控制北太平洋深水中 Pb、Nd 同位素演化的不同因素

近年研究表明，大洋中溶解的 Pb和 Nd 以陆源来源占主导。但对 Pb和Nd 进入大洋的途径存在很大争议。笔者研究了3块中北太平洋铁锰结壳（CJ01，CLD01，CB12）的元素含量和 Pb、Nd 同位素组成。根据 Co 含量经验公式法定年，结合几块结壳的剖面 Pb 同位素演化曲线与 Os 同位素演化曲线，确定所研究的中北太平洋铁锰结壳的底部年龄约为 75Ma。3块结壳不论磷酸盐化与否，其 Pi、Nd 同位素随时间的演变曲线均十分相似，且 Pb 同位素演化趋势与北太平洋岩心（LL44－GPC3）中的风沙的 Pb 同位素演化趋势相似。这些结壳的 Nd 同位素演化趋势也相似，但与岩心 LL44－GPC3 中风沙的 Nd 同位素的演化曲线完全不同。由此得到以下结论:(1)通过研究2块结壳，首次提出太平洋铁锰结壳的年龄超过70Ma，得到了白垩纪末及整个新生代中北太平洋深水 Pb、Nd 同位素的演化。并且揭示磷酸盐化不会明显改变结壳中的 Pb、Nd 同位素组成。（2）风沙是中太平洋深水溶解 Pb 的主要来源。太平洋中的 Pb 由来自大陆风沙富放射成因 Pb 和来自火山弧非放射性成因 Pb 之混合，二者的量随时间变化。60Ma 之前，北美大陆粉尘是太平洋 Pb 的主要来源，而从40 Ma 开始，亚洲大陆粉尘对 Pb 总量的贡献日益重要。在约55 Ma 期间是大陆粉尘对海水 Pb 贡献最小的时期，与温暖气候相吻合。（3）风成粉尘对中北太平洋深水中的 Nd 的贡献可以忽略。新生代太平洋边缘火山岩风化侵蚀作用加强，是中北太平洋ENd值升高的主要原因。     

海洋Nd同位素演化及古洋流循环示踪研究

海洋Nd同位素演化已经成为示踪陆源风化输入和洋流循环改变的最重要的手段之一,得到了越来越多的应用,并取得了许多重要的成果。海水的Nd同位素组成主要受陆源输入物质控制,热液输入几乎可以忽略。由于Nd在海洋中的停留时间(约500～1000a)略小于海水的平均混合时间(约1500a),且各洋盆有不同的Nd同位素风化输入,因此现代各大洋海水具有不同的Nd同位素组成。在陆源输入稳定的情况下,可以利用海水的Nd同位素组成和演化来示踪水体的混合或洋流循环的改变。目前主要依靠对海洋中水成铁锰结壳、海洋钙质有孔虫壳体、磷酸质鱼骨头或鱼牙齿化石以及沉积物中铁锰氧化物组分等的研究来恢复和反演古海水的Nd同位素组成和演化。4种分析材料各有其优缺点。其中,通过对水成铁锰结壳的Nd同位素分析,基本建立了各大洋新生代以来的主要洋流的Nd同位素组成的长尺度演化。通过有孔虫壳体、鱼化石碎片和沉积物中Fe-Mn氧化物组分可以进行高时间分辨率的古海水Nd同位素演化示踪。利用海水Nd同位素演化可以示踪古洋流通道的开启或闭合,以及获得水体交换的直接信息,为研究构造运动与气候变化之间的关系提供指示。同时,将海水Nd同位素演化与气候变化的指标结合起来,可以用于示踪各种气候条件下洋流循环的改变,将洋流循环的改变与气候变化联系起来,研究两者之间的成因关系。对表层水体的Nd同位素组成的研究则可以示踪不同气候条件下大陆陆源风化输入的改变。     

