地球科学进展  2018 , 33 (1): 42-51 https://doi.org/10.11867/j.issn.1001-8166.2018.01.0042

综述与评述

大河影响下的边缘海反风化作用

赵彬12, 姚鹏13*, 杨作升4, 于志刚13

1.中国海洋大学海洋化学理论与工程技术教育部重点实验室, 山东 青岛 266100
2.中国海洋大学化学化工学院, 山东 青岛 266100
3.青岛海洋科学与技术国家实验室海洋生态与环境科学功能实验室, 山东 青岛 266071
4.中国海洋大学海洋地球科学学院, 山东 青岛 266100

Reverse Weathering in River-dominated Marginal Seas

Zhao Bin12, Yao Peng13*, Yang Zuosheng4, Yu Zhigang13

1.Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Ocean University of China, Qingdao 266100, China
2.College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, China
3.Laboratory of Marine Ecology and Environmental Science, Qingdao National Laboratory for Marine Science and Technology, Qingdao 266071,China
4.College of Marine Geosciences, Ocean University of China, Qingdao 266100, China

中图分类号:  P734

文献标识码:  A

文章编号:  1001-8166(2018)01-0042-10

通讯作者:  *通信作者:姚鹏(1977-),男,山东菏泽人,教授,主要从事海洋有机地球化学和生物地球化学研究.E-mail: yaopeng@ouc.edu.cn

收稿日期: 2017-07-18

修回日期:  2017-12-13

网络出版日期:  2018-01-10

版权声明:  2018 地球科学进展 编辑部 

基金资助:  国家自然科学基金面上项目“长江口—东海内陆架沉积有机碳的再矿化作用研究”(编号:41676063)国家自然科学基金重点国际(地区)合作研究项目“长江口及邻近海域沉积有机碳的保存机制研究”(编号:41620104001)资助

作者简介:

First author:Zhao Bin(1988-), male, Qingdao City, Shandong Province, Ph.D student. Research areas include oceanography and biogeochemistry.E-mail:zhaobin1988@hotmail.com

作者简介:赵彬(1988-),男,山东青岛人,博士研究生,主要从事海洋有机生物地球化学研究.E-mail:zhaobin1988@hotmail.com

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摘要

在河口与边缘海区域,大量陆源风化产物的输入和强烈的有机物再矿化作用加速了自生硅酸盐矿物和碳酸盐矿物的生成,这一过程与陆地风化作用相反,被称为反风化作用(Reverse weathering)。反风化作用所导致的自生矿物形成通常在短时间内完成,被认为是平衡大气二氧化碳含量,控制海洋中元素平衡的重要过程。反风化作用的研究方法主要分为直接观察法和化学检测法,前者主要用于自生矿物的结构和元素组成的分析,后者则用于自生铝硅酸盐矿物等定量的研究。反风化作用对海洋环境中碳、硅、常量离子(F-,Li+,Na+,K+,Ca2+和Mg2+等)和金属元素(Fe,Mn和Al等)等的循环具有重要影响,并促使它们在海洋沉积物中长久埋藏。富含金属氧化物的风化产物的输入,大量易降解有机物和生物硅的沉降,强烈的再矿化作用和次氧/厌氧的成岩条件使得河口与边缘海区域成为反风化作用发生的主要场所。

关键词: 边缘海 ; 反风化作用 ; 自生矿物形成 ; 铝硅酸盐矿物 ; 碳酸盐矿物

Abstract

In estuarine regions and marginal seas, reverse weathering refers to the formation of authigenic aluminosilicate and carbonate minerals promoted by large inputs of terrestrial weathering products and intense remineralization of Sedimentary Organic Carbon (SOC), which is opposite to land weathering process. Compared with the process in open ocean, the formation of authigenic aluminosilicate and carbonate minerals caused by reverse weathering in estuarine regions and marginal seas is rather rapid, playing an important role in the maintenance of ocean acidity and elements cycles. At present, there are two research methods regarding the reverse weathering process, i.e., direct observation and chemical detection. The first method is used to study the structure and chemical composition of authigenic minerals and the second is mainly used to do quantified studies of authigenic minerals. The reverse weathering is very important to the cycles of Si, C, major ions (F-, Li+, Na+, K+, Ca2+ and Mg2+), and alkali metal cations (Fe, Mn and Al) in marine environments, which promotes the burial of these elements in marine sediments. Due to large inputs of weathering products rich in Fe, Mn and Al oxides, precipitation of labile OC and biogenic silica, intense remineralization process and suboxic/anoxic conditions, estuarine and marginal seas are suitable sites for reverse weathering studies. The reverse weathering studies in sub-tropical and temperate estuaries should be emphasized in the future.

Keywords: Marginal seas ; Reverse weathering ; Formation of authigenic minerals ; Aluminosilicate minerals ; Carbonate minerals.

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赵彬, 姚鹏, 杨作升, 于志刚. 大河影响下的边缘海反风化作用[J]. 地球科学进展, 2018, 33(1): 42-51 https://doi.org/10.11867/j.issn.1001-8166.2018.01.0042

Zhao Bin, Yao Peng, Yang Zuosheng, Yu Zhigang. Reverse Weathering in River-dominated Marginal Seas[J]. Advances in Earth Science, 2018, 33(1): 42-51 https://doi.org/10.11867/j.issn.1001-8166.2018.01.0042

1 引言

海洋沉积物中的早期成岩作用包含一系列化学、物理和生物过程,这些过程能够改变上层沉积物中有机物的含量和组成,并向间隙水释放营养盐、金属离子、H2S和二氧化碳(CO2)等氧化还原产物,促使新的矿物生成[1]。自生矿物的形成是海洋早期成岩过程中的重要阶段,尤其是自生黏土矿物(铝硅酸盐矿物)的形成。由于其在形成过程中能够释放CO2,并结合多种海洋环境中的重要元素,因而对全球碳循环及其他元素循环均具有重要影响[2]。对于碳酸盐矿物,由于其相对快速的风化和沉积,在长时间尺度上(>106年)对大气CO2的影响较小;然而,在短时间尺度上(102~105年),尤其是在近几百年来人类活动输送大量CO2进入大气的背景下,碳酸盐矿物的风化与沉积对于气候变化的影响也不可忽视[3~5]。研究表明,海洋自生矿物的形成受到物质来源、沉积速率、氧化还原条件和底层水温等多种因素的影响[6,7]。在沉积速率较低的开阔大洋中,自生矿物的形成通常需要经历千年甚至万年[6,8]。然而,在沉积速率较高的陆缘海的早期成岩过程中,大量陆源风化产物的输入和强烈的有机物再矿化作用加速了这一过程,使沉积物中的多种元素快速地通过化学反应结合到一起重新形成新的自生矿物,这一过程与陆地上的矿物风化作用恰好相反,因此被称为反风化作用(Reverse weathering)[6]

反风化理论在20世纪60年代就已经提出,随着近年来对有机碳在河口与边缘海中再矿化作用研究的逐步深入,反风化作用越来越受到人们的重视[6,7,9~12]。前人的研究大多集中于铝硅酸盐矿物的反风化过程,而对于碳酸盐矿物,由于其在河口与边缘海的生产量只占海洋中总生产量的小部分(约11%)[13],所以河口与边缘海自生碳酸盐矿物的形成过程长期被忽略。然而,近期的研究表明,在河口与边缘海区域的移动泥带,沉积物中存在快速的自生碳酸盐矿物的形成,碳酸盐矿物的反风化作用同样也很重要[11,12,14~16]。另外,全球河流每年都会携带大量元素(如K,Na,Ca,Mg,Al,Fe,F,Li和Si等)进入海洋,同时沉积有机碳的降解过程会产生大量HC,反风化作用有效地将这些元素沉积,并调节了海水的酸碱平衡,使海水的元素组成在长时间尺度下保持稳定[17,18]。近年来的研究发现,在温带、亚热带和热带河口,尤其是河口移动泥带,强烈的有机碳再矿化过程可能加速了反风化作用的发生,一方面促进了碳酸盐矿物的生成,另一方面在生成铝硅酸盐黏土矿物的过程中有效地结合了F,K和Si等元素,促进了它们在海洋环境中的埋藏[7,19~23]。但是,目前对于反风化作用的相关定量研究并不多见,对于温带和亚热带河口反风化作用的特性(如速率、过程和机制的时空变化及影响因素)及其对元素循环的影响还不清楚。本文针对海洋环境中硅酸盐和碳酸盐反风化作用的机理和研究方法进行了总结和分析,以期更好地理解反风化作用对全球元素地球化学循环的影响。

2 反风化作用机理及其影响因素

早在50多年前,Mackenzie等[17]发现河流会携带大量风化产物进入海洋,但海洋中这些元素的浓度和海水酸碱度却能保持长时间的稳定,因此推断出海洋环境中存在这些元素的去除过程,并根据海水中的元素质量守恒首次发现了反风化作用的存在。海洋环境中的反风化作用是指经陆地风化作用而分解形成的各种离子或简单矿物成分在输送到海洋之后重新结合,形成新的自生矿物的过程[17]。以硅酸盐反风化作用为例,河流带来的无定型铝硅酸盐与碱性阳离子、HC和溶解二氧化硅(SiO2)反应生成富含阳离子的铝硅酸盐矿物,同时释放CO2进入大气[17]。由于碱性阳离子、HC和溶解SiO2等是硅酸盐风化的重要产物,它们与硅酸盐矿物颗粒重新合成新的铝硅酸盐矿物的过程,与硅酸盐风化作用正好相反(图1)[18,24]。对于碳酸盐反风化作用来说,快速的海洋碳酸盐矿物沉积过程,同样结合了多种碱性阳离子,如Ca2+,Mg2+,Fe2+和Mn2+等,并同时释放CO2[4,14] (图1)。

图1   硅酸盐和碳酸盐风化和反风化作用反应机理[4,18]
图中碳酸盐矿物以CaCO3为例

Fig.1   The mechanisms of reverse weathering and weathering of silicate and carbonate minerals[4,18]
Taking CaCO3 as an example for carbonate minerals in the figure

与大多数自生矿物的形成一致,物质供给、温度和氧化还原条件等是反风化作用的主要影响因素[6,7]。其中,氧化物/铝硅酸盐矿物、溶解硅酸盐、碱性阳离子和HC等物质的供给尤为重要[4,6]。研究表明,反风化作用主要发生在河口和边缘海的环境。由于河流水体富含阳离子、SiO2和氧化铝,这些元素的输入为反风化作用提供了反应原料;并且,河口移动泥区有机碳强烈的再矿化作用释放了大量金属离子(如铁、锰和铝)、硅酸盐和碳酸氢根,为反风化作用提供了底物,促进了反风化作用的发生,其自生矿物形成时间通常在几十年甚至几年或更短的时间[6,19~21,25]。因此,快速的反风化作用使河流入海元素重新结合到固体矿物中,是其重要归宿,并保持了海水中元素含量的长时间平衡,而其消耗作为弱酸的碳酸氢根(生成CO2)还有效调节了海水中的酸碱度,维持了海水pH的长期稳定。

3 反风化作用的研究方法

海洋环境中自生矿物在沉积物中所占的比例很小,很难检测出其在沉积物中的含量,因此通常运用一些间接方法来证明反风化作用的发生,这些方法主要包括直接观察法和化学检测法2类。

