouse effect of atmospheric CO2might have contributed to the F-F mass extinction.

1. Introduction

  1. Top of page
  2. Abstract
  3. 1. Introduction
  4. 2. Sampling and Methodology
  5. 3. Results
  6. 4. Discussion
  7. 5. Conclusions
  8. Acknowledgments
  9. References
  10. Supporting Information

[2] The Frasnian-Famennian (F-F) mass extinction is one of the five big mass extinctions in the Phanerozoic, during which a significant reduction in biodiversities occurred, though the extinction extensity is not as large as those in end Ordovician, end Permian, and end Cretaceous [Bambach et al., 2004; Racki, 2005; Stigall, 2010]. The cause of this bioevent remains a subject of intensive debate with both external (bolide impact) and internal (e.g., increased hydrothermal-volcanic activities, climate changes) mechanisms invoked [McGhee, 1996; Racki, 2005]. Most mechanisms are involved in a δ13Ccarbpositive excursion around the F-F boundary [McGhee, 1996; Joachimski et al., 2002; Ma and Bai, 2002; Racki et al., 2002; Goddéris and Joachimski, 2004; Riquier et al., 2006; van Geldern et al., 2006; Xu et al., 2008; John et al., 2010; Zeng et al., 2011]. The δ13Ccarb positive excursion, together with organic rich horizons known as the Upper Kellwasser horizons in biostratigraphy [Schindler, 1990; Walliser, 1996], is interpreted as the result of increased carbon burial [McGhee et al., 1986; Joachimski et al., 2002; Ma and Bai, 2002; Racki et al., 2002; Xu et al., 2008]. It is suggested that atmospheric CO2 level would decease with increased organic carbon burial [Kump and Arthur, 1999], leading to climate change and thus mass extinction [Joachimski et al., 2002; Racki et al., 2002]. However, to our knowledge, no direct evidence supports a decrease of pCO2level around the F-F boundary, complicating the interpretation of the F-F mass extinction by the global carbon cycle change.

[3] Δ13C is often used as reliable paleo-pCO2 barometer [Cramer and Saltzman, 2007; Young et al., 2008], because the isotopic difference between carbonate and organic matter is dominated by photosynthetic fractionation, which partly depends on the concentration of dissolved CO2 in seawater [e.g., Popp et al., 1989; Freeman and Hayes, 1992; Hayes et al., 1999]. Unfortunately, most previous studies focused separately on the changes of inorganic and organic carbon isotope [McGhee et al., 1986; Joachimski and Buggisch, 1993; Wang et al., 1996; Racki et al., 2002; Xu et al., 2003; Buggisch and Joachimski, 2006; Izokh et al., 2009], few examined the variations of Δ13C. Even the few Δ13C data seem to change geographically [Joachimski, 1997; Chen et al., 2005]. In the Baisha and Fuhe sections from south China, Δ13C shows high-frequency vibrations around the F-F boundary [Chen et al., 2005], but it is suggested that there is no obvious change in Europe [Joachimski et al., 2002].

[4] In this study, high-resolution analyses of coupled inorganic and organic carbon isotope were carried out on two late Devonian carbonate sequences (Dongcun and Yangdi) in south China. The primary aims of this study are to characterize the changes of atmospheric CO2level during the F-F transition and address the links between the perturbation of the global carbon cycle and the mass extinction.

2. Sampling and Methodology

  1. Top of page
  2. Abstract
  3. 1. Introduction
  4. 2. Sampling and Methodology
  5. 3. Results
  6. 4. Discussion
  7. 5. Conclusions
  8. Acknowledgments
  9. References
  10. Supporting Information

[5] Dongcun section (N24.95°, E110.42°) is located at the Dongcun village, about 20 km northwest of Yangshuo (Figure 1). A total of 12 conodont zones from transitants to crepida are recognized [Wang, 1994; Wang and Ziegler, 2002]. The F-F (triangularis/linguiformis) boundary is located at 2.0 m above a thin dark micritic limestone from which most of conodonts of the linguiformis fauna disappeared [Wang and Ziegler, 2002]. The Yangdi section is situated to the northeast of the Dongcun section (Figure 1). The conodont zones of Yangdi section is identified by Ji [1994].


Figure 1. Paleogeographic location of south China (SC) [Joachimski et al., 2002] and depositional context of the Dongcun and Yangdi sections.

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[6] Total 451 samples were collected in this study, 201 from Dongcun section and 250 from Yangdi section. Eighty-nine samples were selected for paired analysis of inorganic and organic carbon isotope (51 from Dongcun section, 38 from Yangdi section). Onlyδ13Ccarb was analyzed for the rest samples. All specimens were cleaned by ultrasonication and dried under room temperature. Micritic components were preferentially sampled for carbon isotope analysis because of their little diagenetic alteration [Marshall, 1992]. For the specimens with limited micritic components (marlstone and grainstone), the nonrecrystallized or insignificantly recrystallized parts were sampled by drilling under microscope. The sample powders were reacted with 100% phosphoric acid for 12 h under 50°C. The produced CO2 was collected with liquid nitrogen, and isotopic ratios of 13C/12C were measured by MAT 252 mass spectrometer. For organic carbon isotope analysis, 50–100 g sample powder reacted with 1 M HCl for removing carbonate. The HCl-insoluble residues of samples were combusted offline, and the evolved CO2 gas was submitted to mass spectrometric measurement. The isotopic data were reported in the conventional δ notation as per mil (‰) deviation relative to the PDB standard. The precision measured by multianalysis of both GBW04405 (National stable isotope of carbon and oxygen in carbonate) and replicate samples is better than 0.1‰ for carbon isotope.

