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1 Vol.30 No.5 : Acta Geoscientica Sinica Oct. 2009: www. 地球学报.com (CaCO 3 ),,,,,,,, 摘要 : (1995~2000 ) 2 a 13 2, (CaCO 3 ) :, 13 C ;, 13 C, C 3 ( C 4 ), 13 C,,, 13 C, ; 13 C 12.23, 14.5 ;,, 13 C, ( ), 13 C 10 ~ 11, ( ), 1, 13 C, CO 2 关键词 : ; ; ; 中图分类号 : P ; P597.2 文献标志码 : A 文章编号 : (2009) Cave Dripping Water and Carbon Isotopic Records of Modern Carbonate (CaCO 3 ) Deposits: Stalagmite in Panlong Cave of Guilin and Its Environmental Significance ZHANG Mei-liang, ZHU Xiao-yan, LIN yu-shi, CHENG Kun-kun, HE Si-yi, WANG Hua, YANG Yan Key Laboratory of Karst Dynamics, Institute of Karst Geology,, Guilin, Guangxi Abstract: The trend monitoring of cave dripping water and modern carbonate deposits at 13 monitoring points of dripping water in Panlong Cave of Guilin during the pre-phase (1995~2000) and nearly two hydrological years reveal that there exist two types of modern carbonate (CaCO 3 ) deposits: the first is the modern carbonate (CaCO 3 ) deposit of the perennial dripping water in the cave whose 13 C values have recorded climate change characteristics of the whole year, and the second is the modern carbonate (CaCO 3 ) deposit of the seasonal dripping water in the cave with the seasonal change characteristics of 13 C values. The monitoring and isotope analysis of modern carbonate (CaCO 3 ) deposits show that the exterior mountain peaks of the Panlong cave in Guilin are mainly C 3 plants (with almost no C 4 plants), and the 13 C records of modern carbonate (CaCO 3 ) indicate that the summer monsoon is strong, the rainwater is relatively rich, the biologic activities are strong, and the modern carbonate deposits are fairly well developed in the half year of summer, and the average 13 C value is in the half year of summer. The 13 C values of the modern carbonate (CaCO 3 ) deposits are somewhat negative, with the an- ( : ) ( : ) ( : ) ( : ) : ; : :,, 1956 : , 50 : mlzh@karst.edu.cn

2 : (CaCO 3 ) 635 nual average 13 C value being and the maximum negative value being 14.5 for the whole year. The 13 C values of the modern carbonate (CaCO 3 ) deposits are somewhat positive ( 10 ~ 11 ) due to less rainwater in the half year of winter. In addition, the 13 C values of modern carbonate (CaCO 3 ) formed by dripping water with a lag of one month or half a month show a sudden negative trend and mainly reflect the influence of the CO 2 effect, which results in the effect of meteoric precipitation when heavy rain falls or rainstorm occurs no matter whether in the half year of summer or in the half year of winter. Key words: Modern carbonate deposit; carbon isotope; environmental significance; Panlong cave of Guilin, ( ) (, 1995; Marfia et al., 2004; Coplen et al., 1994; Yuan et al., 2004;, 2006; Cerling, 1984;, 2001;, 2004;, 2005) ( ), Cerling CO 2 13 C C 3 C 4, ( ) 13 C (Cerling,1984), 13 C 18 O, ( ),,, CO 2 ( ) CO 2,, CO 2,,, ( ),, ( ), CO 2, CaCO 3, ( ) (CaCO 3 ) ( ),,,,,,,,, 38 km,, 60~150 m, 1868 mm, 1268 mm, 76%, 1285 h, , 90%~98%, ( 1), 13 18, CaCO 3 1 现代碳酸盐样品的采集与分析, 3 ( ), 3 ( ), CaCO 3 3 ( ), 3 CaCO 3,, 20 mg 100% CO 2, MAT253, 13 C 18 O PDB, <0.1 2 碳同位素基本理论,,,, Ca 2+ HCO 3, CO 2,, ( ),, :