3.1 直接观察法

直接观察法是研究反风化作用的重要手段,该方法通常是运用显微镜、扫描电镜(Scanning Electron Microscope, SEM)和透射电镜(Transmission Electron Microscope, TEM)观察不同化合物在反风化作用中的变化。例如,Michalopoulos等[6]将不同材料的颗粒,如石英颗粒、玻璃颗粒(用以模仿硅藻细胞璧)和带有氧化铁(FeOOH)涂层的石英颗粒附着在丙烯酸板上,并将其插入装有亚马逊三角洲沉积物的小瓶中,在厌氧和常温条件下进行了沉积物培养实验(12~36个月),发现石英颗粒的缝隙生成了富含阳离子的铝硅酸盐矿物,表层的氧化铁涂层转化成含铝硅铁的混合物,玻璃颗粒则发生了明显的溶解,这些结果表明陆源风化的颗粒会与二价铁、溶解硅和阳离子快速生成新的矿物。Michalopoulos等[26]之后又运用相似的方法,将带有硅藻的聚碳酸酯片插入到沉积物中,观察了硅藻细胞的成岩转化过程。进一步地,Michalopoulos等[7]通过显微镜对亚马逊三角洲上层沉积物(0~80 cm)中新鲜的硅藻细胞和被自生矿物改变的硅藻细胞分别进行计数,将沉积物中改变的硅藻细胞数和总硅藻细胞数之比定义为硅藻细胞改变指数AI(Alteration Index),以此来评价反风化作用的强度,结果表明在某些富含硫酸铁的深层沉积物中,AI值可达1,表明几乎所有的硅藻细胞都发生了成岩改变,证明了亚马逊沉积物中强烈的反风化作用。

相同的方法也被应用于自生碳酸盐矿物生成的研究中,通过能量色散X射线光谱(Energy Dispersive Spectroscopy,EDS)和TEM等技术可以直接观察不同种类的自生碳酸盐矿物的生成。如Wang等[27]通过SEM观察了长江口存在明显的自生方解石和白云石的生成。直接观察的结果与X射线衍射技术相结合,还可以估算不同种类碳酸盐矿物的质量分数。例如,杨克红等[28]通过X射线衍射技术研究了南海甲烷渗漏区自生碳酸盐的种类,发现该区域沉积物中存在晶形完好的自生高镁方解石和文石矿物,这些矿物都是典型的冷泉自生碳酸盐,表明该海域的自生碳酸盐矿物的形成受甲烷渗漏作用影响很大。不过,直接观察法主要用于定性研究,只能得到反风化作用的强度和自生矿物的结构特征及元素组成,自生矿物的定量分析还需要结合化学检测法进行。

3.2 化学检测法

化学检测法是研究反风化作用最常用的手段。由于反风化作用发生时会结合大量的常量离子、金属离子和硅酸盐等,所以沉积物间隙水中溶质随深度或培养时间变化明显,不仅能够定性地有效检测出反风化作用的信号,还可以定量地计算反风化作用对不同元素的消耗速率。常量离子的间隙水剖面受到底层水盐度的影响,所以最常用的定性方法是以常量离子与Cl-的比值,或者不同元素之间的比值(如K+/F-和K/Si)来去除盐度的影响。如Zhao等[12]通过测定长江口沉积物间隙水中Ca2+/Cl-和Mg2+/Cl-随深度不断减少,发现了该区域沉积物中存在显著的自生碳酸盐的生成,而K+/Cl-的减少则暗示了铝硅酸盐矿物的生成。

对于定量的研究,由于间隙水剖面还受到诸如溶质扩散、平流输运和生物扰动等多种输运和扰动过程影响[29],因此通常借助早期成岩模型去除传输过程对溶质剖面的扰动,或者利用稳态沉积物培养的方法准确地计算不同元素的消耗速率。例如,对亚马逊河口的研究表明,沉积物间隙水中F-和K+的扩散通量之比与EDS-TEM的结果一致,表明类似铝硅酸盐矿物的形成[6,19]。长江口的沉积物培养实验的结果显示,伴随着间隙水中溶解无机碳(Dissolved Inorganic Carbon,DIC)含量随着培养时间的延长而增加,Ca2+和Mg2+存在显著的降低,表明有机碳的降解加快了自生碳酸盐的形成[11]。根据不同元素的消耗速率还可以推测不同区域反风化作用所形成矿物的化学式,如Mackin等[21]分析了长江口和邻近东海陆架表层沉积物间隙水中溶解Al-Si-H+的关系,根据不同离子间的比例,推测出长江口反风化作用生成的自生铝硅酸盐矿物的平均组成为EX0.91Mg0.77Al5.0Si2.7O10(OH)8(EX指可交换的阳离子)。值得注意的是,间隙水中元素随深度和培养时间的变化虽然可以对自生矿物进行定量的研究,但元素浓度通常受到吸附作用的影响或者与其他矿物结合生成新的矿物,如Mg2+可以与碳酸钙反应生成白云石[11],K+可以被高电荷的伊利石或蒙脱石固定[30],这些都不是反风化作用。因此,在利用间隙水溶质剖面探讨反风化作用时,需要根据不同区域的矿物种类特征以及不同元素间化学计量关系等(如之前提到的K+/F-和K/Si),通过仔细地分析和计算,排除这些因素的影响[7]

活性硅的早期成岩改造是硅酸盐反风化作用的重要指示。如图2所示,生物硅向铝硅酸盐矿物的转化主要分为3个过程,最初细胞膜之间存在明显的孔洞结构,细胞膜也较完整;之后自生铝硅酸盐矿物逐步填充了孔洞并且替代了部分的细胞膜;最后大部分的细胞膜被自生矿物所替代,孔洞结构也完全被自生矿物所填满(图2)[26]。在传统生物硅提取方法中,早期成岩改造后的生物硅并没有被提取,因此严重地低估了硅在沉积物中的埋藏[7]。Michalopoulos等[7]结合前人的方法,用0.1 mol/L 的盐酸(弱酸提取)和0.1 mol/L 的碳酸钠(弱碱提取)对亚马逊三角洲沉积物的活性硅(生物硅+早期成岩改造的生物硅)进行了连续提取,并定义了生物硅早期成岩指数:(TRSi-BSi)/TRSi。式中TRSi代表沉积物在弱酸和弱碱的连续提取下的活性硅总值;BSi为弱碱单独提取的值,只代表生物硅的含量。结果表明,亚马逊河口沉积物中生物硅早期成岩指数为0.31,硅藻细胞改变指数为0.90,证明了反风化作用有效地增强了活性硅的埋藏,从而影响了硅在近岸环境中的地球化学循环[7]

图2   生物硅向自生铝硅酸盐矿物转化不同阶段的示意图 (据参考文献[26]修改)

Fig.2   Interpretive schematic diagram that different stages of biogenic silica alteration process (modified after reference[26])

近年来,同位素分析的应用丰富了反风化研究的手段。32Si进入海洋后绝大部分被硅藻等浮游植物吸收,并逐步转化为硅质介壳,少量的32Si会随着硅质介壳的溶解进入到水体中,而大量的32Si能够以生物硅的形式进入到沉积物中,并且伴随着生物硅的矿化过程进入到自生黏土矿物中[20,31,32]32Si的丰度不会因生物硅的早期成岩改造而造成损失,通过计算可以同时得到生物硅和经历早期成岩改造后的生物硅的含量,因此运用32Si的丰度研究海洋环境中活性硅的保存更加准确。Rahman等[20]对亚马逊三角洲沉积物研究后发现,以32Si的丰度计算出的早期成岩改造的生物硅含量为933 μmol Si/g,远高于弱酸弱碱提取法的结果(约300 μmol Si/g),进一步证明了反风化作用对活性硅埋藏的重要性。对于自生碳酸盐矿物的同位素示踪,现阶段的研究大多集中于深海和生物壳体,如深海冷泉区甲烷成因的自生碳酸盐矿物的δ13C值较亏损,大多介于-70‰~20‰,而δ18O值则较富集,通常为正值,因此可以指示深海冷泉自生碳酸盐矿物的形成[33,34]。由于沉积物中自生碳酸盐矿物在近岸的生产量只占海洋中总生产量的小部分,所以对于河口与边缘海区域由强烈的有机碳再矿化作用引起的自生碳酸盐矿物的研究长期被忽略[13],其碳、氧同位素的分馏机制还不清楚,亟待进一步的探索。

4 反风化作用对海洋环境中元素循环的影响

反风化作用对海洋环境中C、Si、常量离子(K+,Mg2+,Li+和F-)、金属元素(Fe和Al)的循环具有重要影响,促使它们在海洋沉积物中长久埋藏。

4.1 碳

反风化作用对全球碳循环和平衡海水酸碱度具有重要意义[6,18]。陆地岩石的风化作用会吸收大量大气CO2,并将其转化为HC随河流进入海洋,海洋中,作为弱酸的HC的积累会导致海水pH降低,而反风化作用的发现表明,该过程消耗了HC,这解释了海水长期保持酸碱平衡的原因[17,18]。海洋沉积物中存在多种形式的碳转化,当河流输入和初级生产所产生的有机碳进入沉积物后会通过一系列化学和生物降解过程转化为无机碳,这些产生的无机碳一部分会通过扩散或者生物/物理扰动进入到上层水体[12,15],而另一部分则会与K+,Ca2+,Mg2+,Fe2+和Mn2+等离子生成铝硅酸盐矿物和碳酸盐矿物埋藏在沉积物中[11,12,15]。在河口及边缘海,大量活性有机碳的沉降造成了次氧或厌氧的早期成岩环境,并且移动泥的存在也加强了有机碳的再矿化作用,这些条件都加速了沉积物中的碳循环,同时促进了碳酸盐矿物和铝硅酸盐矿物的生成[6,7,9,12]。例如,在长江口泥质区开展的沉积物再矿化培养的结果表明,表层间隙水DIC浓度随时间不断增加,而深层的间隙水中DIC浓度则随时间变化逐渐降低,同时伴随着Ca2+和Mg2+也逐渐减少,这表明自生碳酸盐矿物的形成(方解石或白云石);而Mg2+和K+的消耗速率显著高于Ca2+的消耗速率,这也证明了该区域同样存在快速的自生铝硅酸盐矿物的生成(图3)[11]。长江口沉积物厌氧培养的结果表明Ca2+的消耗速率为-7.1 mmol/(m2·d),这与DIC的产生速率相近(9.1 mmol/(m2·d))[11],假设总沉积有机碳的降解速率为DIC产生速率与Ca2+的消耗速率之和(16.2 mmol/(m2·d)),河口及边缘海大约有25%的自生碳酸盐矿物会溶解再次进入到水体(以Ca2+的消耗速率计算,约1.8 mmol/(m2·d))[13],也就是说保存下来的约占75%,那么,总的来说,再矿化作用产生的DIC中有超过30%(7.1×75%/16.2≈33%)会以碳酸盐的形式保存在沉积物中。因此,反风化作用与有机碳的再矿化作用具有密切联系,是沉积物中碳循环的重要组成部分。

图3   长江口泥质区沉积物时间序列厌氧培养过程中间隙水溶质的变化(据参考文献[11]修改)

Fig.3   The change of pore-water solutes with time in sediments of anoxic incubation experiments(modified after reference[11])