3. Results

  1. Top of page
  2. Abstract
  3. 1. Introduction
  4. 2. Sampling and Methodology
  5. 3. Results
  6. 4. Discussion
  7. 5. Conclusions
  8. Acknowledgments
  9. References
  10. Supporting Information

[7] In both Dongcun and Yangdi sections, δ13Ccarb exhibits an increasing pattern from Frasnian to Famennian with two peaks in the late rhenanazone and around the F-F boundary (Figure 2). These two positive excursions are comparable with the records from other continents including Europe, America, and Africa [McGhee et al., 1986; Joachimski and Buggisch, 1993; Joachimski, 1997; Joachimski et al., 2002; Wang et al., 1996; Buggisch and Joachimski, 2006], and correspond to the two Kellwasser horizons in biostratigraphy [Xu et al., 2008]. Detailed observation shows that the δ13Ccarbexcursion that occurred around the F-F boundary is composed of two-stepwise increases (Figure 2). In Dongcun section, δ13Ccarb, first increases from 0.8‰ to 1.5‰ during the interval of 2.4–1.9 m below the F-F boundary, and then remains a relative stable value before it increases again at the F-F boundary (Figure 2).


Figure 2. Distributions of δ13Ccarb and δ13Corg along the sequences of the Dongcun and Yangdi sections (δ13Ccarb data adopted from Xu et al. [2008]).

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[8] The δ13Corg parallels δ13Ccarb along the profiles of the Dongcun and Yangdi sections, and also shifts to positive in the late rhenanazone and around the F-F boundary (Figure 2). Noteworthily, the amplitudes of the δ13Corg excursions are larger than those of δ13Ccarb shifts (Table 1). At the F-F boundary,δ13Corg has an increase of 4.0‰ and 4.5‰ in the Dongcun and Yangdi sections, respectively, while their corresponding shifts of δ13Ccarb are less than 3.0‰ (Figure 2). In the rhenana zone, the excursions of δ13Ccarb are smaller than 2.0‰ in both sections, but the shifts of δ13Corg are individually more than 4.0‰ in the Dongcun section and 3.5‰ in the Yangdi section (Figure 2).