北半球大冰期(约2.73 Ma)前后北太平洋风尘沉积突变

距今约2.73 Ma,北半球高纬地区冰盖急剧发展,北半球大冰期来临,成为最引人注目的事件。北半球大冰期成因已有诸多解释,其中之一是大陆干旱化加剧,输入到大洋的粉尘增多引起海洋铁肥效应增强和生物量增多,吸收了更多大气CO2,使得地球变冷和冰盖增加。作为全球第二大粉尘释放中心,亚洲内陆干旱区释放的粉尘是北太平洋沉积物中主要陆源组分之一。开展北半球大冰期前后西北太平洋沉积物记录的亚洲粉尘研究,有助于深入认识风尘铁肥效应对北半球大冰期形成的可能贡献。文章依据大洋钻探计划(Ocean Drilling Program,简称ODP)198航次西北太平洋1208钻孔(共钻取沉积物392.3 m;本研究深度121.3 m至130.1 m,时间段为2.62 Ma至2.85 Ma)北半球大冰期前后的高分辨率(约2500年)样品,提取了沉积物中的"风尘组分",计算了风尘通量,研究了风尘通量变化和海洋生产力之间的关联。研究结果显示,约2.73 Ma以来,1208钻孔风尘通量快速增加,已发表的该孔的海洋生产力也表现出快速增加,海水表面温度也快速降低,说明粉尘对海洋的铁肥效应可能是触发北半球大冰期形成的重要因素。文章还测试了"风尘组分"的Nd和Sr同位素,研究了粉尘物源变动。结果显示,塔克拉玛干沙漠是北半球大冰期前后1208钻孔粉尘的主要物源,其中2.73 Ma至2.85 Ma期间Nd和Sr同位素波动较大,推测与火山灰含量较多和戈壁粉尘沉积有关,位置偏北的西风可能是部分戈壁粉尘长距离运输至北太平洋的主要营力。2.73 Ma以来,北极冰盖大量发育,西风位置南移,主要运输塔克拉玛干沙漠粉尘至北太平洋,使得Nd和Sr同位素波动较小,但其中2.72 Ma至2.70 Ma期间出现的Nd同位素偏正、Sr同位素变小很可能是火山灰的突然大量沉积造成的。     

新生代古海洋Nd同位素演化及其古环境意义

本文对当前在新生代古海洋Nd同位素演化及其古环境意义研究方面的最新成果进行了简明的阐述，说明在巴拿马海峡于5－3Ma关闭前后，太平洋和大西洋洋流的变化与其海水Nd同位素的变化相对应。但同期的印度洋Nd同位素没有明显变化，其原因需要进一步研究。     

东南沿海地区古近纪大陆岩石圈地幔特征及成因

东南沿海地区新生代玄武岩中的橄榄岩包体来自岩石圈地幔 ,上地幔橄榄岩包体的岩石学及地球化学特征都记录了地幔演化的历史。普宁橄榄岩包体斜方辉石含量与太古宙克拉通地幔类似 ,但在矿物学、REE、痕量元素和Sr Nd同位素上又与太古宙岩石圈地幔不同。橄榄岩包体的岩相学、矿物学、REE、痕量元素特征都提供了含H2 O富Si流体交代橄榄岩的证据 ,这种流体可能主要是洋壳物质局部熔融而成。流体交代使橄榄岩富Si,同时富Sr、Pb和强不相容元素等大洋岩石圈物质。这表明普宁大陆岩石圈地幔既保留太古宙岩石圈地幔的特征 ,又具有大洋俯冲地幔的特征 ,它是古老岩石圈地幔向大洋岩石圈地幔转换的一部分 ,这种转换可能是大洋岩石圈与大陆岩石圈地幔相互作用的结果。     

福建明溪石榴石二辉橄榄岩包体的REE 及Pb Sr Nd同位素研究

本文研究了明溪地区尖晶石二辉橄榄岩、尖晶石-石榴石二辉橄榄岩和金云母-石榴石二辉橄榄岩包体的REE及Pb,Sr,Nd同位素。它们的Pb,Nd同位素成分表明该区上地幔在67—82km深度上是,MORB型亏损地幔。标本中放射性Sr同位素成分高于“地幔系列”可能解释为岛弧区俯冲大洋板块物质的加入。包体的sm-Nd、Rb-Sr年龄可能与十亿年前地幔亏损事件、早古生代H_2O,K_2O等地幔交代作用以及新生代的火山作用过程有关。     