4.2 硅

海洋硅藻能够吸收河流输送的硅酸盐并将其转化为生物硅,少部分的生物硅会在沉降过程中溶解,重新生成硅酸盐进入到水体中,而大部分则会进入到沉积物中[35]。反风化作用在生成新的铝硅酸盐矿物时,会结合大量硅酸盐,而这些硅酸盐主要来自于沉积物中生物硅的溶解[6,17,36]。在早期成岩过程中,生物硅可以快速转化为铝硅酸盐矿物,这种生物硅的快速转化反应控制着沉积物中溶解硅的浓度和通量;并且,由于河流会带来大量富含铁和铝元素的风化岩石碎屑,足以支持反风化作用的发生,所以生物硅的溶解成为自生铝硅酸盐矿物形成的主要控制因素[6,20]。据估算,在亚马逊河口约有22%的生物硅是通过反风化作用保存下来,如果将这一比例应用于其他热带河口,由于热带河口贡献了全球河流入海硅总量的74%,那么在全球尺度上热带河口埋藏的硅占河流入海总量的15%[7]。从目前的结果来看,反风化作用有效地吸收了陆地来源的硅酸盐,极大地限制了陆地硅酸盐向大洋的输送,是影响生物硅在海洋中保存的重要因素。据估算,在全球范围内,有4.5×1012~4.9×1012 Tmol/a的Si通过反风化作用埋藏在近岸沉积物中,因此被称为“硅失汇”(The Missing Silica Sink)[32]。近期的研究显示,在亚热带河口—长江河口和密西西比河河口生物硅早期成岩指数为0.4左右,与亚马逊河口的结果(0.31)相近,表明在这些区域沉积物中生物硅同样经历了早期成岩作用的改造[22,37]。由于这些亚热带河口每年同样会输送与热带河口相同量级的硅酸盐入海(表1),并发生快速的反风化作用,因此现阶段的分析也可能严重低估了活性硅在温带、亚热带河口的埋藏,亟待深入研究。

表1   不同河口活性硅的埋藏通量和生物硅早期成岩指数

Table 1   The burial fluxes and diagenetic alteration ratios of reactive silica in different estuarine regions

区域河流输入硅酸盐通量/(mol Si/a)活性硅埋藏通量/(mol Si/a)生物硅早期成岩指数参考文献
亚马逊三角洲7.67×10111.70×10110.31[7]
密西西比河口三角洲1.06×10111.45×10100.40[22,38]
长江口及东海内陆架7.29×10112.66×10110.42[37,39]

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4.3 常量离子

铝硅酸盐矿物和碳酸盐矿物的形成会吸收大量常量离子,所以反风化作用是海洋环境中重要的离子消耗机制[6,17]。在亚马逊河口、长江口、卡内奥赫湾和鄂霍次克海等陆海交界区域的研究表明,沉积物间隙水中F-,Li+,Na+,K+,Ca2+和Mg2+等离子浓度随深度显著减少[19,21,36]。对于硅酸盐的反风化作用,其过程对常量离子的吸收大致可分为2类,一类是与铝硅酸盐矿物原组分的交换,如F-替换伊利石中的OH-[25]:

Ky(Al, Mg, Fe)2 (Aly,Si4-y) O10 (OH)2+ 2xF- ↔Ky(Al, Mg, Fe)2 (Aly,Si4-y) O10 (OH1-x, Fx)2+2xOH-。 (3)

另一类是黏土碎屑的转化和重组,如高岭石碎屑转化成带有Mg-Fe-Al层的硅酸盐矿物[40]:

0.45 Al2Si2O5 (OH)4 + 0.95FeOOH +1.0H4SiO4+0.56Mg2+ + 0.88OH- + 4xF- + 0.24 e-

Mg0.56F e0.242+F e0.713+Al0.89Si1.90O5 (OH1-x, )4+1.83H2O + 4xOH-。 (4)

在上述2个公式中,根据不同的矿物类型,通常y<1,x在0.25~0.5之间[19,25]。对于碳酸盐的反风化作用,一方面Ca2+和Mg2+会直接与无机碳生成方解石或高镁方解石;另一方面,方解石还可以与间隙水中Mg2+进一步反应生成白云石[11,41]。由于强烈的反风化作用,河流输送的离子大都在河口及三角洲区域埋藏。例如,在巴布亚湾的研究显示,Li+的吸收扩散通量占当地河流入海总量的60%[6,7]。在亚马逊三角洲的研究表明,通过反风化作用每年K+的埋藏通量为1.24×1011 mol,占亚马逊河入海总量的84%(1.48×1011 mol),占全球河流K+入海总量的10% [6,42];每年F-离子的埋藏通量为0.34×1010 mol,假设把亚马逊三角洲的埋藏比例应用于所有的热带河口,那么F-通过反风化作用在热带河口的埋藏量占海洋环境中总埋藏量的接近40%[19]。因此,反风化作用对保持海水中离子浓度的平衡与稳定具有重要作用,自生铝硅酸盐矿物是这些离子在海洋环境中的重要归宿。

4.4 金属元素

铝硅酸盐矿物的沉积常伴随着金属元素的吸收,生物硅在早期成岩改造过程中也会在其细胞膜表面生成富含Fe和Al的矿物表面,之后再逐步转化为铝硅酸盐矿物(图2),而碳酸盐矿物生成时可以直接结合间隙水中的Fe2+和Mn2+,生成菱铁矿和菱锰矿,因此反风化作用对金属元素在河口与边缘海的循环也具有重要影响[7,15,26]。Mackin等[21]的沉积物培养实验表明,间隙水中溶解态铝处于过饱和状态,并且能够与Si(OH)4和阳离子(Na+,Mg2+和K+等)快速生成自生铝硅酸盐矿物,证明了在自生矿物形成的过程中会吸收大量溶解态铝。反风化作用在生成自生矿物时还可以结合二价铁,是海洋沉积物中高活性铁的重要保存手段[14~16]。Zhu等[16]检测了东海内陆架沉积物中不同形态二价铁的含量,结果显示,碳酸铁和硫化铁只占了早期成岩二价铁总量的45%~79%,这表明存在大量的二价铁参与到硅酸盐的反风化作用中,形成了富铁的硅酸盐矿物。河口及三角洲会接收大量来自陆源的富含铁、锰和铝氧化物的风化产物,一方面,这些风化产物本身即可以与其他离子结合生成新的铝硅酸盐矿物;另一方面,河口移动泥的存在加强了这些金属氧化物的还原作用,使更多的铁和锰进入到间隙水中,与有机碳降解生成的无机碳生成碳酸盐矿物。

5 长江口反风化作用研究进展

大河影响下的陆架边缘海(River-dominated Ocean Marigins, RiOMars)一直被认为是存在反风化作用的重要区域,一般具有以下特征:河流输送丰富的活性金属氧化物,有大量活性有机质的输入和较高的再矿化速率,存在大量生物硅的沉降以及碱金属和碱土金属等离子的持续供给,次氧化或厌氧的成岩条件等[9,10,43~45]。因此,RiOMars是反风化作用研究的重要区域(图4)。

我国长江口及邻近陆架是典型的RiOMars系统,大量陆源风化碎屑的输入提供了富含铁和铝的氧化物[16];长江口及东海内陆架频繁发生藻华,并且硅藻是其中的主要藻类[46],从而产生了大量易降解的海源有机质和生物硅的沉降[46];强烈的有机碳再矿化作用提供了足够的HC(图4)[11,12];随季节变化的水动力条件形成了由长江口至浙闽沿岸的移动泥带,其较强的物理扰动增强了金属元素在沉积物中的循环效率[11,12,47],以上这些因素都为反风化作用的发生提供了有利条件。现有的研究证据也表明了长江口反风化作用的存在。例如,早期SEM的结果表明,长江口存在明显的自生方解石、白云石和类似海绿石的富铁自生黏土矿物,它们在河口和陆架沉积中含量较高,在不同区域这种自生矿物的结构存在显著差异[30,48]。最近的研究显示,长江口沉积物间隙水的中常量离子(K+,Ca2+和Mg2+)随着溶解无机碳的增加而减少,这表明强烈的再矿化作用可能加速了反风化作用的发生[11,12]。另外,依据现有文献中的数据,长江口活性硅的埋藏比例可以被估算出来。长江口表层沉积物中的活性硅的平均含量为112 μmol Si/g[46],沉积物的埋藏速率为0.99 g/(m2·a)[49],长江口及东海内陆架的面积约为2.4×1011m2,那么该区域河口活性硅埋藏通量达2.66×107 mol Si/a,占长江输送硅酸盐通量的37%(表 1),如果再与早期成岩指数(0.42)相乘,那么长江口通过反风化作用去除的硅酸盐与亚马逊三角洲的量级相同。尽管以上只是粗略的估计,但是仍能反映出反风化作用对长江口活性硅埋藏的重要性。

图4   大河影响下的边缘海反风化作用示意图

Fig.4   Interpretive schematic diagram of reverse weathering in RiOMars

6 总结与展望

总的来说,反风化作用相较于开阔大洋自生矿物的形成,通常在短时间内完成。反风化作用的研究方法可分为直接观察法和化学分析法,前者主要用于自生铝硅酸盐矿物和碳酸盐矿物的结构和元素组成分析,后者则用于自生矿物定量的研究。反风化作用对多种元素的地球化学循环过程具有重要影响,自生铝硅酸盐矿物和碳酸盐矿物是生物硅、常量离子(F-,Li+,Na+,K+,Ca2+和Mg2+)和金属元素(Fe,Mn和Al)在海洋环境中的重要归宿,并有效地将HC转化为CO2,维持海水酸碱平衡。

目前对热带河口反风化作用的机制已经有所了解,但研究主要聚焦于亚马逊河口,针对温带、亚热带河口的反风化作用的研究还很少见。与热带河口相比,亚热带和温带河流受陆地风化作用影响较大、河流输送的陆源有机碳年龄较老、水动力条件季节变化明显、人类活动所引起的赤潮和低氧现象更加频繁,这些因素可能使亚热带和温带河口具有不同的反风化作用特征[10~12,50~52]。尽管初步的研究结果表明这些河口也存在显著的反风化作用[10~12,21,37],但对于温带、亚热带河口反风化作用对全球不同元素的地球化学循环的影响还不清楚,许多问题亟待解决。例如,控制亚热带、温带河口控制反风化作用的主导因素是什么?亚热带、温带河口通过反风化作用生成的自生矿物特征是什么?是否与热带河口有所区别?人类活动是如何影响河口的反风化作用?河口移动泥带具有频繁的物理和生物扰动,对反风化作用有何影响?自生铝硅酸盐矿物与自生碳酸盐矿物在有机碳再矿化过程中是如何竞争和共存的?这些问题都是今后需要深入研究的重点,也是深入理解不同元素在海洋环境中循环与平衡的关键。

The authors have declared that no competing interests exist.


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[J]. 第四纪研究, 2011, 31(3): 426-430.]

DOI      Magsci      [本文引用: 4]      摘要

至今人们仍普遍认为: 是硅酸盐的化学风化碳汇作用在控制着长时间尺度的气候变化,而碳酸盐的化学风化作用不具有这一功能,因为碳酸盐溶解过程中消耗的所有CO2又通过海洋中相对快速的碳酸盐沉积而返回大气。本研究发现,碳酸盐溶解的快速动力学特性(比硅酸盐快100倍以上)以及硅酸盐流域中少量碳酸盐矿物在控制流域溶解无机碳(DIC)上的重要作用,再加上水生生物光合作用对DIC的利用,使得由碳酸盐风化形成的大气CO2汇以往被严重地低估至实际值的 1/3 左右,达到4.77亿吨 C/a,从而使得碳酸盐风化碳汇占整个岩石风化碳汇达到94%,而硅酸盐风化碳汇仅6%左右。因此,我们认为碳酸盐风化碳汇不仅控制了人类社会目前关注的短时间尺度的气候变化,而且在自水生光合生物出现以来的地质长时间尺度气候变化的控制上可能也是主要的。这无疑对传统的观点,即&quot;只有钙硅酸盐风化才能形成长久的碳汇并控制地质长时间尺度的气候变化&quot;提出了质疑。
[5] Liu Z H, Dreybrodt W, Wang H J.

A new direction in effective accounting for the atmospheric CO2 budget: Considering the combined action of carbonate dissolution, the global water cycle and photosynthetic uptake of DIC by aquatic organisms

[J].Earth Science Reviews,2010, 99(3/4):162-172.

DOI      URL      [本文引用: 1]     

[6] Michalopoulos P, Aller R C.