Table 1. Carbon Isotope Data of the Dongcun and Yangdi Sections
CodeDepthδ13Ccarbδ13CorgΔ13CFossil AgeCodeDepthδ13Ccarbδ13CorgΔ13CFossil Age
Dongcun Section
DC43528.581.26   DC40911.881.61   
DC43427.831.43   DC40811.531.21   
DC43226.331.30−26.7828.08 DC40510.482.01   
DC43125.581.29   DC40410.131.33−25.0126.34 
DC43024.831.37   DC4039.782.01   
DC42924.081.25   DC4029.431.77   
DC42823.331.33−26.8928.22 DC4019.081.73   
DC42722.581.09   DC3988.031.89−25.1327.02 
DC42621.831.28   DC3977.681.97   
DC42521.081.33   DC3967.331.93   
DC42420.331.48   DC3956.981.71−24.7626.47 
DC42319.581.54−26.5928.13 DC3946.631.83   
DC42218.831.46   DC3936.281.77   
DC42118.081.34   DC3925.932.07−24.1426.21 
DC41815.831.21−25.8427.05 DC3915.582.04   
DC41715.081.53   DC3905.232.40   
DC41614.331.15   DC3894.882.10−24.7226.82 
DC41513.981.40−25.9327.33 DC3884.622.00  Crepida
DC41413.631.69   DC3874.442.07   
DC41313.281.60   DC3864.252.19   
DC41212.931.73−25.9527.68 DC3854.072.29−24.1526.44 
DC41112.581.86   DC3833.552.34   
DC41012.231.65   DC3823.312.73   
DC3782.402.75−24.0926.84 DC349−0.941.30−26.4527.75 
DC3772.073.03   DC348−1.061.54   
DC3762.032.57−24.3826.95 DC347−1.181.22   
DC3721.872.71   DC346−1.300.84−25.4726.31 
DC3711.772.71   DC345−1.421.51   
DC3691.492.51−24.4326.94 DC344−1.490.59   
DC3671.212.40   DC343−1.561.63−26.8928.52 
DC3661.072.53   DC342−1.661.27   
DC3650.952.32−24.4926.81 DC341−1.761.65   
DC3640.832.40   DC333−2.241.31−26.5627.87 
DC3630.632.05   DC331−2.420.54   
DC3620.502.39   DC330−2.500.68−26.2226.90 
DC3610.352.46   DC329−2.590.76   
DC3600.251.51−24.4325.94 DC328−2.680.73   
DC3590.150.86  TriangularisDC327−2.760.61−27.7628.37 
DC3580.000.94−25.2226.16 DC326−2.850.40   
DC357−0.151.66−25.1226.78 DC325−2.930.63   
DC356−0.251.85   DC324−3.020.54−27.5628.10 
DC355−0.351.57−25.5227.09 DC323−3.150.56   
DC354−0.421.01   DC322−3.280.80 28.24 
DC353−0.541.38−24.4625.84 DC321−3.410.70−27.54  
DC352−0.661.41   DC320−3.540.60   
DC351−0.740.82−25.7326.55 DC319−3.670.62   
DC350−0.821.68   DC318−4.030.61−28.1228.73 
DC317−4.390.71   DC291−10.360.43   
DC316−4.750.75−27.9528.70 DC290−10.710.59   
DC315−5.110.67   DC289−11.060.29   
DC313−5.830.60−28.2928.89 DC288−11.410.04   
DC311−6.550.83   DC286−12.110.00−27.9427.94 
DC310−6.910.47   DC285−12.460.52   
DC309−7.060.40−27.9428.34 DC284−12.810.41   
DC308−7.210.54   DC283−13.160.50   
DC307−7.360.42   DC282−13.510.55   
DC306−7.510.58   DC281−13.860.40−27.1727.57 
DC305−7.660.54   DC280−14.210.29   
DC304−7.810.41−27.5627.97 DC279−14.560.11   
DC303−7.960.55   DC278−14.910.65−27.5028.15 
DC302−8.110.53   DC277−15.260.60   
DC301−8.260.69   DC276−15.610.50   
DC300−8.411.06   DC275−15.960.53−25.7926.32 
DC299−8.560.53   DC274−16.311.26   
DC298−8.710.40   DC273−16.661.61  Linguiformis
DC297−8.860.43   DC272−17.011.22−24.3625.58 
DC296−9.010.14   DC270−17.711.58   
DC295−9.160.15−27.7027.85 DC265−19.460.26−24.9825.24 
DC294−9.310.21   DC263−20.16−0.50   
DC293−9.660.41−27.2527.66 DC262−20.51−0.52−25.3124.79 
DC292−10.010.60   DC261−20.86−0.63   
DC260−21.21−0.73−28.0227.29 DC234−31.610.30−28.7829.08 
DC259−21.56−0.36   DC233−33.110.10   
DC258−21.91−0.84−28.7527.91L. RhenanaDC232−33.460.60   
DC257−22.26−0.35   DC231−33.810.16   
DC256−22.61−0.14   DC230−34.16−0.10   
DC255−22.96−0.64   DC229−34.510.20   
DC254−23.31−0.25   DC228−34.860.10   
DC253−23.66−0.20   DC227−35.211.07   
DC252−24.01−0.30   DC226−35.560.30   
DC250−24.36−0.50−28.3127.81 DC225−35.910.50   
DC249−24.710.20   DC224−36.260.02   
DC248−25.060.50   DC223−36.610.28   
DC247−25.41−0.02   DC222−36.960.16−28.6528.81 
DC246−25.760.10   DC221−37.310.18   
DC245−26.11−0.30   DC220−37.660.17   
DC244−26.460.50−28.6929.19 DC219−38.010.20   
Yangdi Section
YT-001−24.451.36−26.3627.72 YT-027−19.251.44   
YT-002−24.250.86   YT-028−19.051.63   
YT-003−24.050.43−28.4728.90 YT-029−18.851.53   
YT-004−23.852.77   YT-030−18.651.60   
YT-005−23.652.75−24.3127.06 YT-031−18.451.65   
YT-006−23.452.66   YT-032−18.251.47−28.4229.89 
YT-007−23.252.97−25.8128.78 YT-033−18.051.30   
YT-008−23.053.30   YT-034−17.851.37   
YT-009−22.852.81   YT-035−17.651.32   
YT-010−22.653.15   YT-036−17.451.41   
YT-014−21.852.36   YT-037−17.251.13   
YT-015−21.652.21−25.3427.55 YT-038−17.051.18   