西太平洋海底海山富钴结壳惰性气体同位素组成及其来源

采用高真空气体质谱系统测定了西太平洋麦哲伦海山富钴结壳不同层圈及其基岩的惰性气体丰度和同位素组成,结果显示:(1)西太平洋富钴结壳主要是水成成因,其中惰性气体来源不同,He 绝大多数来自宇宙尘(IDPs),少量来自陆源风成微粒;Ar 主要来自海水溶解的大气,少量来自陆源风成微粒或沉积岩建造水;Ne 和 Xe 主要来自海水中溶解大气, 少量来自宇宙尘;(2)在具三层结构的结壳中,亮煤层(致密层)的惰性气体同位素相对外层和疏松层有较大的不同,显示大洋磷酸岩化对早期沉积的结壳惰性气体组成有较大的影响,如导致~4He 的升高和~3He/~4He 的显著降低;(3)太平洋富钴结壳玄武岩基岩的~3He/~4He 非常低,为0.0095～0.074Ra,与本区磷块岩基岩(0.087Ra)相似,而远低于正常海底玄武岩的~3He/~4He 比值,显示这些基岩曾与富含放射性成因~4He 和 P 的上升洋流或沉积物中建造水发生过水/岩反应,这个过程将释放出较多的成矿元素,有利于富钴结壳的形成,海底海山玄武岩中较低的 He 同位素组成可作为富钴结壳的找矿标志之一。     

五大连池钾质火山岩的Sr、Nd、Pb同位素地球化学及岩浆的化学演化

五大连池火山岩是我国东部新生代最典型的钾质玄武岩。以富Ti、Na、K为特点，结晶分异使岩浆向富Si、富碱方向演化。岩石中Rb、Sr、Sin、Nd丰度与熔岩的碱质同步增长。Pb、Sr、Nd同位素组成很特殊，富放射成因Sr和Nd，但贫放射成因Pb，^37Sr/^34Sr，高于全球未分异现代值,^143Nd/^144Nd为0．512381-0.512433，低于全球未分异现代值；^206Pb/^204Pb,^207Pb/^204Pb,^208Pb/^204Pb分别对16.712-16.992,115,371-15.407,36.315-36.948,比许多大洋玄武岩和大陆玄武岩偏低。上述数据表明，其源区为无明显地壳物质混染的，未遭改造的原始富集地幔，同大洋玄武岩明显不同，暗示地幔的物质组成有区域性和不均匀性。     