Rapid clay mineral formation of Amazon delta sediments: Reverse weathering and oceanic elemental cycles

[J]. Science, 1995, 270(5 236): 614-617.

DOI      URL      [本文引用: 16]      摘要

Formation of aluminosilicate minerals in marine sediments was proposed over 30 years ago as a potentially important control on the chemistry of the oceans. Until now, this reverse weathering process has been largely discounted because of insufficient direct evidence for its existence. Experiments with unaltered, anoxic, Amazon delta sediments showed that substantial quantities of K-Fe-Mg clay minerals precipitated on naturally occurring solid substrates over times of 6512 to 36 months at 6528°C. A range of pore-water, solute-flux, and solid-phase criteria indicates that comparable clay mineral precipitation processes occur throughout Amazon shelf sediments, contributing $\gtrsim$3 percent of the weight of the deposits and consuming 6510 percent of the global riverine K$^+$ flux.
[7] Michalopoulos P, Aller R C.

Early diagenesis of biogenic silica in the Amazon delta: Alteration, authigenic clay formation, and storage

[J].Geochimica et Cosmochimica Acta, 2004, 68(5): 1 061-1 085.

DOI      URL      [本文引用: 13]      摘要

The mild 1% Na 2 CO 3 alkaline leach procedure commonly used to estimate biogenic silica was modified to include an initial mild leach step with 0.1N HCl to remove metal oxide coatings and to activate poorly crystalline authigenic phases for alkaline dissolution. Well-crystallized clays are not significantly affected by this modification nor is bulk Amazon River bed sediment. The two-step procedure indicates that 6590% of the biogenic silica originally present in deposits is converted to clay or otherwise altered, raising the effective quantity of biogenic silica stored from 6533 to 65296 μmol Si g 611 (651.8% SiO 2 ). Biogenic Si stored in the delta increases away from the river mouth, across shelf and along the dispersal system where primary production is highest. The K/Si ratio of labile authigenic material is 650.19 mol mol 611 , far higher than Amazon River suspended matter (650.07 mol mol 611 ). Diagenetic models indicate formation rates in the mobile sediment layer of 652.8 μmol K g 611 yr 611 (6516 μmol Si g 611 yr 611 ). Inclusion of authigenic alteration products of biogenic silica in estimates of reactive Si burial increases the deltaic storage of riverine Si to 6522% of the Amazon River input. The rapid formation of aluminosilicates from biogenic SiO 2 , seawater solutes, and remobilized Fe, Al-oxides represents a form of reverse weathering. Rapid reverse weathering reactions in tropical muds and deltaic deposits, the largest sediment depocenters on Earth, confirms the general importance of these processes in oceanic elemental cycles.
[8] Higgins J A, Schrag D P.

Constraining magnesium cycling in marine sediments using magnesium isotopes

[J].Geochimica et Cosmochimica Acta, 2010, 74(17): 5 039-5 053.

DOI      URL      [本文引用: 1]      摘要

Magnesium concentrations in deep-sea sediment pore-fluids typically decrease down core due to net precipitation of dolomite or clay minerals in the sediments or underlying crust. To better characterize and differentiate these processes, we have measured magnesium isotopes in pore-fluids and sediment samples from Ocean Drilling Program sites (1082, 1086, 1012, 984, 1219, and 925) that span a range of oceanographic settings. At all sites, magnesium concentrations decrease with depth. At sites where diagenetic reactions are dominated by the respiration of organic carbon, pore-fluid δ 26 Mg values increase with depth by as much as 2‰. Because carbonates preferentially incorporate 24 Mg (low δ 26 Mg), the increase in pore-fluid δ 26 Mg values at these sites is consistent with the removal of magnesium in Mg-carbonate (dolomite). In contrast, at sites where the respiration of organic carbon is not important and/or weatherable minerals are abundant, pore-fluid δ 26 Mg values decrease with depth by up to 2‰. The decline in pore-fluid δ 26 Mg at these sites is consistent with a magnesium sink that is isotopically enriched relative to the pore-fluid. The identity of this enriched magnesium sink is likely clay minerals. Using a simple 1D diffusion–advection–reaction model of pore-fluid magnesium, we estimate rates of net magnesium uptake/removal and associated net magnesium isotope fractionation factors for sources and sinks at all sites. Independent estimates of magnesium isotope fractionation during dolomite precipitation from measured δ 26 Mg values of dolomite samples from sites 1082 and 1012 are very similar to modeled net fractionation factors at these sites, suggesting that local exchange of magnesium between sediment and pore-fluid at these sites can be neglected. Our results indicate that the magnesium incorporated in dolomite is 2.0–2.7‰ depleted in δ 26 Mg relative to the precipitating fluid. Assuming local exchange of magnesium is minor at the rest of the studied sites, our results suggest that magnesium incorporated into clay minerals is enriched in δ 26 Mg by 0‰ to +1.25‰ relative to the precipitating fluid. This work demonstrates the utility of magnesium isotopes as a tracer for magnesium sources/sinks in low-temperature aqueous systems.
[9] Yao Peng, Yu Zhigang, Guo Zhigang.

Research progress in transport, burial and remineralization of organic carbon at large river dominated ocean margins

[J].Marine Geology and Quaternary Geology, 2013, 33(1): 153-160.

[本文引用: 3]     

[姚鹏, 于志刚, 郭志刚.

大河影响下的边缘海沉积有机碳输运与埋藏及再矿化研究进展

[J].海洋地质与第四纪地质, 2013,33(1): 153-160.]

[本文引用: 3]     

[10] Yao Peng,Guo Zhigang,Yu Zhigang.

Research process in transport, burial and remineralization of organic carbon at large river dominated ocean margins

[J]. Acta Oceanologica Sinica,2014,36(2):23-32.

[本文引用: 3]     

[姚鹏,郭志刚,于志刚.

大河影响下的陆架边缘海沉积有机碳的再矿化作用

[J].海洋学报,2014,36(2):23-32.]

DOI      URL      [本文引用: 3]      摘要

大河影响下的陆架边缘海(RiOMars)是陆源有机碳的主要沉积汇,是陆海相互作用最重要的区域,在全球碳的生物地球化学循环中发挥着重要作用。受到RiOMars系统内频繁的物理和生物等改造作用的影响,该区沉积的有机碳并没有得到很好地保存而被永久埋藏,而是发生了显著的再矿化分解。本文首先对目前常用的基于 O2消耗速率和CO2产生速率的两类测定RiOMars系统沉积有机碳再矿化速率的方法进行了介绍,分析了各自的优缺点和适用性,进而从碳的形态转化、表层沉积物混合均匀、形成次氧化的氧化还原条件、有机碳保存效率低、发生反风化作用和微生物发挥着重要作用等几个方面对RiOMars系统沉积物发生再矿化作用时的主要过程和特征进行了剖析,以期深入认识边缘海的再矿化作用及其对边缘海碳汇的影响。
[11] Yao P, Zhao B, Bianchi T S,et al.

Remineralization of sedimentary organic carbon in mud deposits of the Changjiang Estuary and adjacent shelf: Implications for carbon preservation and authigenic mineral formation

[J]. Continental Shelf Research, 2014, 91: 1-11.

DOI      URL      [本文引用: 10]      摘要

61Preservation of organic carbon in Changjiang Estuary and East China Sea sediments.61Role of organic carbon remineralization in mobile-mud deposits.61Linkages between authigenic mineral formation and organic carbon remineralization.
[12] Zhao B, Yao P, Bianchi T S, et al.

Early diagenesis and authigenic mineral formation in mobile muds of the Changjiang Estuary and adjacent shelf

[J].Journal of Marine Systems, 2017, 172: 64-74.

DOI      URL      [本文引用: 11]      摘要

Large-river delta-front estuaries (LDEs) and their adjacent shelf margins are sites of dynamic diagenetic processes that play a significant role in coastal biogeochemical cycling. In this study, we used dissolved inorganic carbon (DIC), redox sensitive elements (Fe 202+ and Mn 202+ ), dissolved inorganic nitrogen (DIN) nutrients (NH 4 + , NO 3 61 , and NO 2 61 ), major cations and anions (K + , Ca 202+ , Mg 202+ , SO 4 20261 , and Cl 61 ) in bottom-water and sediment pore-waters, to investigate the early chemical diagenesis and authigenic mineral formation in mobile-mud deposits of the Changjiang Estuary and adjacent inner shelf of the East China Sea (ECS). Vertical profiles of DIC and NH 4 + in pore-waters had similar trends at most sites, showing a significant increase with depth near the Changjiang Estuary and being relatively constant at offshore sites. Higher pore-water DIC and NH 4 + concentrations were observed in nearshore sites in winter, which were likely attributed to exposure of deeper deposits by winter coastal erosion. Nitrification was observed at most sites, and AOB (ammonia-oxidizing bacteria) played a leading role in ammonia oxidation in the study areas. The nitrification-denitrification was likely important in contributing to the loss of DIN in offshore sites during summer. Large inputs of organic carbon (OC) and terrestrial materials from Changjiang River resulted in intense sulfate reduction and Fe and Mn reduction in nearshore sites. Lower C/N and C/S ratios coupled with an apparent decrease in pore-water Ca 202+ and Mg 2+ concentrations with depth near the Changjiang Estuary, which indicated that authigenic carbonate formation occurs in these sediments. Decreases in K + and Mg 202+ with depth reflected that reverse weathering was an important process of authigenic mineral formation in these sediments. We conclude that adsorption process, seasonal erosion-redeposition, and summer hypoxic conditions of bottom-waters may play an important role in early diagenesis processes and remineralization of SOC in the Changjiang LDE.
[13] Milliman J D.

Production and accumulation of calcium carbonate in the ocean: Budget of a non-steady state

[J].Global Biogeochemical Cycles, 1993, 7(4): 927-957.

DOI      URL      [本文引用: 3]      摘要

Present-day production of CaCOin tne world ocean is calculated to be about 5 billion tons (bt) per year, of which about 3 bt accumulate in sediments; the other 40% is dissolved. Nearly half of the carbonate sediment accumulates on reefs, banks, and tropical shelves, and consists largely of metastable aragonite and magnesian calcite. Deep-sea carbonates, predominantly calcitic coccoliths and planktonic foraminifera, have orders of magnitude lower productivity and accumulation rates than shallow-water carbonates, but they cover orders of magnitude larger basin area. Twice as much calcium is removed from the oceans by present-day carbonate accumulation as is estimated to be brought in by rivers and hydrothermal activity (1.6 bt), suggesting that outputs have been overestimated or inputs underestimated, that one or more other inputs have not been identified, and/or that the oceans are not presently in steady state. One "missing" calcium source might be groundwater, although its present-day input is probably much smaller than that of rivers. If, as seems likely, CaCOaccumulation presently exceeds terrestial and hydrothermal input, this imbalance presumably is offset by decreased accumulation and increased input during lowered sea level: shallow-water accumulation decreases by an order of magnitude with a 100 m drop in sea level, while groundwater influx increases because of heightened piezometric head and the diagenesis of metastable aragonite and magnesian calcite from subaerially exposed shallow-water carbonates.
[14] Aller R C, Hannides A, Heilbrun C, et al.

Coupling of early diagenetic processes and sedimentary dynamics in tropical shelf environments: The Gulf of Papua deltaic complex

[J].Continental Shelf Research, 2004, 24(19): 2 455-2 486.