YT-016−21.452.39   YT-039−16.851.25   
YT-017−21.252.11   YT-040−16.651.31   
YT-018−21.051.81   YT-041−16.451.17−26.8928.06 
YT-019−20.852.24   YT-042−16.251.30   
YT-020−20.651.24   YT-043−16.050.85   
YT-021−20.451.39−27.9429.33 YT-044−15.850.80   
YT-022−20.251.20   YT-045−15.650.79   
YT-023−20.051.35   YT-046−15.450.75   
YT-024−19.851.44   YT-047−15.250.78   
YT-025−19.651.27   YT-048−15.050.96   
YT-026−19.451.26   YT-049−14.850.88   
YT-050−14.650.96   YT-081−8.450.66  Rhenana
YT-051−14.450.89−28.4629.35 YT-082−8.250.70   
YT-052−14.250.68   YT-083−8.050.76   
YT-053−14.050.86   YT-084−7.950.97   
YT-054−13.850.87   YT-085−7.850.45   
YT-055−13.650.92   YT-086−7.750.54−28.3328.87 
YT-057−13.250.87   YT-087−7.650.52   
YT-058−13.050.75   YT-088−7.550.72   
YT-059−12.850.62   YT-089−7.450.81   
YT-061−12.450.35   YT-090−7.350.81   
YT-063−12.050.26   YT-091−7.250.91   
YT-064−11.850.37   YT-092−7.150.79   
YT-065−11.650.65   YT-093−7.050.58   
YT-066−11.450.61   YT-094−6.950.56   
YT-067−11.250.63   YT-095−6.850.66   
YT-068−11.050.59−27.7028.29 YT-096−6.750.78   
YT-069−10.850.66   YT-097−6.650.66   
YT-070−10.650.71   YT-098−6.550.54   
YT-075−9.650.81   YT-099−6.450.63   
YT-076−9.450.57   YT-100−6.350.70   
YT-077−9.250.59   YT-101−6.250.66   
YT-078−9.050.27   YT-102−6.150.40   
YT-079−8.850.47   YT-103−6.050.24   
YT-080−8.650.52   YT-104−5.950.13   
YT-105−5.850.64   YT-133−3.050.35   
YT-106−5.750.27−28.1328.40 YT-134−2.950.33   
YT-107−5.650.09   YT-135−2.850.42   
YT-111−5.250.74   YT-136−2.750.4254−26.2126.64 
YT-112−5.150.53   YT-137−2.650.81   
YT-113−5.050.44   YT-138−2.550.45   
YT-114−4.950.63   YT-139−2.450.54   
YT-115−4.850.52   YT-140−2.350.49   
YT-116−4.750.61   YT-141−2.250.5236−26.5827.10 
YT-118−4.550.71   YT-142−2.151.04   
YT-119−4.450.85   YT-143−2.050.88   
YT-120−4.350.86   YT-144−1.950.51   
YT-121−4.250.52   YT-145−1.850.52   
YT-122−4.150.64   YT-146−1.750.6804−26.5627.24 
YT-123−4.050.72   YT-147−1.650.69   
YT-124−3.950.79   YT-148−1.550.69   
YT-125−3.850.56   YT-149−1.450.84−26.7727.61 
YT-126−3.750.6718−28.2728.94 YT-150−1.401.81   
YT-127−3.650.26   YT-151−1.352.43   
YT-128−3.550.42   YT-152−1.252.31   
YT-129−3.450.53   YT-153−1.151.64   
YT-130−3.350.53   YT-154−1.051.92   
YT-131−3.250.5334−27.5628.09 YT-155−0.952.03−25.4527.47 
YT-132−3.150.36   YT-156−0.851.9876   
YT-157−0.752.13   YT-1810.503.04   
YT-158−0.651.68−25.7327.42 YT-1820.553.46   
YT-159−0.601.935   YT-1830.602.96   
YT-160−0.552.21   YT-1840.702.76−24.7927.55 
YT-161−0.502.56−25.4728.03 YT-1850.802.4682   
YT-162−0.452.1736   YT-1860.902.01   
YT-163−0.402.54   YT-1871.002.01−24.0526.06 
YT-164−0.352.44−25.2427.68 YT-1881.102.23   
YT-165−0.302.58   YT-1891.202.08   
YT-166−0.252.80   YT-1901.302.12   
YT-167−0.202.59−25.5128.10 YT-1911.402.22   
YT-168−0.152.4624−25.7128.18 YT-1921.502.97−24.1227.09 
YT-169−0.102.51−25.6828.19 YT-1931.602.3548   
YT-170−0.052.29−25.2227.51 YT-1941.702.80   
YT-1710.002.41  LinguiformisYT-1951.802.87   
YT-1720.053.18  TriangularisYT-1961.902.73   
YT-1730.102.98−24.3227.30 YT-1972.002.70−24.2526.95 
YT-1740.152.7778   YT-1982.102.7896   
YT-1750.203.13   YT-1992.202.72   
YT-1760.252.76−24.5527.31 YT-2012.302.30   
YT-1770.302.90   YT-2022.502.66   
YT-1780.353.57   YT-2032.602.72   
YT-1790.402.73−25.4128.13 YT-2042.702.69   
YT-1800.453.037   YT-2052.802.52   
YT-2062.902.65   YT-2305.301.92   
YT-2073.002.32−24.5926.91 YT-2315.402.11   
YT-2083.102.51   YT-2325.502.12   
YT-2093.202.63   YT-2335.601.80   
YT-2103.302.36   YT-2345.701.98   
YT-2113.402.42   YT-2355.801.96   
YT-2123.502.54   YT-2365.902.07   
YT-2133.602.38   YT-2376.001.86   
YT-2143.702.29   YT-2386.101.86   
YT-2153.802.26   YT-2396.201.85   
YT-2163.902.33   YT-2406.301.79   
YT-2174.002.30   YT-2416.401.71   
YT-2184.102.34   YT-2426.501.86   
YT-2194.202.03   YT-2436.601.68   
YT-2204.302.31   YT-2446.701.73   
YT-2214.402.26   YT-2456.801.63   
YT-2224.502.22   YT-2466.901.52   
YT-2234.602.10   YT-2477.001.50−26.2027.70 
YT-2244.702.14   YT-2487.101.63   
YT-2254.802.26   YT-2497.201.44   
YT-2264.902.24   YT-2507.301.62   
YT-2275.002.02−25.4627.48 YT-2517.401.58   
YT-2285.102.12   YT-2527.501.55   
YT-2295.201.91   YT-2537.601.39   