亚洲大陆边缘“源-汇”过程研究:沉积纪录与控制机理

青藏高原的隆起和西太平洋边缘海的形成是亚洲中新生代地质发展史上的重大事件,它们构成地球上一对独特的构造格局。而亚洲大陆边缘是全球独特的复合型大陆边缘,位于欧亚、太平洋和印度-澳大利亚三大板块的汇聚、碰撞边界,西部的青藏高原经历了强烈隆起,东部的西太平洋边缘汇集了全球75%的边缘海。亚洲大陆边缘北起北冰洋的拉普捷夫海、东西伯利亚海、楚科奇海,东部包括太平洋的白令海、鄂霍次克海、日本海、东海(及渤、黄海)和南海,西南部涵盖印度洋的安达曼海、孟加拉湾和阿拉伯海。近10年来,我们基于广泛的国际合作对上述海区进行了初步的沉积地质学调查研究,形成了亚洲大陆边缘"源-汇"过程国际合作研究计划。青藏高原的隆升营造了世界上最大的地球表层"源-汇"体系,大量的陆源物质从亚洲大陆输送到边缘海,进而进入太平洋和印度洋,不仅仅在大陆边缘形成了重要的沉积体系,蕴育大量油气和矿产资源,也显著影响全球海洋物质组成。亚洲大陆边缘具有宽广陆架和边缘海系统,世界性的大陆河流和山地河流并存,气候梯度系统独特,陆海相互作用强烈。因青藏高原的存在,西伯利亚高压、西风急流、亚洲季风等与西太平洋暖池和边界流的相互作用变得异常复杂,控制了亚洲大陆边缘的气候变化,降水、干旱及灾害频率都受其影响。同时,亚洲大陆边缘发育有强大的西部边界流,将海洋中的热量和水汽通过大气传向陆地、从低纬输送到高纬,对亚洲东部的气候、降水和生态环境产生影响,最终影响到陆源物质向海的输运。亚洲大陆边缘区域内以河流为杻带的源-汇系统贡献了全球约2/3的入海物质,这些巨量入海物质对边缘海和全球大洋沉积作用、生物地球化学过程和海洋生态环境等都产生了巨大影响。特别是边缘海作为陆源物质的主要沉积汇,在不同海区发育发育了巨大的浅水三角洲、宽阔陆架沉积体和深水扇沉积体系。它们不仅直接记录了陆源物质入海的源-汇系统过程,也是研究新生代亚洲大陆构造隆升、风化剥蚀、季风演化与大河发育历史的理想载体。本研究计划下一步将选择亚洲大陆边缘的典型地区,通过广泛深入的国际合作,研究亚洲大陆边缘层序地层及沉积体系、大型河流和山地河流对海洋沉积作用的贡献与影响,阐明"源-汇"扩散系统的发育过程及机制,系统对比研究亚洲若干大河与山地河流入海物质的源-汇过程。通过边缘海及其邻近大洋的沉积记录,旨在揭示:1)构造尺度上的新生代亚洲地质形变造成的水系调整和大陆边缘沉积充填历史。2)第四纪冰期旋回的海陆相互作用和源汇过程,及其对海洋环境变化的沉积响应。3)近现代自然变化和人类活动双重因素驱动下的陆源物质源-汇过程与沉积地层形成机制。4)亚洲大陆边缘源-汇系统演化在全球变化研究中的特色与启示。     

太平洋多金属结核和富钴结壳稀土元素地球化学对比及其地质意义

多金属结核和富钴结壳是大洋两类典型的铁锰产物。为探讨不同海区多金属结核和富钴结壳之间稀土元素特点及其揭示的地质意义,利用近年中国在太平洋获取的样品进行对比,采用ICP-AES对稀土元素测试。结果表明,结壳具有正Ce异常明显、LREE富集、∑REE高的特点,而结核表现为HREE相对富集、∑REE相对较低,因成因类型不同,Ce异常或表现为正异常、负异常或异常不明显。结核形成后受到成岩作用的影响,而结壳则为水成作用形成;结核和结壳中REE的存在形式比较复杂,不同海区各不相同,中太平洋东部产出的结壳和位于东太平洋的结核中REE可能主要赋存于铁矿物相,而西太平洋结壳REE可能主要赋存于锰矿物相;结核和结壳REE可能分别来自海水和海山蚀变玄武岩,热液作用影响有限。     