DOI      URL      [本文引用: 3]      摘要

Tropical mobile mud belts represent a major class of biogeochemical and diagenetic systems characterized by extensive and frequent physical reworking of fine-grained, organic-rich deposits underlying oxygenated waters. Large regions of the Gulf of Papua, Papua New Guinea deltaic complex are dominated by such conditions. A reworked mud belt lies within the inner shelf between 6510 and 2002m depth on a sedimentary clinoform derived from coalescing deltas. Deposits across the topset are typically suboxic, nonsulfidic over the upper 650.5–102m, and have low to moderate maximum pore water concentrations of dissolved Fe(II) and Mn(II) (65100–200, but up to 6580002μM). Sediments are reactive, with surficial ΣCO production 650.1–0.302mM02d and benthic O fluxes 6523±1502mmol02m02d (upper 652002cm). The highest rates occur within inner topset deposits (6510–2002m) and near the high accumulation rollover region of the topset–foreset beds (6540–5002m). Lower rates are found inshore along intertidal channels—mangrove fringe and within scoured or exposed consolidated deposits of the middle topset region. Remineralization rate patterns are independent of relative dominance by terrestrial or marine carbon in sediments. Dissolved O usually penetrates 652–502mm into surface sediments when macrofaunal burrows are absent. More than 75% of the highly reactive sedimentary Fe(III) pool (65350–40002μmol02g) is typically diagenetically reduced in the upper 650.502m. Pore water S generally remains below detection over the upper 651–202m. As in other deltaic topset regions, is supplied to the SO reducing zone. Sedimentary C/S ratios are 654–6 within the suboxic topset regions but decrease to ; most reactive Fe is diagenetically reduced (ΣFe(II)/ΣFeR650.7–0.8); the proportion of diagenetically reduced Fe present as pyrite is low (Py–Fe(II)/particle surface area ). These depositional environments must be most common in tropical climates during high sea stand.
[15] Aller R C, Heilbrun C, Panzeca C, et al.

Coupling between sedimentary dynamics, early diagenetic processes, and biogeochemical cycling in the Amazon-Guianas mobile mud belt: Coastal French Guiana

[J].Marine Geology, 2004, 208(2/4): 331-360.

DOI      URL      [本文引用: 3]      摘要

Coastal French Guiana lies within the vast mobile mudbelt that characterizes much of the S. American inner shelf downdrift of the Amazon River. Approximately 6515–20% of the Amazon sediment outfall moves NW along the Guianas, in part as a series of 20–25 coastal mud waves. Seasonal studies of a representative migrating mudwave located between Kourou and Sinnamary, French Guiana demonstrate that diagenetic properties and biogeochemical cycling are closely coupled to sedimentary dynamics and the refluxing of reduced components between the seabed, coastal facies, and well-oxygenated overlying water. An unsteady two-zone diagenetic regime is typically present in the shallow subtidal and low intertidal regions. A surficial layer, usually 650.5–1 m thick, is nonsulfidic, highly reactive, and dominated by Fe, Mn cycling. This suboxic layer unconformably overlies more consolidated sediment in which net SO 4 261 reduction is often observed, and contracts shoreward toward the mangrove fringe as sediments stabilize and become bioturbated. The relatively stable intertidal flats are also sites of significant benthic primary production. Despite suboxic conditions over extensive intervals, anaerobic remineralization rates are high (ΣCO 2 650.2–0.6 mM day 611 ), and often show little evidence of attenuation with depth. Integrated ΣCO 2 fluxes are 6520–235 mmol m 612 day 611 (wet/dry season average 65120), far exceeding diffusive O 2 fluxes into the bottom. High reactivity (650.08 day 611 ) and low C/N remineralization release ratios (655.3) of decomposing material imply fresh substrate of marine origin. Most reduced solid phase Fe is present as nonpyritic authigenic Fe minerals (<20% Fe(II) is in pyrite), and low sedimentary C/S ratios (656–8) reflect the generally nonsulfidic conditions. A broad range of tracers (e.g. 234 Th ( t 1/2 =24 days), 210 Pb ( t 1/2 =22 years), seasonal Cl 61 profiles) and nonsteady state diagenetic models of pore water concentrations and oxidant–reductant relationships demonstrate that the upper 0.1–1 m of deposits are reworked and exchanged with overlying water on timescales of <10 days to seasonally. Thus, the seafloor acts as a massive suboxic batch reactor, entraining and processing reactive marine plankton, regenerating Fe, Mn oxides, exchanging metabolites and nutrients with the oxygenated water column, and generating suites of nonsulfidic authigenic minerals. The apparent paradoxical properties of high remineralization rate, low reductant content (C org 65630 μmol g 611 ), and dominance of suboxic metal cycling are a direct consequence of frequent entrainment of highly reactive organic substrate and simultaneous regeneration of the major Fe oxidants in oxygenated water. The Amazon–Guianas mobile mudbelt is a zone of extraordinarily intense sedimentary and biogeochemical recycling, greatly exceeding stable coastal systems, such as salt marshes, in material exchange with the sea.
[16] Zhu M X, Chen K K, Yang G P, et al.

Sulfur and iron diagenesis in temperate unsteady sediments of the East China Sea inner shelf and a comparison with tropical Mobile Mud Belts (MMBs)

[J].Journal of Geophysical Research: Biogeosciences, 2016, 121(11): 2 811-2 828.

DOI      URL      [本文引用: 4]      摘要

Redox cycling of iron (Fe) and sulfur (S) exerts profound influences on fates of numerous elements in coastal marine sediments. In this study, S and Fe cycling and its geochemical expressions in the East China Sea (ECS) inner shelf, a representative of temperate mobile mud belts (MMBs), were characterized and compared with tropical counterparts (the Amazon shelf and the Gulf of Papua). Fe and S speciation consistently points to the dominance of authigenic nonsulfidized Fe(II) phases (i.e., poorly crystalline clays (PCCs) and carbonates) and the prevalence of Fe redox cycling in the suboxic or weakly sulfidic regimes of the ECS-MMBs. High contents of authigenic magnetite may be a common diagenetic expression in all MMBs. Compared to the tropical MMBs, three main differences of diagenetic expressions in the ECS-MMBs are (i) light Sin the ECS-MMB versus characteristically heavy Sin the Amazon shelf MMBs; (ii) lower total reactive Fe (Fe), total diagenetic Fe(II), and ratio of Feto total Fe in the ECS-MMBs; and (iii) Fe(II) carbonates and PCCs are equally important sinks for nonsulfidized Fe(II) in the ECS-MMBs, whereas PCCs are the predominant sink in the tropical counterparts. These differences are ascribable to factors including low degradability of organic matter, small diffusion scales, less intense chemical weathering in the drainage basin, and/or weaker reverse weathering in the ECS-MMBs. Despite the differences above, Fe and S diagenetic expressions that characterize the prevalence of Fe redox cycling in the unsteady suboxic regimes are shared by the ECS-MMBs and tropical MMBs.
[17] Mackenzie F T, Garrels R M.

Chemical mass balance between rivers and oceans

[J].American Journal of Science, 1966, 264(7): 507-525.

DOI      URL      [本文引用: 7]      摘要

ABSTRACT. The assumption of constancy of the chemical composition of ocean water requires that the excesses of dissolved constituents carried by streams to the ocean be removed." lhe chemical mass balance between streams and oceans is an attempt to
[18] Mackenzie F T, Kump L R.

Reverse weathering, clay mineral formation, and oceanic element cycles

[J].Science, 1995, 270(5 236): 586-587.

DOI      URL      [本文引用: 6]     

[19] Rude P D, Aller R C.

Fluorine uptake by amazon continental shelf sediment and its impact on the global fluorine cycle

[J].Continental Shelf Research, 1994, 14(7/8): 883-907.

DOI      URL      [本文引用: 6]      摘要

Dissolved fluoride concentrations in sediment pore waters are below seawater throughout the Amazon continental shelf sedimentary environment. Calculations of mass fluxes of fluoride between seawater and mud deposits, based on pore water gradients, reaction rate estimates, and selective chemical extraction of sediment, indicate an uptake of 0.2-0.6 脳 10 10 moles F y 鈭1 . The majority of this uptake is apparently due to alteration of detrital alumino-silicate debris or neoformation of authigenic alumino-silicate minerals within the sediment itself. Uptake of fluoride during diagenesis of Amazon River sediment on the Amazon continental shelf equals approximately 7% of the previously defined sinks in the marine environment. If this process occurs in other tropically-derived shelf sediments, then alumino-silicate reactions would represent the most important mechanism of fluoride removal in the sea.
[20] Rahman S, Aller R C, Cochran J K.

Cosmogenic 32Si as a tracer of biogenic silica burial and diagenesis: Major deltaic sinks in the silica cycle

[J].Geophysical Research Letters, 2016, 43(13):7 124-7 132.

DOI      URL      [本文引用: 3]      摘要

Measurements of natural cosmogenic Si (t~ 140 years) in tropical deltaic sediments demonstrate for the first time that most Si is present in rapidly formed authigenic clays and not biogenic opaline silica (bSi). The burial of bSi in deltaic and continental margin sediments has likely been greatly underestimated because of diagenetic alteration of bSi to clay, little of which dissolves in the classically used operational bSi leach. Rapid reverse weathering reactions during early diagenesis must be considered as a significant pathway of reactive Si storage in deltaic deposits. Based on Si, actual storage may be 2-3 times the best recent estimates extrapolated from diagenetic models or attempts to modify operational bSi methods to include authigenic clay (~900 碌mol/g versus ~250 碌mol/g). Measurements of natural Si inventories in sediments and initial specific activities in biogenic silica provide a means to independently constrain the marine Si cycle.
[21] Mackin J E, Aller R C.

Dissolved Al in sediments and waters of the East China Sea: Implications for authigenic mineral formation

[J]. Geochimica et Cosmochimica Acta, 1984, 48(2): 281-297.

DOI      URL      [本文引用: 5]      摘要

Numerous previous studies indicate that several different authigenic aluminosilicates form in the oceans. In this study we show, using dissolved Al distributions in sediments and waters from the nearshore regions of the East China Sea, that the process of aluminosilicate formation probably begins rapidly upon contact of detrital clays with seawater. Statistical analyses of dissolved Al-Si-H + relations in surface sediments indicate that the minerals forming in East China Sea sediments low in dissolved Fe are dioctahedral chlorites with an average composition EX 0.91 Mg 0.77 Al 5.0 Si 2.7 O 10 (OH) 8 (where EX = exchangeable + 1 cation). This composition is also consistent with dissolved Al and Si measurements as a function of salinity in turbid overlying waters. Results suggest a dissolution-攔eprecipitation mechanism for clay mineral reconstitution. This mechanism can help to explain why different authigenic clays are found in different areas of the oceans. In the East China Sea the total amount of authigenic clays present must constitute a very minor fraction of the bottom sediments. Thus, the formation of these minerals has a relatively small impact upon dissolved Si distributions. Clay mineral reconstitution in nearshore regions may provide a mechanism for buffering sediments and overlying waters with respect to pH, as the composition of minerals formed should be a direct function of the H + activity in the surrounding environment.
[22] Presti M, Michalopoulos P.

Estimating the contribution of the authigenic mineral component to the long-term reactive silica accumulation on the western shelf of the Mississippi River Delta

[J].Continental Shelf Research, 2008, 28(6):823-838.

DOI      URL      [本文引用: 1]      摘要

Previous studies have shown how biogenic silica particles undergo conversion to aluminosilicate phases in large tropical deltaic systems, thus affecting the world ocean budget of major seawater cations. This study tackles the important question of the silica budget in the coastal zone of the Mississippi River Delta, providing evidence for the role of biogenic silica diagenesis in this subtropical system from direct examination of individual diatom particles, sediment leachates and pore-water composition. The estimated reactive silica stored in the study area (5990 km 2) is based on operational leaches that account for altered biogenic silica particles and other authigenic aluminosilicate phases in addition to fresh biogenic silica. Early diagenesis of silica in the delta front occurs mainly where more siliceous material is deposited. An inner-shelf area, where hypoxic conditions are found, significantly contributes to the formation of authigenic products of Si alteration. Data suggest that the limiting factor of silica alteration processes is the availability of detrital phases such as Al and Fe. The estimated total reactive silica accumulation in the study area is 1.45×10 10 mol Si year 611, representing 652.2% of the long-term bulk sediment accumulation. On the basis of a conservative appraisal, the authigenic mineral components account for 6540% of the long-term reactive silica storage. This study shows that non-tropical deltaic systems are significantly more important sinks of silica than previously thought and that, where conditions are favourable, a consistent portion of reactive silica not leaving the shelf is stored within the delta in the form of authigenic components.
[23] Aller J Y, Aller R C, Kemp P F, et al.