4. Discussion

  1. Top of page
  2. Abstract
  3. 1. Introduction
  4. 2. Sampling and Methodology
  5. 3. Results
  6. 4. Discussion
  7. 5. Conclusions
  8. Acknowledgments
  9. References
  10. Supporting Information

4.1. Perturbations of the Global Carbon Cycle

[9] Although the carbon isotopic signatures of carbonate might be altered during diagenetic processes, it is safe to assume that the δ13Ccarb of our samples should mainly reflect the original signals. First, the carbon isotope compositions of micritic carbonate are regarded as being resistant to diagenetic influence [Marshall, 1992; Rosales et al., 2001; Saltzman, 2002; Joachimski et al., 2002; Buggisch and Joachimski, 2006]. Second, alterations of original δ13Ccarb signatures usually occur in the rocks containing soil organic matter [Allan and Matthews, 1982; Lohmann, 1988], or in organic carbon rich sediments, such as black shale [Joachimski et al., 2002; Buggisch and Joachimski, 2006]. In both cases, δ13Ccarb would shift to low values because the CO2 derived from these sources is 13C depleted. The absence of organic rich or shaly horizons in both the Dongcun and Yangdi sections suggests fewer alterations of carbon isotope composition. Third, except for methanogenesis, no diagenetic process is known to result in an enrichment of 13C during recrystallization [Buggisch and Joachimski 2006]. Therefore, in most cases, the positive excursions in δ13C of carbonate rocks are representative of the original signatures. Finally, the comparable isotope pattern observed in the Dongcun and Yangdi sections, which are deposited under different environmental conditions, also supports little alteration of primary signals [Buggisch and Joachimski, 2006].

[10] For the organic carbon isotope, the respiratory remineralization of organic matter in sediment column under oxic condition can produce an enrichment in 13C. This enrichment increases in sediments deposited beneath an anoxic water column [Hayes et al., 1989; Gong and Hollander, 1997; Fischer et al., 1998], where it can reach as high as 3‰. In the Dongcun and Yangdi sections, δ13Corg shows an increasing pattern with the decrease of oxygenation level at the beginning, but it still increases after the water mass return to oxic condition [Xu et al., 2008], indicating respiration of organic matter could not be the controlling factor for the δ13Corg shifts.

[11] An obvious decrease in Δ13C occurs near the F-F boundary in both the Dongcun and Yangdi sections due to a larger amplitude shift ofδ13Corg than δ13Ccarb (Figure 3). This differs from the previous observations on other sections [Joachimski et al., 2002; Chen et al., 2005]. Early paired analysis on the Berner section showed that the onset of δ13Corg excursion predated that of δ13Ccarbaround the F-F boundary [Joachimski, 1997]. The later organic carbon isotope analyses on the Kowala section showed that the δ13Corg displayed similar amplitude excursion with the δ13Ccarb shifts measured in other sections [Joachimski et al., 2002]. Based on the above evidence, Joachimski et al. [2002] proposed that the high atmospheric and oceanic CO2 concentrations of the Devonian resulted in the maximum photosynthetic fractionation, and thus any change in CO2 concentration would not affect isotope fractionation during photosynthesis. However, the obvious Δ13C excursion, together with larger amplitude shift of δ13Corg than δ13Ccarb measured in the end Ordovician [Young et al., 2008] and Early Silurian [Cramer and Saltzman, 2007] suggested that photosynthetic fractionation might not reach maximum in the late Devonian, because the atmospheric CO2 levels of the former are much higher than the latter [Banner and Hanson, 1990; Berner and Kothavala, 2001]. Furthermore, the conclusion of Joachimski et al. [2002] relies on an assumption that the carbon isotope records from different regions reflect a global carbon cycle change. This assumption, however, is potentially flawed, because the carbon isotope composition of dissolved carbon and organic matter is controlled not only by global but also by local carbon cycle [Panchuk et al., 2006]. Factors controlling local carbon cycle, such as circulation patterns, changes in primary productivity and phytoplankton community, can lead to carbon isotope variations [Freeman and Hayes, 1992; Laws et al., 1997; Bidigare et al., 1997; Popp et al., 1989; Hayes et al., 1999; Des Marais, 2001; Panchuk et al., 2006]. Circulation patterns influence the exchange rates of dissolved inorganic carbon between water mass, particularly in regions of epeiric seas [Panchuk et al., 2006]. Different species of phytoplankton, even the same species with different growth rate, might have different photosynthetic fractionations [Freeman and Hayes, 1992; Francois et al., 1993; Laws et al., 1997; Bidigare et al., 1997; Popp et al., 1989; Hayes et al., 1999], causing variations of δ13Corg. As a result, the values and patterns of carbon isotope compositions might be different among various regions due to the difference in signal strength of the regional carbon cycle. This point is supported by the inconsistence in the amplitude of δ13Ccarbshifts around the F-F boundary measured in different regions. For example, at the Cinquefoil Mountain section, Alberta, Canada [Wang et al., 1996], the excursion is from 1‰ to 5‰, whereas it is about 3‰ in some sections from Europe [Joachimski et al., 2002]. In addition, there is a potential for partial alteration of original isotope signals during deposition and diagenetic processes. For these reasons, it is more reasonable to use the whole trend of the difference between δ13Ccarb and δ13Corg of the same stratum to decipher the carbon cycle change [Cramer and Saltzman, 2007], and the consistent pattern of carbon isotope records from various sections should have a global significance. In the Kowala section, amplitude of the δ13Corgexcursion around the F-F boundary is not only larger than theδ13Ccarb, but also larger than the difference between the maximum and minimum values of δ13Ccarb for all samples [Joachimski et al., 2002]. Furthermore, the δ13Ccarb shifts recorded in the Plucki, Psie Górki, and Dębnik sections (around or less than +2‰), which are located in the same area with the Kowala section (around Kielce), are also less than the δ13Corg excursion recorded in the Kowala section [Racki et al., 2002]. Therefore, the carbon isotope records from Poland also support a decrease in Δ13C around the F-F boundary, and indicate that the photosynthetic fractionation might not reach maximum in the late Devonian.