黄土高原黄土和太平洋沉积物 Nd，Sr 同位素变化的比较

东亚季风环流引起的风尘物质的搬运和堆积，形成了我国的黄土高原。最近几年发表了一些对太平洋沉积物 Nd和 Sr同位素的研究结果(Asahara,1999；Asahara 等，1995；Pettke 等，2000)。由于亚洲大陆是太平洋沉积物中风尘物质的主要来源之一，所以将黄土高原研究结果和太平洋沉积物的研究结果相比较，可以得出一些有益的结论。探讨黄土的源区，采用全岩样品进行 Sr 同位素研究不适合。对黄土样品进行了一系列酸淋洗实验（盛雪芬等，2000；Yang 等，200结果证明，选用弱醋酸淋洗，可以有效地去除黄土和古土壤中的方解石，而对白云石、粘土矿物和长石等结构的破坏程度可以忽略。本次研究的灵台剖面位于黄土土高原中部甘肃省平凉地区灵台县以南约13 km 的五星塬任家坡村，它是迄今为止在黄土高原发现的厚度最大的记录最完整的风尘堆积序列之一，其最早时代可达7.8 Ma B P。灵台剖面古土壤酸不溶物的87Sr/86Sr一般高于黄土的87Sr/86Sr。此次测试的黄土、古土壤和红粘土样品分粒级实验（杨杰东等，2005）显示，小于2μm的细颗粒部分具有最高的87Sr/86Sr，而其他颗粒部分的87Sr/86Sr均较低。因此，黄土高原剖面的87Sr/86Sr与小于2μm颗粒部分的比例，或与粘土矿物的含量有关，因为在小于m的细颗粒部分中主要是粘土矿物（图。     

8Ma以来黄土高原风尘堆积的物源变化与上地壳演化的关系

第三纪的红粘土和第四纪黄土同为风成沉积,二者是否有相同的物质来源?长尺度风尘的加积与上地壳演化之间有怎样的联系?二者均是非常重要的科学问题.由于Sr, Nd同位素可以有效示踪沉积岩的物质来源,我们近年研究了8Ma以来黄土高原泾川剖面红粘土-黄土序列《20靘的细粒硅酸盐组分的Sr, Nd同位素变化.结果表明:1)黄土高原的黄土与北太平洋中部的硅酸盐组分的Nd同位素组成非常接近,二者应在一定程度上具有相似的物质来源,即来自蒙古国南部及中国境内的戈壁、沙漠地区,所不同的是前者由近地面风搬运,而后者为远距离输送的风尘;2)Sr同位素在8.00～2.58Ma期间呈现略为增加的趋势,应当与红粘土的来源物质经受了较长时间的化学风化有关,而Sr同位素自2.58Ma以来的显著降低趋势与第四纪时期黄土-古土壤的物质来源和第三纪红粘土不同有关,新构造运动使更多相对年轻的造山带褶皱成山,第四纪冰期来临使更多高海拔的年轻造山带遭受剥蚀而成为黄土的来源物质,这是导致黄土、红粘土物源不同的重要原因.     

New constraints on the sources and behavior of neodymium and hafnium in seawater from Pacific Ocean ferromanganese crusts

The behavior of dissolved Hf in the marine environment is not well understood due to the lack of direct seawater measurements of Hf isotopes and the limited number of Hf isotope time-series obtained from ferromanganese crusts. In order to place better constraints on input sources and develop further applications, a combined Nd-Hf isotope time-series study of five Pacific ferromanganese crusts was carried out. The samples cover the past 38 Myr and their locations range from sites at the margin of the ocean to remote areas, sites from previously unstudied North and South Pacific areas, and water depths corresponding to deep and bottom waters.For most of the samples a broad coupling of Nd and Hf isotopes is observed. In the Equatorial Pacific ε_Nd and ε_Hf both decrease with water depth. Similarly, ε_Nd and ε_Hf both increase from the South to the North Pacific. These data indicate that the Hf isotopic composition is, in general terms, a suitable tracer for ocean circulation, since inflow and progressive admixture of bottom water is clearly identifiable.The time-series data indicate that inputs and outputs have been balanced throughout much of the late Cenozoic. A simple box model can constrain the relative importance of potential input sources to the North Pacific. Assuming steady state, the model implies significant contributions of radiogenic Nd and Hf from young circum-Pacific arcs and a subordinate role of dust inputs from the Asian continent for the dissolved Nd and Hf budget of the North Pacific.Some changes in ocean circulation that are clearly recognizable in Nd isotopes do not appear to be reflected by Hf isotopic compositions. At two locations within the Pacific Ocean a decoupling of Nd and Hf isotopes is found, indicating limited potential for Hf isotopes as a stand-alone oceanographic tracer and providing evidence of additional local processes that govern the Hf isotopic composition of deep water masses. In the case of the Southwest Pacific there is evidence that decoupling may have been the result of changes in weathering style related to the buildup of Antarctic glaciation.     

