南海无机碳代谢及其在碳循环中的作用初探
摘要
无机碳代谢(钙化／溶解作用)和有机碳代谢(光合／呼吸作用)是调节海洋碳循环的两个主要生物过程。其中，光合／呼吸作用的净效应将表层海洋中的二氧化碳(CO_2)以有机碳形式固定至深层海洋，而净碳酸钙(CaCO_3)生产却驱使海洋CO_2增加。本论文首次从无机碳代谢出发，调查了南海多个区域的颗粒无机碳(PIC，主要为CaCO_3)和溶解钙离子(Ca~(2+))，旨在描绘南海CaCO_3和Ca~(2+)分布，比较不同区域间两者行为的差异；初步探讨控制CaCO_3和Ca~(2+)行为的过程，评估无机碳代谢活动在南海的重要性，并与有机碳代谢进行比较。
本论文的研究区域包括以南海北部海盆为代表的深水区域，以南海北部陆架为代表的近岸河口区域，及以西沙永兴岛周边礁盘为代表的珊瑚礁生态系统。测定参数除PIC和Ca~(2+)外，还包括颗粒有机碳(POC)和碳酸盐系统，如CO_2分压(pCO_2)、总碱度(TAlk)、总溶解无机碳(DIC)等相关支持数据，所有参数都采用国际标准方法测定。
我们的实验结果表明，秋季南海北部海盆这一半封闭寡营养盐海区的表层PIC浓度范围为0．14-0．24μmol CL~(-1)，低于POC近一个量级。而冬季由于南海水体混合增强，浮游植物初级生产力相应提高，各调查区域PIC和POC均有不同程度的增加。2006年12月，吕宋深海区真光层内的PIC浓度约为1μmol C L~(-1)，高出秋季北部海盆一个量级，PIC／POC浓度比值可达1：2；而南海西部上层水体的PIC浓度更高，可达2μmol C L~(-1)，PIC／POC浓度比值也一般大于1：2，暗示了这些区域应有较强的钙化作用；在南海北部陆架至陆坡区域，由于同时受珠江冲淡水陆源输入的影响，PIC最高可达0．8μmol C L~(-1)，整体水平高出北部海盆3-4倍。PIC最高值发生在西沙珊瑚礁这一钙化生态系统中，冬季表层水体的PIC浓度一般大于1μmol C L~(-1)，最高可达3μmol C L~(-1)，PIC／POC浓度比值接近1。
根据碳酸盐系统等相关数据，我们估算出南海北部海盆真光层内和西沙珊瑚礁生态系统的钙化／光合比值分别为～1：14和1：4-1：3，指示了有机碳生产在海盆区占绝对主导地位，而珊瑚礁系统的钙化作用不可忽视。另外，南海北部海盆100m水深处的CaCO_3和有机碳输出通量比仅为0．12，与该区域真光层内的PIC／POC浓度比值吻合，也证明了该区域无机碳生产力较低。
南海Ca~(2+)分布显示，北部海盆区水深500 m之下的实测Ca~(2+)显著高出基于保守行为假设下的计算值(两者之差即所谓的超额钙，Excess Ca)，超额钙的形成可能是热力学因素和质子通量共同控制下的CaCO_3溶解导致。吕宋深海区500m以深水体中也存在超额钙，但南海西部深水区域的超额钙并不明显，这可能与该区域具有较高的PIC浓度相关。而在南海北部陆架至陆坡表层水体中，Ca~(2+)分布受到河海水混合的影响，近岸浓度低(最低约为9．80 mmol kg~(-1))，远岸浓度高(最高接近10．00 mmol kg~(-1))，但在陆坡深水海区也存在超额钙，其量级与北部海盆区接近。西沙珊瑚礁生态系统的Ca~(2+)部分呈现亏损状态(Depletion)，指示了该珊瑚礁系统具有较强的钙化作用。
总之，南海北部海盆区域的无机碳代谢并不显著，表现出一般大洋的特征。但是，垂直混合、陆源输入、生物活动等因素又会造成南海其它区域的CaCO_3和Ca~(2+)行为产生差别。其中，珊瑚礁生态系统的信号最为强烈，生物钙化导致高PIC和低Ca~(2+)浓度的同时，对群落代谢和系统碳循环也具有潜在的影响。
Both inorganic carbon metabolism (calcification/dissolution) and the organic carbon metabolism (photosynthesis/respiration) are two primary biological processes modulating the ocean carbon cycle. While the photosynthesis/respiration drives a net flux of fixed organic carbon from the surface to the deep ocean, the net CaCO_3 production counteracts the organic carbon export by shifting the carbonate system toward a higher CO_2 concentration. This research is attempting to for the first time, examine the relative importance of these two processes in the world's largest tropic-subtropical marginal sea - the South China Sea (SCS), based on our measurements of particulate inorganic and organic carbon (PIC and POC), dissolved calcium ion (Ca~(2+)) and carbonate system parameters including partial pressure of CO_2 (pCO_2), total alkalinity (TAlk) and dissolved inorganic carbon (DIC).