Figure 3. Variations of the Δ13C in the Dongcun, Fuhe, and Yangdi sections (the data from the Fuhe section are adopted from Chen et al. [2005]). The solid line is the weighted average.

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[12] In the Baisha and Fuhe sections, Δ13C displays high-frequency vibrations across the F-F boundary [Chen et al., 2005]. However, this pattern of Δ13C is caused by several negative shifts of δ13Ccarb. As suggested by Buggisch and Joachimski [2006], the lower values observed during the increase of δ13Ccarb are usually diagenetic signatures. In addition, the molecular isotope records [Joachimski et al., 2002], which are believed to be less affected by diagenesis, do not show negative shifts during the period of δ13Ccarb increase. More importantly, the Δ13C in the Fuhe section displays a decreasing trend at the F-F boundary, if the abnormal negative values ofδ13Ccarb are discarded (Figure 3).

[13] Summarily, the carbon isotope records from south China (Dongcun, Yangdi, Fuhe) and Poland (Kowala, Psie Górki, Plucki, and Dębnik) show a similar pattern near the F-F boundary, which is characterized by a larger amplitude excursion ofδ13Corg than δ13Ccarb, indicating that the decrease of Δ13C might have a global significance.

[14] The larger amplitude shifts of δ13Corg compared to δ13Ccarb and its resultant Δ13C decrease could be caused by the changes of atmospheric CO2 level [Bidigare et al., 1997], and/or kinetic isotope effect from varying metabolic pathways, as well as the change in dominant sources of marine sedimentary organic matter, particularly the input of terrestrial organic matter [Sackett and Thompson, 1962; Hinga et al., 1994; Hayes et al., 1999; Kienast et al., 2001].

[15] The input of terrestrial organic matter could not interpret the δ13Corg shifts observed in this study. The Frasnian sequences of the Dongcun and Yangdi sections were deposited under different sedimentary environments [Chen et al., 2001; Wang and Ziegler, 2002]. The Dongcun section was deposited under pelagic depositional condition, while the Yangdi section was deposited under a platform environment. Theoretically, the influx of terrestrial organic matter into the Yangdi section should be larger than that of the Dongcun section. Therefore, δ13Corg values of the Yangdi section would be higher than those of the Dongcun section if the terrestrial organic matter were the dominant source of the sedimentary organic carbon, because the δ13C of terrestrial organic materials is often higher than that of contemporaneous marine organics. However, the fact is that there are no observable differences in δ13Corg between the Dongcun and Yangdi sections. Furthermore, the maximum values of δ13Corg in the Dongcun (−24.08‰) and Yangdi sections (−24.05‰) are larger than that of the Devonian terrestrial organic matter (−24.8‰ to −26.8‰) [Maynard, 1981]. The low δ13Corg of terrestrial organic matter can hardly explain the larger δ13Corgvalues near the F-F boundary.

[16] Though changes in metabolic pathway biomass community and growth rate have a potential for causing δ13Corg shifts, carbon isotope analysis of total organic matter has been shown to faithfully record the original isotopic trend when compared with compound specific δ13Corganalysis of short-chain n-alkanes as well as acyclic isoprenoids pristane, phytane, and hopane from identical samples [Joachimski et al., 2002]. The baseline values of the different biomarkers varied by a few per mille but the trends shown were practically identical, suggesting that Δ13C changes cannot be explained by variation in metabolic pathway and biomass community [Cramer and Saltzman, 2007]. Increased growth rate of the phytoplankton can also cause positive excursions of δ13Corg. The increased growth rate often increases primary productivities, leading to high influx of organic matter into sediments. The previous analysis on the Dongcun section showed that the carbon isotope shifts around the F-F boundary mainly resulted from the development of reducing conditions (Figure 2) [Xu et al., 2008]. Therefore, the concentrations of organic matter would increase at the F-F boundary if the growth rate were the major factor forδ13Corg shifts, because both reducing conditions and increased productivity favor for organic matter burial. However, there is no significant changes in organic matter contents during the interval with δ13Corg shifts (Figure 2), suggesting changes in growth rate should not the major cause for the δ13Corg changes. In addition, a study of a model versus measurement also indicates that the concentrations of dissolved CO2 play a major role in the changes of δ13Corg, though growth rate and/or other biotic factors might cause some of the shifts in δ13Corg [Rau et al., 1997].