3 636 Fig. 1 图 1 桂林盘龙洞平面图及滴水监测点 Plan of Panlong cave in Guilin and monitoring sites of dripping water CaCO 3 ( )+H 2 O( )+CO 2 ( ) Ca 2+ +2HCO 3 (1) Ca 2+ +2HCO 3 CaCO 3 ( )+ H 2 O+CO 2 (2) (1),, (1) (2), ( 13 C) CO 2 ( ), ( 13 C), ( CO 2, CO 2 ) CO 2 (Genty et al., 2001) 2, CaCO 3 13 C, 0~+1,, ( ) 13 C, CO 2 CO 2 13 C 13 C 图 2 洞穴石笋中的碳源及其运移途径示意图, CO 2 13 C 7, CO 2 Fig. 2 Stalagmite carbon source and its moving route 13 C,, C 3 ( ), Calvin, 13 C -32 ~-22, 27 ; C 4 ( ) Hatch-Slack, 13 C 16 ~ 10, 13 (Marion et al., 1991) Cerling (1984), CO 2, C 3 CO 2 13 C 22.2, C 4 CO 2 13 C 8.5, CO 2 13 C 6 CO 2 13 C,, CO 2 13 C, CO 2, ( ) 13 C C 3 C 4 13 C,

4 : (CaCO 3 ) , CO 2 13 C (C 3 /C 4 ),,, CO 2, C 3 /C 4 13 C, CO 2 CO 2 ( C 4 ), C 3 /C 4 13 C 3 现代洞穴碳酸盐 (CaCO 3 ) 沉积物石笋的 δ 13 C 值 (2), (CaCO 3 ), 13 C DIC ( ) 13 C,, 13 C CO 2 13 C CO 2 (Friedman et al., 1977), CO 2 13 C ab = 1000lna = a b (3), a, a b, CO 2,, ( ) 13 C CO 2 13 C, ( ) 13 C, : 13 C CaCO3 = 13 C CO2 ε CO2 CaCO3 (4), ε CO2 CaCO3 CO 2 CaCO , Friedman O'Neil (2), εco 2 CaCO 3 (1000lna) , 10, 1.44, Dreybrodt (1980) (CaCO 3 ), C 3 Calvin, (CaCO 3 ) 13 C 14 6 ; C 4 Hatch-Slack, (CaCO 3 ) 13 C 6 +2, 13 C ( ), C 3 /C 4, C 3 CO (PDB), (CaCO 3 ) 13 C, 10.4 (15 ) (25 ) 13 C 0 ~+1.02, 19.5, (CaCO 3 ) 13 C (Li et al., 2004) (CaCO 3 ) 250, (CaCO 3 ) 13 C, 13 ( 10 ; 3 ) 9 ~ ( 5.58,, ), ~ 12.23, 1996~2000 ( 10.5 ~ 11.0 ) 13 C ( ) 1.0 ~ 1.2, ( 2000, 100 cm, 2~4 m),, (, 2003;, 2001), ( 1868 mm), (CaCO 3 ) (CaCO 3 ) 13 C, (CaCO 3 ) : (CaCO 3 ) ; (CaCO 3 ), (CaCO 3 ) 13 C (CaCO 3 ) 13 C, P1-2 P2-1 P2-2 P2w P4-1 P6-1 PS2 PS1 8, 1~4 m,,, 15~50 /min, 120~150 /min,, 3~6 /min (CaCO 3 ), CO 2, (CaCO 3 ) 13 C ( 3), 13 C , 12.23, 3~4.5 3, C ( ), 3 4, 13 C, 6~8, 9, 10~12, 2,,,,

5 638 Fig. 3 图 3 桂林盘龙洞 8 个快速滴水点的现代碳酸钙沉积物的碳同位素动态曲线图 Carbon isotope records of modern carbonate (CaCO 3 ) stalagmite from 8 fast dripping water sites in Panlong Cave, Guilin P1-2, P2-1, P2-2, P2w, P4-1, P6-1, PS2 PS1 P1-2, P2-1, P2-2, P2w, P4-1, P6-1, PS2 and PS1 are monitoring sites for dripping water,, 13 C, 3 ~4.5, P2-1 P2w,,, ( 160 mm 100 mm; ), 1, ( ) 13 C 12 14,,,,,, CO 2,, 13 C ( ) 13 C ( 4), ( 3 ),,,,, CO 2,, (EC) Ca +2 HCO 3,,, CaCO 3,, (CaCO 3 ) 13 C, 8 ( ) 13 C ( 3),, 13 C, (2003), ( ),, ( ) ;, ( ) ;, ; C 3 13 C (, 2001;, 2006;, 2005),,,, C 3 13 C, ;