Long-term records of erosional change from marine ferromanganese crusts

Ferromanganese crusts from the Atlantic, Indian and Pacific Oceans record the Nd and Pb isotope compositions of the water masses from which they form as hydrogenous precipitates. The¹⁰Be/⁹Be-calibrated time series for crusts are compared to estimates based on Co-contents, from which the equatorial Pacific crusts studied are inferred to have recorded ca. 60 Ma of Pacific deep water history. Time series of ɛNd show that the oceans have maintained a strong provinciality in Nd isotopic composition, determined by terrigenous inputs, over periods of up to 60 Ma. Superimposed on the distinct basin-specific signatures are variations in Nd and Pb isotope time series which have been particularly marked over the last 5 Ma. It is shown that changes in erosional inputs, particularly associated with Himalayan uplift and the northern hemisphere glaciation have influenced Indian and Atlantic Ocean deep water isotopic compositions respectively. There is no evidence so far for an imprint of the final closure of the Panama Isthmus on the Pb and Nd isotopic composition in either Atlantic or Pacific deep water masses.     

Pb, Sr AND Nd-ISOTOPIC COMPOSITIONS OF PALEO AND NEO-TETHYAN OCEANIC CRUSTS IN THE EASTERN TETHYAN DOMAIN: IMPLICATION FOR THE INDIAN OCEAN-TYPE ISOTOPIC SIGNATURE

Pb, Sr AND Nd-ISOTOPIC COMPOSITIONS OF PALEO AND NEO-TETHYAN OCEANIC CRUSTS IN THE EASTERN TETHYAN DOMAIN: IMPLICATION FOR THE INDIAN OCEAN-TYPE ISOTOPIC SIGNATURE     

60 Myr records of major elements and Pb–Nd isotopes from hydrogenous ferromanganese crusts: reconstruction of seawater paleochemistry

We compare the time series of major element geochemical and Pb- and Nd-isotopic composition obtained for seven hydrogenous ferromanganese crusts from the Atlantic, Indian, and Pacific Oceans which cover the last 60 Myr.Average crust growth rates and age–depth relationships were determined directly for the last about 10 Myr using ¹⁰Be/⁹Be profiles. In the absence of other information these were extrapolated to the base of the crusts assuming constant growth rates and constant initial ¹⁰Be/⁹Be ratios due to the lack of additional information. Co contents have also been used previously to estimate growth rates in Co-rich Pacific and Atlantic seamount crusts (Puteanus and Halbach, 1988). A comparison of ¹⁰Be/⁹Be- and Co-based dating of three Co-rich crusts supports the validity of this approach and confirms the earlier chronologies derived from extrapolated ¹⁰Be/⁹Be-based growth rates back to 60 Ma. Our data show that the flux of Co into Co-poor crusts has been considerably lower. The relationship between growth rate and Co content for the Co-poor crusts developed from these data is in good agreement with a previous study of a wider range of marine deposits (Manheim, 1986). The results suggest that the Co content provides detailed information on the growth history of ferromanganese crusts, particularly prior to 10–12 Ma where the ¹⁰Be-based method is not applicable.The distributions of Pb and Nd isotopes in the deep oceans over the last 60 Myr are expected to be controlled by two main factors: (a) variations of oceanic mixing patterns and flow paths of water masses with distinct isotopic signatures related to major paleogeographic changes and (b) variability of supply rates or provenance of detrital material delivered to the ocean, linked to climate change (glaciations) or major tectonic uplift. The major element profiles of crusts in this study show neither systematic features which are common to crusts with similar isotope records nor do they generally show coherent relationships to the isotope records within a single crust. Consequently, any interpretation of time series of major element concentrations of a single crust in terms of paleoceanographic variations must be considered with caution. This is because local processes appear to have dominated over more basin-wide paleoceanographic effects. In this study Co is the only element which shows a relationship to Pb and Nd isotopes in Pacific crusts. A possible link to changes of Pacific deep water properties associated with an enhanced northward advection of Antarctic bottom water from about 14 Ma is consistent with the Pb but not with the Nd isotopic results. The self-consistent profiles of the Pb and Nd isotopes suggest that postdepositional diagenetic processes in hydrogenous crusts, including phosphatization events, have been insignificant for particle reactive elements such as Pb, Be, and Nd. Isotope time series of Pb and Nd show no systematic relationships with major element contents of the crusts, which supports their use as tracers of paleo-seawater isotopic composition.     