[17] Most important, the large amplitude excursion of δ13Corg and its resulting Δ13C decrease are considered to be the two typical characteristics of the carbon isotope variations caused by lowering pCO2 level [Popp et al., 1989; Freeman and Hayes, 1992; Hayes et al., 1999]. The isotopic fractionation of 13C during photosynthesis is a function of extracellular and intracellular CO2 concentrations [Popp et al., 1989; Freeman and Hayes, 1992; Hayes et al., 1999; Pagani et al., 1999] and the photosynthetic fractionation factor is negatively correlated with atmospheric CO2 level [Popp et al., 1989]. As a result, δ13Corg would display a larger amplitude excursion than δ13Ccarb with decreasing atmospheric CO2 level, and thus Δδ13C shifts to negative.

[18] Consequently, the decrease of Δ13C caused by larger amplitude of δ13Corg than δ13Ccarb should mainly reflect the changes of atmospheric CO2 level rather than the variations of metabolic pathways and/or dominant organic matter sources.

4.2. Associations of Carbon Cycle Change With Mass Extinction

[19] As reviewed by Sandberg et al. [2002], the F-F mass extinction had a close association with sea level changes. A stepwise extinction began with the severe sea level fall and the ultimate mass extinction took place well during severe eustatic falls that immediately followed major eustatic rises. These rapid changes of sea level are documented not only at the Steinbruch Schmidt section in a deep water, submarine-rise setting in Germany, but also at sections in inner shelf and outer shelf and slope settings in Belgium, Nevada, Utah [Sandberg et al., 2002]. This evidence, together with the worldwide positive δ13Ccarbexcursion, suggests that the F-F mass extinction might be associated with both the sea level and global carbon cycle changes.

[20] The detail eustatic changes and conodont evolution across the F-F boundary were reconstructed based on the records from the Dongcun section [Wang and Ziegler, 2002]. The sea level curve drawn based on the integrated analysis of biofacies, lithofacies, and sequence stratigraphy in the Dongcun section [Wang and Ziegler, 2002] is comparable with the most widely accepted sea level curve produced by Sandberg et al. [2002], further supporting that the records in the Dongcun section have a global signification. These data, together with the carbon isotope records, make it possible for scrutinizing the associations of the carbon cycle changes with biomass extinction through analyzing the phase differences among the global carbon cycle change, sea level change, and conodont extinctions.

[21] The conodont extinction displays a close association with the eustatic changes around the F-F boundary in the Dongcun section [Wang and Ziegler, 2002] (Figure 4). In the early linguiformis zone, Palmatolepis, a pelagic genus which favored the farthest offshore and deep water setting [Sandberg and Ziegler, 1996], is dominant with an average more than 85% of total fauna, indicating a typical palmatolepid biofacies. Based on the analysis of sequence stratigraphy, this interval is a highstand systems tract, corresponding to the upper part of eustatic rise Event 5 of Sandberg et al. [2002] [Wang and Ziegler, 2002]. Then the “Upper KW Horizon” (−2.04 to −1.84 m) event suddenly happened, the facies instantaneously changed into dark limestone, indicating the beginning of remarkable sea level fall (Figure 4). A thick-bedded shallow water limestone developed from −2.0 to 0 m. The fauna in this interval is a typical reduced or impoverished in Frasnian fauna. Conodonts are low in diversities, scarce in number of individuals, and all are surviving taxa from the underlying sequence. The deposition from −2.0 to −0.8 m corresponds to Event 7 ofSandberg et al. [2002] (Figure 4). The final extinction of Palmatolepis linguiformis is at –0.82 m, corresponding to the beginning of the more rapid shallowing (Event 8 of Sandberg et al. [2002]) (Figure 4). The stratum of −0.4 to 0 m is an important interval of sea level changes, indicating the most pronounced shallowing facies. No conodonts have been found at the F-F boundary; this interval could actually be a big extinction, corresponding to Event 9 ofSandberg et al. [2002] (Figure 4). From the base of the triangulariszone, the strata thin upward and consist of dark thin-bedded limestones, representing a relatively rapid sea level rise (Figure 4). From the late triangularis zone to the early crepida zone, the facies changes into deeper water, but is still much shallower than the depositional facies below −1.98 m [Wang and Ziegler, 2002].


Figure 4. Relationships among δ13Ccarb, Δ13C, conodont evolution, and sea level changes across the F-F boundary in the Dongcun section. The patterns of conodont evolution and sea level changes are comparable with the records from other continents and have a global signification. The numbers represent the events identified bySandberg et al. [2002].

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[22] The direct effect of marine regression is reducing the habitat areas on continental shelves for shallow marine species. However, this assumption can hardly explain species loss of terrestrial ecosystem because the areal extent and habitat of the terrestrial realm should increase with the marine regression [Boulter et al., 1988; Raymond and Metz, 1992, 1995] In addition, Jablonski [1986]suggested that only 13% of modern families would become extinct even if all the modern shelf biota were eliminated. Thus, the sea level fall alone could not cause the F-F mass extinction.