6 : (CaCO 3 ) 639 图 4 桂林盘龙洞常年性滴水的电导率 Ca 2+ 和 HCO 3 含量变化 Fig. 4 Variations in electrical conductivity, Ca 2+ and HCO 3 ion concentrations of perennial cave dripping water sites in Panlong Cave, Guilin (a)- ; (b)- ; (c)-ca 2+ ; (d)-hco 3 (a)-temperature and rainfall; (b)-electrical conductivity; (c)-ca 2+ ion concentrations; (d)-hco 3 ion concentrations,,, C 3 13 C,, C 3 13 C, (, 2006),,, 10, ( ) 13 C 1.44, ( ) 13 C 3 ~4.5, 19.5~20, 10~12, 0.5~1, 1~2.5,,,,, ( ) 13 C 3 4,, ( ) 13 C Ca +2, HCO ;,, 7, CO 2, 13 C CO 2,,, 13 C (CaCO 3 ) 13 C P5-1 P6-2 ( ) 15 m 12 m, 5 m 10 m, 1~3 /min, 3~7 /min, 0.25 /min 2 13 C , 6.4 ( 5), 3.4, 2 13 C CO 2 13 C ( 7 ~ 8 ), 8 13 C, 5.5 ~7.5, 2 (CaCO 3 )

7 640 图 5 慢速滴水 P5-1 和 P6-2( 点 ) 沉积的碳酸盐岩的 δ 13 C 曲线图 Fig. 5 Carbon isotope records of modern carbonate (CaCO 3 ) rocks from P5-1 and P6-2 sites for slowly dripping water in Panlong cave, Guilin 13 C, 8 13 C, 2 ( 13 C ) 1 ( 13 C ),, 2 (CaCO 3 ) 13 C, : 2,,, ( ), ( <5~30 cm), ( ), CO 2, 13 C CO 2,, C 3,,,, 2 ( ) 12 m,, 1~3 /min, 0.25 /min 2, CO 2, 13 C,, -,,, (CaCO 3 ) 13 C,,,, (CaCO 3 ) 13 C, 3.2 (CaCO 3 ) 13 C,, ( ), P3 P7-2 (2~3 ),, 13 C, 10 ~ 14.6, 13.1 ( 6), 4.6 ( ), P3 P7-2 1~3, (CaCO 3 ) ;,,,, 2 13 C 2 13 C ( ) 0.9, 13 C ( ) 2 (CaCO 3 ) 13 C, 13 C, 2 ( 13 C ),,,, ; (9~11 ), P3 P7-2, 1~3,,, 2 13 C 2 13 C, ( 13 C );,,, CO 2, 13 C 13 C 4 现代洞穴碳酸盐沉积物石笋的 δ 13 C 值与沉积速率 ( 或沉积量 ) CO 2,, 2~4, 10 (4~9 ), 70%,, CO 2,, Ca 2+ HCO 3,, CaCO 3, (0.22~0.46 g/month), (, 2007),

8 : (CaCO 3 ) 641 图 6 季节性滴水 P3 和 P7-2( 点 ) 的物化指标及沉积的碳酸钙的 δ 13 C 动态曲线图 Fig. 6 Physical and chemical indexes and carbon isotope records of modern carbonate (CaCO 3 ) from P3 and P7-2 sites of seasonal dripping water in Panlong Cave, Guilin (a),(b),(c)-p3 P7-2 Ca 2+ EC HCO 3 ; (d),(e)-p3 P7-2( ) 13 C (a), (b), (c)-physical, chemical indexes of Ca 2+,EC and HCO 3 ; (d), (e)-δ 13 C values of modern carbonate (CaCO 3 ) from P3 and P7-2 sites, ;,, 13 C ( 3, 5);,,,, CO 2,,, Ca 2+ HCO 3,, CaCO 3, CaCO 3 (0.042g/month),, 13 C ( 3, 5), 13 C, 13 C Pco 2 Ca 2+ HCO 3,, 5 结论 2, Pco 2 Ca 2+ HCO 3 13 C, CO 2 - (1) Pco 2 Ca 2+ HCO 3,,,, Pco 2 Ca 2+ HCO 3, ;,,,, (2) 13 C,,, CO 2,,,, 13 C, 13 C 13 C CO 2,,, (3) 13 C 18 O, 13 C,, CaCO 3 13 C,,