Our results showed that, in autumn, surface PIC concentration in the northern SCS (NSCS) basin, which is oligotrophic and permanently stratified, ranged from 0.14 to 0.24μmol C L~(-1), nearly one order of magnitude lower than POC. In the wintertime, however, SCS is characterized by enhanced wind-induced mixing, resulting in the relatively higher primary production as compared to other seasons. For example, in December 2006, we observed that, PIC in the euphotic layer of the deep-sea zone off Luzon was approximately 1μmol C L~(-1), which was one magnitude higher than the NSCS basin, and the PIC/POC concentration ratio was as high as 1:2. PIC in the shallow water of the western SCS off Vietnam was much higher, nearly 2μmol C L~(-1), and the average PIC/POC concentration ratio was higher than 1:2, suggesting strong calcification in this region. In the northern shelf and slope region, affected by the terrestrial inputs, the PIC content was 3 to 4 times more than in the NSCS basin, with the highest PIC concentration close to 0.8μmol C L~(-1). PIC in the surface waters of the Xisha coral reef system was comparable to POC, which was on average >1μmol C L~(-1) and the highest among all the study areas.
It is also demonstrated that, the ratio of calcification to photosynthesis in the NSCS basin and the Xisha coral reef system was -1:14 and 1:4-1:3, respectively, indicating the organic carbon production was dominant in the basin area but the CaCO_3 production was a much more important component in the reef system. Using an ocean biogeochemical-transport box model, we estimated the CaCO_3 to organic carbon export ratio of the top 100 m water in the basin area to be -0.12, agreed well with the measured PIC/POC concentration ratio of this area.
Vertical profiles of Ca~(2+) in the NSCS basin showed that excess Ca (defined as the difference between the measured Ca~(2+) concentration and that calculated from salinity) existed in the water below the depth of 500 m. Similar to the scenario in open ocean region, this obvious excess Ca might come from the CaCO_3 dissolution under the control of both thermodynamics and the proton flux. However, unlike excess Ca existing in the mid- and deep water in the deep-sea zone off Luzon, there was no obvious excess Ca in the western SCS. In the northern shelf and slope region, while Ca~(2+) distribution in surface waters was controlled by the mixing process of the Pearl River plume and the SCS water, excess Ca in the slope area was also observable and its magnitude was close to the NSCS basin. Ca~(2+) depletion happened in some time during the time-series observation at the reef flat, which again suggests that calcification was substantial in this typical coral reef system.
In summary, while the inorganic carbon metabolism in the NSCS basin had a similar function with that in the open ocean, CaCO_3 and Ca~(2+) behaviors in other regions were more or less different, due to among others, the effects of vertical mixing, terrestrial inputs and biological activities. The most dynamic behavior was observed in the coral reef system, in which calcification resulted in the highest PIC and lowest Ca~(2+) concentrations, and had a potential effect on the community metabolism and the carbon cycle system.
本论文的研究区域包括以南海北部海盆为代表的深水区域，以南海北部陆架为代表的近岸河口区域，及以西沙永兴岛周边礁盘为代表的珊瑚礁生态系统。测定参数除PIC和Ca~(2+)外，还包括颗粒有机碳(POC)和碳酸盐系统，如CO_2分压(pCO_2)、总碱度(TAlk)、总溶解无机碳(DIC)等相关支持数据，所有参数都采用国际标准方法测定。
我们的实验结果表明，秋季南海北部海盆这一半封闭寡营养盐海区的表层PIC浓度范围为0．14-0．24μmol CL~(-1)，低于POC近一个量级。而冬季由于南海水体混合增强，浮游植物初级生产力相应提高，各调查区域PIC和POC均有不同程度的增加。2006年12月，吕宋深海区真光层内的PIC浓度约为1μmol C L~(-1)，高出秋季北部海盆一个量级，PIC／POC浓度比值可达1：2；而南海西部上层水体的PIC浓度更高，可达2μmol C L~(-1)，PIC／POC浓度比值也一般大于1：2，暗示了这些区域应有较强的钙化作用；在南海北部陆架至陆坡区域，由于同时受珠江冲淡水陆源输入的影响，PIC最高可达0．8μmol C L~(-1)，整体水平高出北部海盆3-4倍。PIC最高值发生在西沙珊瑚礁这一钙化生态系统中，冬季表层水体的PIC浓度一般大于1μmol C L~(-1)，最高可达3μmol C L~(-1)，PIC／POC浓度比值接近1。
根据碳酸盐系统等相关数据，我们估算出南海北部海盆真光层内和西沙珊瑚礁生态系统的钙化／光合比值分别为～1：14和1：4-1：3，指示了有机碳生产在海盆区占绝对主导地位，而珊瑚礁系统的钙化作用不可忽视。另外，南海北部海盆100m水深处的CaCO_3和有机碳输出通量比仅为0．12，与该区域真光层内的PIC／POC浓度比值吻合，也证明了该区域无机碳生产力较低。
南海Ca~(2+)分布显示，北部海盆区水深500 m之下的实测Ca~(2+)显著高出基于保守行为假设下的计算值(两者之差即所谓的超额钙，Excess Ca)，超额钙的形成可能是热力学因素和质子通量共同控制下的CaCO_3溶解导致。吕宋深海区500m以深水体中也存在超额钙，但南海西部深水区域的超额钙并不明显，这可能与该区域具有较高的PIC浓度相关。而在南海北部陆架至陆坡表层水体中，Ca~(2+)分布受到河海水混合的影响，近岸浓度低(最低约为9．80 mmol kg~(-1))，远岸浓度高(最高接近10．00 mmol kg~(-1))，但在陆坡深水海区也存在超额钙，其量级与北部海盆区接近。西沙珊瑚礁生态系统的Ca~(2+)部分呈现亏损状态(Depletion)，指示了该珊瑚礁系统具有较强的钙化作用。