[23] Figure 4shows the associations of conodonts extinction with the carbon cycle, eustatic change, and the detailed evolution of condonts across the F-F boundary in the Dongcun section. The onset of eustatic fall postdates the beginnings ofδ13Ccarb and Δ13C shift, and the largest marine regression occurs during the interval with lowest Δ13C values (Figure 4). These characteristics provide key evidence for interpreting the relationship between sea level change and increased organic carbon burials. The increased organic carbon burial can lead to decrease in atmospheric CO2 level [Kump and Arthur, 1999], which is commonly taken to be the main driver of climate change on geological timescales [Berner and Kothavala, 2001; Royer et al., 2004]. The lower pCO2 would lead to temperature decrease through weakening greenhouse effect. With temperature decrease, an ice cap would develop in high altitude and latitude, causing sea level fall. This postulation is supported by the temperature decrease indicated by the δ18O of conodont apatite across the F-F boundary [Joachimski and Buggisch, 2002]. Significant temperature decline would decimate reefal and tropical ecosystems, as species inhabiting these places have no refuge against cold. In contrast, the high-latitude species could migrate to lower latitudes and maintain their tolerable temperature. Each of these expected patterns of ecological selectivity in survival are observed in the F-F event [McGhee, 1996], suggesting that the temperature decline should be an important factor for the mass extinction.

[24] For the causes of the increased carbon burial around the F-F boundary, our previous high-resolution investigations [Xu et al., 2008] revealed that the reducing conditions predate the onset of the carbon isotope excursions, suggesting that the two positive carbon isotope shifts are likely caused by the expansion of anoxic conditions. The low Al/(Al+Fe) ratio across the F-F boundary leads the U/Al and Cu/Al anomalies in timing, implying that this anoxic event might have resulted from a long-term cumulative effect of intense hydrothermal-volcanic activities. Therefore, long-term cumulative effect of intense hydrothermal-volcanic activities lead to development and expansion of anoxic water mass, which in turn cause increased organic carbon burial and thus atmospheric CO2 level decrease.

[25] In the late rhenana zone, a positive δ13Ccarb excursion has been detected on the worldwide. This positive excursion, together with organic rich sediments (lower Kellwasser horizon), indicates another perturbation of global carbon cycle in the late rhenana zone. However, no obvious positive shift of δ13Corg has been detected in the late rhenana zone in most previous studies. Joachimski et al. [2002] suggest the δ13Corg maximum might be missed due to the broader sampling interval. The carbon isotope records in the Dongcun and Yangdi sections provide critical evidence for the above postulation. The carbon isotope records in the Dongcun and Fuhe sections display a similar pattern in the late rhenanazone with that at the F-F boundary, which is characterized by a relatively larger positive shift inδ13Corg than δ13Ccarb (Figure 2) and negative Δ13C shift (Figure 3). These characteristics suggest that a perturbation of carbon cycle like that at the F-F boundary might occur in the laterhenana zone.

5. Conclusions

  1. Top of page
  2. Abstract
  3. 1. Introduction
  4. 2. Sampling and Methodology
  5. 3. Results
  6. 4. Discussion
  7. 5. Conclusions
  8. Acknowledgments
  9. References
  10. Supporting Information

[26] The negative Δ13C shifts and the larger amplitude shift of δ13Corg positive excursion than δ13Ccarb document the decreases in pCO2 level with increased organic carbon burial in the late rhenanazone and at the F-F boundary. The timing of carbon isotope excursions, eustatic change, and conodont evolution across the F-F boundary provides key evidence for identifying the association of carbon cycle with the mass extinction. The onset of conodonts extinction coincides with the sea level fall, while it postdates that of atmospheric CO2 level decrease. Furthermore, the severest extinction occurs during the interval with the lowest pCO2 level and sea level. These observations suggest that the environmental changes induced by lowering pCO2level, such as temperature decrease and marine regression, might be the important factors for the F-F mass extinction.


  1. Top of page
  2. Abstract
  3. 1. Introduction
  4. 2. Sampling and Methodology
  5. 3. Results
  6. 4. Discussion
  7. 5. Conclusions
  8. Acknowledgments
  9. References
  10. Supporting Information

[27] We gratefully acknowledge Zhang Fusong and Wen Chuanfen's help for stable isotope analyses and the assistance of Lu Hongjin and Li Zhenliang for field work. Special acknowledgment is owed to Grzegorz Racki and two anonymous reviewers for their critical advice and suggestions. This work is funded by National Natural Science Foundation (40972227) and the Major State Basic Research Development Program of China (973 Program) (2010CB950203).


  1. Top of page
  2. Abstract
  3. 1. Introduction
  4. 2. Sampling and Methodology
  5. 3. Results
  6. 4. Discussion
  7. 5. Conclusions
  8. Acknowledgments
  9. References
  10. Supporting Information

Supporting Information

  1. Top of page
  2. Abstract
  3. 1. Introduction
  4. 2. Sampling and Methodology
  5. 3. Results
  6. 4. Discussion
  7. 5. Conclusions
  8. Acknowledgments
  9. References
  10. Supporting Information
jgrg902-sup-0001-t01.txtplain text document10KTab-delimited Table 1.

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