Madrid Fluidized muds: A novel setting for the generation of biosphere diversity through geologic time

[J]. Geobiology, 2010, 8: 169-178.

DOI      URL      PMID      [本文引用: 1]      摘要

Reworked and fluidized fine-grained deposits in energetic settings are a major modern-day feature of river deltas and estuaries. Similar environments were probably settings for microbial evolution on the early Earth. These sedimentary systems act as efficient biogeochemical reactors with high bacterial phylogenetic diversity and functional redundancy. They are temporally rather than spatially structured, with repeated cycling of redox conditions and successive stages of microbial metabolic processes. Intense reworking of the fluidized bed entrains bacteria from varied habitats providing new, diverse genetic materials to contribute to horizontal gene transfer events and the creation of new bacterial ecotypes. These vast mud environments may act as exporters and promoters of biosphere diversity and novel adaptations, potentially on a globally important scale.
[24] Zhang Qianzhu, Tao Zhen, Gao Quanzhou, et al.

A review of the biogeochemical cycles of dissolved silicon in rivers

[J].Advances in Earth Science, 2015, 30(1): 50-59.

Magsci      [本文引用: 1]     

[张乾柱, 陶贞, 高全洲, .

河流溶解硅的生物地球化学循环研究综述

[J].地球科学进展, 2015, 30(1): 50-59.]

DOI      URL      Magsci      [本文引用: 1]      摘要

河流溶解硅(DSi)承载着陆地表生过程的环境信息, 其输入、迁移、转化和输出受多种因素制约。在全球硅酸盐岩风化过程中, 31.53%~64.87%的DSi被陆地植被吸收, 仅12.91%迁移至河流, 在向海洋输送过程中, 河流DSi又受到水生生物吸收、逆风化作用及“人造湖效应”等因素的影响, 输出量进一步减少, 弱化了海洋系统的“生物泵”作用;不多的研究表明全球河流DSi浓度变化介于138~218 μmol/L之间, 空间差异显著, 有必要量化各影响因素的贡献, 建立多因素控制的河流DSi输出通量模型;与地壳主要硅酸盐岩的δ<sup>30</sup>Si值(约为-0.5‰)相比, 全球河流DSi的δ<sup>30</sup>Si值变化范围较大(介于-0.2‰~3.4‰之间)且显著正偏, 分馏系数达0.3‰~3.9‰。这是由于流域内Si同位素的无机分馏和有机分馏2种动力分馏过程所导致。因此, 探讨河流DSi来源、迁移及转化机制是未来深入研究河流DSi循环的关键问题。
[25] Mackin J E, Aller R C.

The effects of clay mineral reactions on dissolved Al distributions in sediments and waters of the Amazon continental shelf

[J]. Continental Shelf Research, 1986, 6(1/2): 245-262.

DOI      URL      [本文引用: 3]      摘要

Reactions involving clay minerals may exert a major control on some aspects of marine water and sediment chemistry. The potential of clay mineral reactions in this regard was investigated in Amazon continental shelf muds and overlying waters using highly sensitive dissolved Al analyses. Data are restricted to low-Fe pore waters from undisturbed and incubated (4-11 days, T = 28 卤 1 掳C) surface sediment at 9 stations, a surface water transect through the Amazon River plume, and water column profiles determined at coring sites. Approximately constant relations between dissolved Al, Si, and H + in pore waters imply that aluminous authigenic clays (Si/Al = 0.83, H + /Al = 0.43) are forming in muddy regions of the Amazon shelf. Equilibrium models based upon the pore water data also predict the correct magnitude of dissolved A1 concentrations in the Amazon River plume in the absence of high biological productivity, indicating that authigenic clays control some characteristics of overlying water chemistry. In water column profiles, dissolved Al increases with depth at high salinities apparently because of sediment resuspension into low dissolved Si waters and subsequent clay dissolution. The results of this study confirm predictions based upon previous laboratory and field studies of dissolved Al behavior. They also point out some of the possible complexities of clay reconstitution reactions where aluminous authigenic clays form from more siliceous precursors in nearshore sediments and waters.
[26] Michalopoulos P, Aller R C, Reeder R J.

Conversion of diatoms to clays during early diagenesis in tropical, continental shelf muds

[J].Geology, 2000, 28(12): 1 095-1 098.

DOI      URL      [本文引用: 3]      摘要

In coastal muds downdrift from the Amazon River mouth, marine diatom frustules are rapidly converted to various forms of authigenic aluminosilicate phases during burial. The dominant neoformed crystalline phases have a composition similar to K-smectite, yield electron diffraction patterns characteristic of clay minerals, and exhibit a range of crystal sizes and morphologies, including euhedral pseudohexagonal crystals and anhedral flakes replacing biogenic silica. A poorly crystalline or microcrystalline K-rich and Fe-rich aluminosilicate material also replaces the siliceous frustules. The conversion process is not always complete, leaving relics of the original frustule in the resulting authigenic aluminosilicate phases. Laboratory incubation experiments with cultured diatoms demonstrate that the conversion process occurs in 20 23 months. The conversion of biogenic silica to authigenic clays occurs throughout the Amazon deltaic deposits and presumably takes place in other comparable depositional settings. Biogenic silica alteration provides proof for a direct link between the biogeochemical cycle of silica in nearshore environments and the neoformation of cation-rich aluminosilicate phases, and it may prove to be important for oceanic geochemical cycles as a sink for Si, K, and other elements incorporated in the authigenic aluminosilicates. Rapid formation of authigenic K-smectite may also represent a reaction stage leading to eventual formation of illitic clays during later diagenesis.
[27] Wang C H, Xu L Z, Jin J C.

An initial study of relationship between sulfate reduction and carbonate mineralization

[C]∥Proceedings of the International Symposium on Sedimentation on the Continental Shelf, With Special Reference, 1983:795-806.

[本文引用: 1]     

[28] Yang Kehong, Chu Fengyou, Ye Liming, et al.

Implication of methane seeps from sedimentary geochemical proxies(Sr/Ca & Mg/Ca)in the Northern South China Sea

[J].Journal of Jilin University, 2014, 44(2):469-479.

[本文引用: 1]     

[杨克红,初凤友,叶黎明,.

南海北部甲烷渗漏的沉积地球化学指标(Sr/Ca 和 Mg/Ca)识别

[J].吉林大学学报,2014, 44(2):469-479.]

DOI      URL      [本文引用: 1]      摘要

自生碳酸盐矿物是揭示甲烷渗漏过程及其周期性变化的重要指标。为了方便、快速地识别出自生碳酸盐矿物,在探讨了前人建立的端元组分模型(文石、高镁方解石、生物成因方解石和碎屑)在我国南海北部适用性的基础上,利用沉积物全样中Sr/Ca和Mg/Ca值计算了南海北部神狐海域两支沉积物柱状样中自生碳酸盐矿物的质量分数,计算结果表明,在不同沉积深度均有含量不等的自生碳酸盐矿物。这一结果被X射线衍射结果和沉积物中存在晶形完好的自生高镁方解石和文石矿物所验证,表明利用前人建立的端元组分模型计算的结果具有可靠性。自生碳酸盐矿物的出现显示该海域深受甲烷渗漏作用影响。利用地球化学指标(Sr/Ca和Mg/Ca)获得的自生碳酸盐矿物含量垂向变化显示该区域甲烷渗漏具有强弱交替的周期变化。运用端元组分模型来获取沉积物柱状样中自生碳酸盐矿物的高分辨率剖面,从而识别甲烷渗漏信息非常方便,在大范围寻找甲烷渗漏和天然气水合物方面具有较大潜力。
[29] Boudreau B P.

Diagenetic Models and Their Implementation: Modelling Transport and Reactions in Aquatic Sediments

[M]. Berlin: Springer, 1997.

[本文引用: 1]     

[30] Hover V C, Walter L M, Peacor D R.

K uptake by modern estuarine sediments during early marine diagenesis, Mississippi Delta Plain, Louisiana, U.S.A

.Journal of Sedimentary Research, 2002, 72(6): 775-792.

DOI      URL      [本文引用: 2]     

[31] Zhou Peng, Li Dongmei, Liu Guangshan,et al.

Study on a cosmic-ray-produced silicon-32 as a tracer for ocean processes

[J]. Journal of Isotopes, 2015,28(1): 7-19.

Magsci      [本文引用: 1]     

[周鹏, 李冬梅, 刘广山, .

应用宇生放射性同位素硅-32示踪海洋过程的研究

[J].同位素, 2015, 28(1): 7-19.]

DOI      Magsci      [本文引用: 1]      摘要

<sup>32</sup>Si是一种宇生放射性核素,半衰期约150年。由于其来源单一、生产速率相对恒定,并具有与稳定硅相同的化学和生物特性,一直被视为研究50~1 000年尺度海洋过程的一个理想的计时钟和示踪剂。本文介绍了<sup>32</sup>Si在海洋学的应用,主要包括示踪近岸和大洋水体的混合,河口和大洋中硅的地球化学行为和循环,深海海底颗粒物的混合,及利用其计算沉积速率/混合速率,建立年代序列来反映环境变化的信息。
[32] Rahman S, Aller R C, Cochran J K.

The missing silica sink: Revisiting the marine sedimentary Si cycle using cosmogenic 32Si

[J]. Global Biogeochemical Cycles, 2017,31: 1 559-1 578.

DOI      URL      [本文引用: 2]     

[33] Tong H, Feng D, Cheng H, et al.

Authigenic carbonates from seeps on the northern continental slope of the South China Sea: New insights into fluid sources and geochronology

[J]. Marine and Petroleum Geology, 2013, 43(946): 260-271.

DOI      URL      [本文引用: 1]      摘要

Seep carbonates represent excellent archives of seepage activities near seafloors. In order to provide insights on sources of seeping fluids, stable carbon and oxygen isotopes and 87 Sr/ 86 Sr ratios were applied to seep carbonates from Shenhu, SW Dongsha, and NE Dongsha on the northern continental slope of the South China Sea. U/Th dating was selected to constrain the time involved in carbonate formation and the potential driving force. The δ 13 C values of the Shenhu and NE Dongsha carbonates vary from 6152.3‰ to 6132.6‰ (V-PDB), indicating that biogenic methane is the primary carbon source at both locations. The δ 13 C values of the SW Dongsha carbonates are much higher, ranging from 6118.8‰ to 6111.4‰ (V-PDB), suggesting that thermogenic methane is the predominant carbon source in this region. A relatively deep origin of thermogenic methane for the SW Dongsha seeps is also supported by somewhat lower 87 Sr/ 86 Sr ratios of the samples (from 0.709025 to 0.709097). The δ 18 O values of the Shenhu and NE Dongsha carbonates vary from 1.4‰ to 5.1‰ (V-PDB), while the δ 18 O values of the SW Dongsha carbonates range from 2.5‰ to 3.4‰ (V-PDB). Many samples from Shenhu and NE Dongsha demonstrate an 18 O-enriched fluid source that most likely originated from waters released from the dissociation of locally abundant gas hydrate. U/Th ages of the Shenhu carbonates show a large range from 330ka to 152ka BP and the NE Dongsha carbonates have ages from 77ka to 63ka BP. Interestingly, U/Th ages of most samples are either within times of sea-level lowstands or correspond to periods when the sea-level was falling. Taken together, our data suggest that in the South China Sea gas hydrate dissociation during sea-level lowstands or falling stages resulted from reduced hydrastastic pressures, which in turn enhanced the seep activities and promoted the formation of authigenic carbonates close to the seafloor.
[34] Chen Duofu, Chen Xianpei, Chen Guangqian.