总之，南海北部海盆区域的无机碳代谢并不显著，表现出一般大洋的特征。但是，垂直混合、陆源输入、生物活动等因素又会造成南海其它区域的CaCO_3和Ca~(2+)行为产生差别。其中，珊瑚礁生态系统的信号最为强烈，生物钙化导致高PIC和低Ca~(2+)浓度的同时，对群落代谢和系统碳循环也具有潜在的影响。
Both inorganic carbon metabolism (calcification/dissolution) and the organic carbon metabolism (photosynthesis/respiration) are two primary biological processes modulating the ocean carbon cycle. While the photosynthesis/respiration drives a net flux of fixed organic carbon from the surface to the deep ocean, the net CaCO_3 production counteracts the organic carbon export by shifting the carbonate system toward a higher CO_2 concentration. This research is attempting to for the first time, examine the relative importance of these two processes in the world's largest tropic-subtropical marginal sea - the South China Sea (SCS), based on our measurements of particulate inorganic and organic carbon (PIC and POC), dissolved calcium ion (Ca~(2+)) and carbonate system parameters including partial pressure of CO_2 (pCO_2), total alkalinity (TAlk) and dissolved inorganic carbon (DIC).
Our results showed that, in autumn, surface PIC concentration in the northern SCS (NSCS) basin, which is oligotrophic and permanently stratified, ranged from 0.14 to 0.24μmol C L~(-1), nearly one order of magnitude lower than POC. In the wintertime, however, SCS is characterized by enhanced wind-induced mixing, resulting in the relatively higher primary production as compared to other seasons. For example, in December 2006, we observed that, PIC in the euphotic layer of the deep-sea zone off Luzon was approximately 1μmol C L~(-1), which was one magnitude higher than the NSCS basin, and the PIC/POC concentration ratio was as high as 1:2. PIC in the shallow water of the western SCS off Vietnam was much higher, nearly 2μmol C L~(-1), and the average PIC/POC concentration ratio was higher than 1:2, suggesting strong calcification in this region. In the northern shelf and slope region, affected by the terrestrial inputs, the PIC content was 3 to 4 times more than in the NSCS basin, with the highest PIC concentration close to 0.8μmol C L~(-1). PIC in the surface waters of the Xisha coral reef system was comparable to POC, which was on average >1μmol C L~(-1) and the highest among all the study areas.
It is also demonstrated that, the ratio of calcification to photosynthesis in the NSCS basin and the Xisha coral reef system was -1:14 and 1:4-1:3, respectively, indicating the organic carbon production was dominant in the basin area but the CaCO_3 production was a much more important component in the reef system. Using an ocean biogeochemical-transport box model, we estimated the CaCO_3 to organic carbon export ratio of the top 100 m water in the basin area to be -0.12, agreed well with the measured PIC/POC concentration ratio of this area.
Vertical profiles of Ca~(2+) in the NSCS basin showed that excess Ca (defined as the difference between the measured Ca~(2+) concentration and that calculated from salinity) existed in the water below the depth of 500 m. Similar to the scenario in open ocean region, this obvious excess Ca might come from the CaCO_3 dissolution under the control of both thermodynamics and the proton flux. However, unlike excess Ca existing in the mid- and deep water in the deep-sea zone off Luzon, there was no obvious excess Ca in the western SCS. In the northern shelf and slope region, while Ca~(2+) distribution in surface waters was controlled by the mixing process of the Pearl River plume and the SCS water, excess Ca in the slope area was also observable and its magnitude was close to the NSCS basin. Ca~(2+) depletion happened in some time during the time-series observation at the reef flat, which again suggests that calcification was substantial in this typical coral reef system.
In summary, while the inorganic carbon metabolism in the NSCS basin had a similar function with that in the open ocean, CaCO_3 and Ca~(2+) behaviors in other regions were more or less different, due to among others, the effects of vertical mixing, terrestrial inputs and biological activities. The most dynamic behavior was observed in the coral reef system, in which calcification resulted in the highest PIC and lowest Ca~(2+) concentrations, and had a potential effect on the community metabolism and the carbon cycle system.
引文
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