9 642, 13 C,,,, 参考文献 : Mei-liang Oxygen and carbon isotopic characteristics of rainwater, drip water and present speleothems in a cave in Guilin area and their environmental meanings[j]. Science in China (D). 43(3): MARFIA A M, KRISHNAMURTHY R V, ATEKWANA E A, PANTON W F Isotopic and geochemical evolution of,,, C ground and surface waters in a karst dominated geological setting: a ease study from Belize, Central America[J]. Applied [J].. 13( ): Geochemistry. 19 (6): ,,,,,, LIN Yu-shi, YUAN Dao-xian, ZHANG Mei-liang, QIN Jia-ming, 4 CHANG Hai, WANG Zhao-rong, RAN Jing-cheng [J].. 25 (4): Sedimentary Characteristics of Cave Stalagmite: A Case Study, of No.4 Stalagmite in the Dongge Cave of Libo, Guizhou [J]..58(1): Province[J]. Acta Geoscientia Sinica.25(4): (in Chinese with English abstract).,,, [J].. 2(3): MARION GM, INTRONE DS, VAN CLEVE K The stable, C 3 isotope geochemistry of CaCO 3 on the Tanana river floodplain [J].. 36(4): of interior Alaska, U.S.A: Composition and mechanisms of,, C 3 formation[j]. Chemical Geology. 86: C [J].. 26(6): PIAO Shi-long, FANG Jing-yun Seasonal changes in vegetation activity response to climate changes in China between ,,,, and 1999[J]. Acta Geographica Sinica. 58(1): (in 14 C [J].. 26 (4): Chinese with English abstract).,, ka TAN Ming, SHAO Xue-mei, LIU Xiao-hong, CAI Bing-gui ( ) 13 C CO 2 [J].. A 1000-year temperature record synthesized by combining 22 (5): stalagmite and tree rings from China[J]. Advances In Climate,, Change Research. 2 (3): (in Chinese with English abstract). [J].. 20(7): ,,,, ( ) WANG Guo-an, HAN Jia-mao Relations between 13 C value [J].. 26(4): of C 3 plants in northwestern China and annual precipitation[j] Chinese Journal Geology. 36(4): References: CERLING T E The stable isotopic compocition of soil carbonate and its relationship to climate[j]. Earth Planet Sci. Lett. 71: COPLEN T B, WINOGRAD I J, LANDWEHR J M, RIGGS A C , 000-year stable carbon isotopic record from Devils Hole, Nevada[J]. Nature. 263: DREYBRODT W Deposition of calcite from thin films of calcareous solution and the growth of speleothems[j]. Chemical Geology. 29: FRIEDMAN I, O NEIL J R Compilation of stable isotope fractionation factors of geochemical interest[m]. IN: M. FLEISCHER(Ed.) Data of Geochemistry, 6th Ed., US Geological Survey Professional Paper. 440kk. GENTY D, BAKER A, MASSAULT M, PROCTOR C, GILMOUR M,BRANCHU EP, HAMELIN B Dead carbon in stalagmites:carbonate bedrock paleodissolution vs. ageing of soil organic matter. Implications for 13 C variations in speleothems[j]. Geochimica et Cosmochimica Acta. 65(20): LI Chun-yuan, WANG Xian-bin, CHEN Jian-fa, ZHANG Tong-wei The Carbon isotopic composition of ΔC in Loess sediments and the estimating of CO 2 concentration in paleoatmosphere[j]. Acta Sedimentologica Sinica. 13 (Sup): (in Chinese with English abstract). LI Bin, YUAN Dao-xian, LIN Yu-shi, QIN Jia-ming, ZHANG WANG Li-xia, LEE Xin-qing, GUO Lan-lan The distribution of 13 C value of C 3 plant and its response to climate in arid and semiarid central east Asia[J]. Quaternary Science. 26(6): (in Chinese with English abstract). WANG Hua, ZHANG Hui-ling, TU Lin-ling, QIN Jia-ming, FENG Yu-mei A Study of the 14 C Age of Tufa Layer in the Zengpiyan Cave Site of Guilin[J]. Acta Geoscientica Sinica. 25(4): (in Chinese with English abstract). ZHANG Mei-liang, LIN Yu-shi, QIN Jia-ming The δ 13 C isotopic composition of cave stalagmite carbonate and the estimation of the atmospheric CO 2 concentration since 44ka in Guilin area[j]. Acta Geoscientia Sinica. 22(5): (in Chinese with English abstract). ZHANG Dong-qiu, SHI Pei-li, ZHANG Xian-zhou Some advance in the main factors controlling soil respiration[j]. Advances in Earth Scince. 20(7): (in Chinese with English abstract). ZHANG Mei-liang, ZHU Xiao-yan, LIN Yu-shi, TIAN Ming-chong, WANG Hua Drip water deposits and erosion-dissolution processs by drip water in karst cave[j]. Carsologica Sinica. 26(4): (in Chinese with English abstract). YUAN Dao-xian, CHENG Hai, EDWARDS R L, DYKOSKI CA, KELLY MJ, ZHANG Mei-liang, QING Jia-ming, LIN Yu-shi, WANG Yong-jin, WU Jian-yin, DORALE JA, AN Zhi-sheng, CAI Yan-jun Timing, Duration, and Transitions of the Last Interglacial Asian Monsoon[J]. Science. 304(23):

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