Geology and geoche mistry of cold seepage and venting-related carbonates

[J].Acta Sedimentologica Sinica, 2002, 20(1): 34-40.

Magsci      [本文引用: 1]     

[陈多福, 陈先沛, 陈光谦.

冷泉流体沉积碳酸盐岩的地质地球化学特征

[J]. 沉积学报, 2002, 20(1): 34-40.]

Magsci      [本文引用: 1]      摘要

冷泉流体是指来自海底沉积界面之下的低温流体以喷涌和渗漏方式注入盆地, 并产生系列的物理和化学及生物作用, 这种作用及产物称为冷泉?它是继洋中脊以盆下源中高温流体的热泉被发现和研究之后的又一个新的盆地流体沉积领域?日前研究较多的是以水? 碳氢化合物 (天然气和石油) ? 硫化氢? 细粒沉积物为主要成分, 温度与海水相近的流体, 广泛发育于活动和被动大陆边缘斜坡海底?冷泉流体沉积体系发育高密度的化学自养生物群, 以碳酸盐岩和天然气水合物为主, 有少量的硫化物和硫酸盐等?冷泉碳酸盐岩的产状有丘? 结核? 硬底? 烟囱? 胶结物和小脉等, 以化学自养生物碎屑和多期次的自生碳酸盐胶结物组成的生物丘最为常见, 它在物质来源? 形成环境? 形成作用等方面与传统来源于海水碳的碳酸盐岩建隆不同, 用术语 C h e r m o h e r m 表示, 以区别于传统海水碳酸盐岩建隆术语b i o h e r m s ? l i t h o h e r m s ? p s e u d o b i o h e r m s 和 b i o s t r o m e s ?地层中石化的化学自养生物丘常是含有大量底栖生物化石的碳酸盐岩建隆产于深水相沉积地层中, 在沉积环境和相分析上出现纵向和横向的不连续, 甚至出现反常现象?矿物以镁方解石? 白云石和文石为主, 与传统的碳酸盐岩相似, 在地球化学组成上最大的区别是冷泉流体沉积碳酸盐岩的碳来源于冷泉体系中的细菌生物成因碳, 具有特别负的碳同位素值?冷泉在海底主要沿构造带和高渗透地层呈线性群, 或围绕泥火山或盐底劈顶部呈圆形或不规则状冷泉群分布,或以海底地形低凹处和峡谷转向处呈孤立冷泉形式产出?冷泉流体以沉积建造流体为主?上覆快速堆积? 成岩压实和胶结作用? 构造挤压和变形作用? 深部的后生作用和成岩作用? 海底沉积物中的天然气水合物分解作用是建造流体向上运移进入海底成为冷泉的驱动力?冷泉碳酸盐岩的沉积作用主要有胶结作用? 充填作用和生物化学沉积作用?冷泉流体中的碳主要是以甲烷为主的碳氢化合物形式存在, 经微生物作用转变为 C O2 ,最终形成冷泉碳酸盐岩?
[35] Demaster D J, Pope R H.

Nutrient dynamics in Amazon shelf waters: Results from AMASSEDS

[J].Continental Shelf Research, 1996, 16(3): 263-289.

DOI      URL      [本文引用: 1]      摘要

Four hydrographic cruises were conducted on the Amazon shelf as part of the AMASSEDS field program. During each cruise, approximately 55 stations were occupied and nutrients, as well as other hydrographic parameters, were measured. The results of this time series sampling program indicate that the nutrient concentrations in the riverine end-member (silicate = 144 渭mol kg , phosphate = 0.7 渭mol kg , nitrate = 16 渭mol kg , ammonium = 0.4 渭mol kg , and urea = 0.9 渭mol kg ) remain relatively constant, despite a two-fold seasonal variation in river water discharge rate. Of the major nutrients (nitrate, phosphate, ammonium and silicate), nitrate shows the greatest seasonal change in riverine end-member concentration with a high value (23 渭mol kg ) during the March cruise (rising river discharge) and a low value (12 渭mol kg ) during the November cruise (falling river discharge). Nitrate is the dominant nutrient form of inorganic nitrogen throughout most of the river/ocean mixing zone, however, in the outershelf area, where nitrate has been depleted by biological production, this nutrient occurs at concentrations comparable to the other nitrogen species (ammonium, nitrite and urea), which are at levels < 1 渭mol kg . Nearshore, high turbidity inhibits phytoplankton production because of light limitation, whereas on the outershelf, nitrate appears to be limiting growth more than silicate or phosphate. Nutrient uptake was observed during all four cruises, however, nearly all of this production must be regenerated in shelf bottom waters, because very little of the biogenic materials are buried in the seabed (silicate burial <4% of flux to algal blooms; 藴10% burial of biologically available inorganic nitrogen reaching the river/ocean mixing zone; and <3% burial of phosphate flux to shelf environment). Clearly the Amazon shelf is not an efficient nutrient trap. Initial estimates of primary production on the Amazon shelf suggest that algal blooms are sustained by regeneration to a large extent (up to 83%, 69% and 59% for N, P and Si, respectively) as well as by riverine and upwelled sources. Nutrient budget calculations have been used to establish the dominant external source of nutrients to the algal blooms occurring on the outer shelf. Based on flux core measurements, diffusive nutrient fluxes from Amazon shelf sediments are very low relative to riverine supply rates (silicate flux out = 1.3% of riverine flux, the nitrate plus ammonium flux is essentially zero, and the phosphate seabed flux shows removal of 藴2% of the riverine flux). Inventories of naturally occurring Pb were used to estimate the onshore flow of subsurface water onto the Amazon shelf. The radiochemical data indicate that the flux of water onto the shelf may be as much as five to ten times greater than the annual flow of the Amazon River. The nutrient flux from this shoreward movement of ocean water (originating at a depth of 60-100 m water depth) accounts for about 80% of the externally supplied ammonium, 52% of the externally supplied phosphate, 38% of the externally supplied nitrate, and 17% of the externally supplied silicate reaching the outer shelf, with the remainder of the nutrient fluxes coming from the river. Therefore, the outershelf algal blooms are supported to a significant extent by the shoreward flux of nutrients from offshore, subsurface waters.
[36] Ristvet B L.

Reverse Weathering Reactions Within Recent Nearshore Marine Sediments, Kaneohoe Bay, Oahu[D].

New Mexico: Kirtland Air Force Base,Test Directorate Field Command, 1978:314.

[本文引用: 2]     

[37] Wang C, Zhu H, Wang P, et al.

Early diagenetic alterations of biogenic and reactive silica in the surface sediment of the Yangtze Estuary

[J].Continental Shelf Research, 2015, 99:1-11.

DOI      URL      [本文引用: 2]      摘要

Sedimentary biogenic silica (BSi) is an important parameter for understanding biogeochemical processes in estuarine ecosystems. In this study, a two-step mild acid–mild alkaline extraction procedure was used to leach BSi and its early diagenetic products from the sediments of the Yangtze Estuary. A Si/Al correction of the mild alkaline leachable silica (Si-Alk) was applied to estimate the contents of BSi in the sediments. The BSi contents varied from 18.90 to 120.1002μmol02Si/g in the sediments, whereas mild acid leachable silica (Si-HCl) and Si-Alk levels ranged from 17.43 to 73.56 and from 19.56 to 185.6302μmol02Si/g, respectively. Furthermore, the degrees of diagenetic alteration of biogenic and reactive silica were also calculated and discussed. The diagenetic alteration ratios of biogenic and reactive silica increased seaward during May, August and November 2012, whereas an opposite trend was observed in March 2013. The diagenetic alteration of the biogenic and reactive silica was mainly controlled by the redox conditions in benthic sediments. Additionally, the deposition of fresh diatoms and authigenic products could temporarily affect the distribution of silica pools in the sediments and ultimately affect the diagenetic alteration ratios of biogenic and reactive silica. Detailed investigations are still necessary to understand the early diagenetic processes of biogenic and reactive silica in this warm temperate area.
[38] Turner R E, Rabalais N N, Alexander R B, et al.

Characterization of nutrient, organic carbon, and sediment loads and concentrations from the Mississippi River into the northern Gulf of Mexico

[J]. Estuaries and Coasts, 2007, 30(5): 773-790.

DOI      URL      摘要

We synthesize and update the science supporting the Action Plan for Reducing, Mitigating, and Controlling Hypoxia in the Northern Gulf of Mexico (Mississippi River/Gulf of Mexico Watershed Nutrient Ta
[39] Chen Y, Shi M L, Zhao Y G.The Ecological and Environmental Atlas of the Three Gorges of the Changjiang[M]. Beijing:Science Press,1989.

[40] Rude P D, Aller R C.

Early diagenetic alteration of lateritic particle coatings in Amazon continental shelf sediment

[J].Journal of Sedimentary Petrology, 1989, 59(5): 704-716.

DOI      URL      [本文引用: 1]      摘要

ABSTRACT Intense chemical weathering in the tropical Amazon River basin strips crustal material of alkali and alkaline earth metals, leaving a residue composed predominantly of oxyhydroxides of Fe, hydroxides of Al, and cation poor clays. This lateritic residue often coats soil particles. Within the marine environment, lateritic particle coatings on sand undergo, or have the capacity to undergo, rapid reaction and mineralogical alteration. Mg uptake by lateritic particle coating reactions could account for up to 67% of the Mg discharged in solution by the Amazon River. Evidence for Mg-Fe-Al layer silicate formation supports the hypothesis that ancient ironstone minerals formed in some cases by direct alteration of lateritic material. -from Authors
[41] Li J F, He Q, Xiang W H, et al.

Fluid mud transportation at water wedge in the Changjiang Estuary

[J].Science in China (Serisei B),2001, 44: 47-56.

DOI      URL      [本文引用: 1]     

[42] Bales R C.

The Global Water Cycle: Geochemistry and Environment

[M]. New Jersey: Prentice-Hall, 1989.

[本文引用: 1]     

[43] Bianchi T S, Allison M A.

Large-river delta-front estuaries as natural “recorders” of global environmental change

[J].Proceedings of the National Academy of Sciences of the United States of America, 2009, 106(20): 8 085-8 092.

DOI      URL      PMID      [本文引用: 1]      摘要

Large-river delta-front estuaries (LDE) are important interfaces between continents and the oceans for material fluxes that have a global impact on marine biogeochemistry. In this article, we propose that more emphasis should be placed on LDE in future global climate change research. We will use some of the most anthropogenically altered LDE systems in the world, the Mississippi/Atchafalaya River and the Chinese rivers that enter the Yellow Sea (e.g., Huanghe and Changjiang) as case-studies, to posit that these systems are both "drivers" and "recorders" of natural and anthropogenic environmental change. Specifically, the processes in the LDE can influence ("drive") the flux of particulate and dissolved materials from the continents to the global ocean that can have profound impact on issues such as coastal eutrophication and the development of hypoxic zones. LDE also record in their rapidly accumulating subaerial and subaqueous deltaic sediment deposits environmental changes such as continental-scale trends in climate and land-use in watersheds, frequency and magnitude of cyclonic storms, and sea-level change. The processes that control the transport and transformation of carbon in the active LDE and in the deltaic sediment deposit are also essential to our understanding of carbon sequestration and exchange with the world ocean--an important objective in global change research. U.S. efforts in global change science including the vital role of deltaic systems are emphasized in the North American Carbon Plan (www.carboncyclescience.gov).
[44] McKee B A, Aller R C, Allison M A, et al.