Hafnium isotopes in Arctic Ocean water

The first isotopic compositions of dissolved hafnium in seawater from across the Arctic Ocean are reported. Most samples from the four sub-basins of the Arctic Ocean have values within error of an average of ε_Hf = +0.8. Combined Hf-Nd isotope compositions do not fall on the well-established positive correlation for mantle and crustal rocks. Instead, Arctic waters have Hf that is more radiogenic than that typically found in rocks with similar Nd isotope compositions, a feature previously found in ferromanganese crusts and waters from the Pacific Ocean. Arctic seawater samples generally fall on the lower part of the ferromanganese crust array, reflecting influences of inputs from Arctic rivers and interactions of shelf waters with underlying sediments. Arctic rivers have much higher Hf concentrations (7-30 pM) than Arctic seawater (0.36-4.2 pM). Water from the Mackenzie River has the least radiogenic Hf, with ε_Hf = −7.1 ± 1.7, and plots furthest away from the ferromanganese crust array, while waters from the Ob, Yenisey, and Lena Rivers have values that are indistinguishable from most Arctic waters. In the Amundsen, Makarov, and Canada basins, Hf concentrations are highest at the surface and lowest in the deeper waters, reflecting the influences of riverine inputs and of waters that have flowed over the extensive Siberian continental shelves and have Nd and Hf characteristics that reflect water-sediment interactions. This is in contrast to the relatively low near surface Hf concentrations reported for locations elsewhere. The Pacific water layer in the Canada Basin exhibits the highest value of ε_Hf = +6.8 ± 1.8, reflecting the Hf isotopic composition of waters entering the Arctic from the Pacific Ocean. Mixing relationships indicate that a substantial fraction of the Hf in the Mackenzie River is lost during estuarine mixing; the behaviour of Hf from other rivers is less constrained.     

The hafnium isotope composition of Pacific Ocean water

The first Hf isotope data for seawater are reported for a series of stations in the Northwestern Pacific and define a range from ε_Hf = 3.5 ± 1.4 to 8.6 ± 1.6. Most samples have values within error of the average of ε_Hf = 5.9, but significant variations are found in intermediate waters at a depth of 600 m, as well as in deep waters. The Nd and Hf isotope compositions of the deep waters fall within the range of values found for surfaces of hydrogenetic ferromanganese crusts in the region, confirming that Hf in the Fe-Mn crusts has been derived from the overlying water column, which thus provide an archive of past seawater compositions. Although the seawater samples are generally close to the global ε_Nd-ε_Hf correlation obtained from ferromanganese crusts, there are significant deviations from this correlation indicating that there is some additional decoupling between Nd and Hf isotope signals, most likely caused by local water mass mixing and differences in residence times. This is not resolved in the crust samples, which integrate seawater signals over 10⁴ years. The combined use of these two isotope systems in seawater therefore provides an additional dimension for tracing water masses in the oceans. Studies of the distribution of oceanic Hf isotope compositions that have been confined to deep water and boundary waters, as recorded in seafloor ferromanganese crusts, can now be extended and aimed at characterising the entire present-day water column. Average Hf concentrations measured in this study are somewhat lower than previously reported, suggesting a shorter residence time for Hf in the global oceans, although the uncertainty in the extent of Hf removal from the water column during estuarine mixing as well as a lack of data on hydrothermal and dust inputs remains a limit on how well the residence time can be defined.