Transport and transformation of dissolved and particulate materials on continental margins influenced by major rivers: Benthic boundary layer and seabed processes

[J].Continental Shelf Research, 2004, 24(7): 899-926.

DOI      URL      摘要

Within the benthic boundary layer (BBL) and seabed of river-dominated ocean margins (RiOMars), the timing, kinetics and extent of important biogeochemical processes are greatly influenced by large riverine inputs of dissolved and particulate terrestrial materials. An examination of our current state of knowledge reveals that the rates of primary productivity, sediment deposition, remineralization and burial in these margins are among the highest of all marine systems. Transport and transformation processes within the benthic region of these RiOMar areas are highly variable (temporally and spatially). As a result, measurement and modeling of these processes are very challenging. A more quantitative understanding of these systems will require coordinated interdisciplinary studies that: (a) better define the quantity and composition of riverine inputs; (b) greatly improve our current knowledge of transport and transformation within the BBL of these systems; (c) focus on the sequential timing of physical forcings (riverine discharge, high energy events); (d) develop new nonclassical diagenetic models; (e) further characterize and delineate differences between sub-environments within a RiOMar and between RiOMar -渢ypes-; and, (f) provide a better mechanistic understanding of what controls the net retention of terrestrial materials (diagenetic transformation vs. burial) within RiOMar systems.
[45] Zhao Bin, Yao Peng, Yu Zhigang.

The effect of organic carbon-iron oxide association on the preservation of sedimentary organic carbon in marine environments

[J].Advances in Earth Science, 2016, 31(11):1 151-1 158.

[本文引用: 1]     

[赵彬, 姚鹏, 于志刚.

有机碳—氧化铁结合对海洋环境中沉积有机碳保存的影响

[J].地球科学进展, 2016, 31(11):1 151-1 158.]

DOI      URL      [本文引用: 1]      摘要

有机碳在海洋环境中的长期保存机制一直是海洋碳循环研究的重点,也是研究气候变化与全球碳循环之间作用和反馈的关键.据估算,表层海洋沉积物中约20%的有机碳是通过与氧化铁的结合而保存下来的,因此与氧化铁结合是有机碳长期保存的关键因素之一.研究表明,有机碳—氧化铁复合物的形成主要通过吸附和共沉淀这2种机制,共沉淀反应是有机碳与氧化铁在海洋环境中结合的主导机制.不同来源的有机物在发生与铁氧化物的共沉淀或吸附作用时是有选择性的,在大部分海洋环境中铁氧化物优先与海洋有机碳结合,但在河口三角洲区域,铁氧化物优先与陆源有机碳结合.大量的陆源输入,较高的初级生产和频繁的再悬浮活动使河口边缘海特别适于开展有机碳—氧化铁结合的相关研究,这也是今后研究的重点方向.
[46] Zhou M J, Shen Z L, Yu R C.

Responses of a coastal phytoplankton community to increased nutrient input from the Changjiang (Yangtze) River

[J].Continental Shelf Research, 2008, 28(12):1 483-1 489.

DOI      URL      [本文引用: 3]      摘要

Nutrient input from the Changjiang River (Yangtze River) has been increasing dramatically since the 1960s. At the mouth of the Changjiang River, the nitrate concentration has increased about three-fold in 40 years, from 20.5 μmol/L in the 1960s to 59.1 μmol/L in the 1980s and to 80.6 μmol/L in 1990–2004. Phosphate concentration increased by a factor of 30%, from 0.59 μmol/L in the 1980s to 0.77 μmol/L in 1990–2004. The increasing nitrate input has arisen mostly from the mid and lower reaches of the Changjiang River, where the river meets one of the most strongly developed agriculture areas in China. Responses of the coastal phytoplankton community to the increasing nutrient inputs are also seen in the available monitoring data. First, a trend of increasing phytoplankton standing stock from 1984 to 2002 appeared in the Changjiang River estuary and adjacent coastal waters, especially in late spring. Secondly, the proportion of diatoms in the whole phytoplankton community showed a decreasing trend from about 85% in 1984 to about 60% in 2000. Finally, red tides/harmful algal blooms increased dramatically in this area in terms of both number and scale. About 30–80 red tide events were recorded each year from 2000 to 2005 in the East China Sea. The scale of some blooms has been in excess of 10,000 km 2.
[47] Liu J P, Li A C, Xu K H, et al.

Sedimentary features of the Yangtze River-derived along-shelf clinoform deposit in the East China Sea

[J].Continental Shelf Research, 2006, 26(17/18): 2 141-2 156.

DOI      URL      [本文引用: 1]      摘要

A predominant sigmoidal clinoform deposit extends from the Yangtze River mouth southwards 800 km along the Chinese coast. This clinoform is thickest (鈭40 m) between the 20 and 30 m isobaths and progressively thins offshore, reaching water depths of 60 and 90 m and distances up to 100 km offshore. Clay mineral, heavy metal, geochemical and grain-size analyses indicate that the Yangtze River is the primary source for this longshore-transported clinoform deposit. 210Pb chronologies show the highest accumulation rates (>3 cm/yr) occur immediately adjacent to the Yangtze subaqueous delta (north of 30 掳N), decreasing southward alongshore and eastward offshore. The interaction of strong tides, waves, the China Coastal Current, winter storms, and offshore upwelling appear to have played important roles in trapping most Yangtze-derived sediment on the inner shelf and transporting it to the south.
[48] Zhang Guijia, Li Congxian.

Formation and distribution of green grains in the Yangtse River

[J].Oil and Gas Geology,1989,10(2):145-153.

[本文引用: 1]     

[张桂甲,李丛先.

长江口地区自生绿色颗粒的形成和分布

[J].石油与天然气地质,1989,10(2):145-153.]

[本文引用: 1]     

[49] Deng B, Zhang J, Wu Y.

Recent sediment accumulation and carbon burial in the East China Sea

[J].Global Biogeochemical Cycles, 2006, 20(3): 466-480.

DOI      URL      [本文引用: 1]      摘要

[1] Sediment and carbon budgets were constructed for the East China Sea (ECS) Shelf based on up-to-date data. The total annual sediment flux in the ECS Shelf is approximately 96% of the terrestrial input. There is high retention of sediment on the ECS Shelf owing to the broad nature of the shelf edge (i.e., 500090009600 km) and because of an along-shore sediment dispersal path driven by the East China Sea Coastal Current (ECSCC) and the Taiwan Warm Current (TWC). Organic carbon (OC) burial was also observed, based on the results for sediment accumulation and the OC proportion in surface sediment. A total of 7.4 0103 106 t of OC is preserved in shelf sediments. Source discrimination of sedimentary OC revealed that the percentage of OC burial for both terrigenous and marine OC sources was higher than the global mean value, at 10% and 5.5%, respectively, presumably owing to high sediment accumulation. High OC flux to sediment in the estuary and shelf break suggests that riverine discharge and upwelling of the Kuroshio intrusion are key factors regulating OC burial over the shelf. Estimated using a mass balance model, 1509000920% of the carbon inventory is buried in the shelf sediment, while &gt;80% of the carbon inventory must be transported out of shelf area in the form of dissolved carbon (organic and inorganic). The accumulation of carbon in sediments and the outflow of dissolved carbon sustain a high carbon sink in the ECS.
[50] Li D J, Zhang J, Huang D J, et al.

Oxygen depletion off the Changjiang (Yangtze River) Estuary

[J]. Science in China (Series D), 2002, 45(12): 1 137-1 146.

DOI      URL      [本文引用: 1]     

[51] Zhu J R, Zhu Z, Lin J, et al.

Distribution of hypoxia and pycnocline off the Changjiang Estuary, China

[J]. Journal of Marine Systems, 2015, 154:28-40.

DOI      URL      摘要

The distributions of hypoxia and the pycnocline off the Changjiang Estuary were investigated by making several field observations from June 2 to 11, from July 18 to 23, from August 20 to 30, from October 3 to 13, 2006, and from August 27 to September 3, 2009. The observations from July 18 to 23, 2006, mainly focused on analyzing the relationship between hypoxia and the extension of the river plume and vertical stratification. In July, the Changjiang diluted water (CDW) was influenced by the easterly typhoon winds, causing it to extend northward rather than northeastward. By using the maximum vertical density gradient as a stratification intensity index, we found that the area of low (022.002kg/m 4 ), which indicated that the summer pycnocline can effectively block vertical DO exchange and maintain hypoxia near the bottom. The observed hypoxic area was 50002km 2 , which was much smaller than the hypoxic areas observed in previous studies, and occurred because of the enhanced mixing that resulted from Typhoon Bill. During the observation period of August 20–30, 2006, the maximum density gradient was weaker due to distinct low river discharge. No hypoxia was observed in the eastern and southeastern sea off the Changjiang Estuary where hypoxia often occurs. However, hypoxia occurred over a large area of 15,40002km 2 in the northern observation domain where hypoxia rarely occurs. During June 2–11 and October 3–13, 2006, the maximum density gradient was weaker, and the area with low DO was smaller than in July 2006. This finding resulted from relatively low river discharge and weaker solar heating. Consequently, no hypoxia occurred in the bottom layer. The area of low DO was similar to that of the maximum vertical density gradient. From August 27 to September 3, 2009, high river discharge and strong solar heating produced a larger and more intense pycnocline. The hypoxic area reached 373502km 2 and was very similar to the area of the pycnocline, which was greater than 3.002kg/m 4 . The seasonal variations of the pycnocline were consistent with those of hypoxia, and the pycnocline played an important role in preserving hypoxic conditions. The seasonal influences of biogeochemical process on hypoxia in 2006 were discussed. The residual current speeds at the bottom were small and favorable for maintaining hypoxia during the summer.
[52] Wang X, Ma H, Li R, et al.

Seasonal fluxes and source variation of organic carbon transported by two major Chinese Rivers: The Yellow River and Changjiang (Yangtze) River

[J]. Global Biogeochemical Cycles, 2012, 26(2):2 025.

DOI      URL      [本文引用: 1]      摘要

[1] A one-year study was carried out to investigate the seasonal fluxes and source variation of organic carbon transported by two major Chinese rivers, the Yellow River and Changjiang. In 2009, the Yellow River and Changjiang transported 3.20 0103 1010g and 1.58 0103 1012 g DOC and 3.89 0103 1011g and 1.52 0103 1012 g POC, respectively. The dominant input of the terrestrial organic matter occurred during the high discharge period from June to July for the Yellow River and from June to August for Changjiang, accounting for 3609000944% of the DOC and 7209000986% of the POC transported by the two rivers in 2009. The Yellow River transported much higher concentrations of inorganic carbon than organic carbon, while a reverse trend was found in the Changjiang, indicating the different sources of carbon discharged by the two rivers. Using radiocarbon and stable carbon isotope measurements, we identified the different sources and seasonal variations of organic carbon transported by the Yellow River and Changjiang. The Yellow River carried old POC with radiocarbon ages ranging from 4000 to 8000 years, while POC transported by Changjiang had a relatively younger 14C age ranging from 800 to 1060 years. The 14C ages of DOC were relatively younger (3050900091570 years) and showed less variation between the two rivers. The seasonal variations found in 14C ages of DOC and POC indicate that a large fraction of recent-fixed labile organic carbon was transported by the two rivers in the spring and summer months. The different sources and seasonal variations in both fluxes and sources of organic carbon transported by the Yellow River and Changjiang could have an important influence on the biogeochemical cycle and ecosystems in the estuaries and adjacent coastal waters of the East China Sea.

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