中北太平洋铁锰结壳钕同位素演化研究

现代海洋中的水成 Fe－Mn 结壳的 Nd 来自当时周围海水，因此利用 Fe－Mn 结壳可以恢复新生海洋 Nd 同位素演化历史，进面了解古海洋环境和古气候变迁信息。海洋中 Nd 的来源包括河流或陆源 Nd、大陆边缘沉积物和风成粉尘中的可溶 Nd，以及洋中脊热液蚀变来源的 Nd。对海水、水成成因铁锰结壳和结核、洋脊热液喷发和河流输入的 Nd 同位素研究发明，陆源物质控制着大洋中溶解的 Nd。对于风尘输入对大洋中的REE的影响还存在争议。有研究表明来自大陆和火山的风尘是某些局部大洋中的 REE 的重要来源，风尘与海水间的 REE 交换引起了某些洋区中 Nd 同位素组成的变化。相反，另有学者认为风尘对北太平洋中的溶解 Nd 总量没有影响。笔者分板子一块来自中北太平洋的铁锰结壳样品（MDD53）的 Nd，Pb 同位素，得到了该区新生代以来的 Nd，Pb 同位素演化历史。通过对比该结壳和岩心 LL44－GPC3 中粉尘的同位素演变曲线，发现二者的 Pb 同位素变化规律十分相似，证明结壳中的 Pb 主要来自粉尘。与 Pb 同位素相反，二者的 Nd 同位素演化完全不同。中国黄土的ENd值远低于中太平洋深水中的ENd值。因此，笔者认为风成粉尘对太平洋深水中溶解的 Nd 总量的影响可以忽略不计。结壳的 ENd值介于大陆和岛弧火山的值之间，说明新生代太平洋海水中的 Nd 主要来自河流、大洋边缘大陆风化及大洋环流携带大源自其他大洋的 Nd，新生代 Nd 同位素比值的增长主要是国为太平洋边缘岛弧的风化剥蚀作用和火山活动的增强。     

海洋沉积物的锌同位素地球化学及其应用

锌同位素体系是海洋地球化学研究的新示踪剂,应用于示踪海水中锌元素的来源及其运移过程.海洋沉积物作为锌元素重要的"源"与/或"汇",其锌同位素组成的研究有助于理解海洋锌元素的地球化学循环.海洋沉积物记录了海水组成的信息,可以反演古海水锌同位素组成的变化,前提是理解沉积物与海水之间的分馏.对海水及海洋不同储库锌同位素研究进行系统总结,包括河流输入、热液体系、不同类型海洋沉积物(如富碳酸盐的沉积物、陆源硅酸盐碎屑、硅质沉积物、铁锰结核、贫氧-缺氧沉积物)的锌同位素组成,阐述了海洋沉积物锌同位素组成变化在古气候、古环境重建以及古海洋学等领域的应用以及重要性.      

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。     

相对相容性:富钴结壳微量元素富集规律研究的新指标

产出于海山表面的富钴结壳是水成成因铁锰氧化物、生物成因组分、碎屑组分等组成的复杂混合物~([1,2]).富钴结壳中金属的最终来源有河流和风输入的大陆物质、海底热液活动输入物质、海底玄武岩的风化产物,海底沉积物中释放的金属元素,以及地外物质~([2]),这些金属部分淋滤进入海水,在由海水进入水成成因铁锰氧化物,部分则以生物成因组分、碎屑组分进入结壳.     

Nd同位素方法应用于示踪古洋流的研究进展

大洋环流在调节全球水热分配方面起着举足轻重的作用,对全球气候变化有着重要影响。为了更好地了解未来的气候变化模式,掌握古洋流变化与气候冷暖交替耦合关系的机理成为当务之急。目前,海水Nd同位素是追踪洋流演化方式的有效指标,获得了越来越多的关注。通过从海洋环境Nd同位素的相关特性以及研究材料与方法方面来阐述Nd同位素应用于示踪古洋流研究的可行性以及最新的进展,并配合实例进行说明。     

铁同位素在现代海洋环境的示踪研究

随着海洋环境介质铁同位素测试技术的发展,特别是海水和沉积物中不同铁赋存形式的同位素组成研究备受重视,铁同位素已经展现出对各类生物地球化学过程的崭新的示踪作用。本文在不同铁价态和赋存形式之间转化的专属分馏机制框架总结基础上,汇总了现代海洋环境中大气沉降、陆源径流、沉积物、地下水和海底热液等不同来源的铁同位素特征范围,探讨了海洋内部铁循环的生物地球化学过程,包括生物吸收、颗粒态/溶解态铁的转化以及清除作用的铁同位素分馏机制,辨析海水剖面在不同层位上铁同位素组成的主导控制因素。另外,应用溯源混合模型甄别大西洋、太平洋和南大洋等多个海域铁来源,以此验证了全球气候变化与海陆多个物理化学过程的密切关系;利用不同结晶度和反应活度的矿物铁同位素数据可示踪早期成岩过程中铁还原的深度和程度,亦有助于辨析古海洋沉积物的铁同位素数据并提高古氧化还原环境的重建精度。     

锂同位素与大陆风化

气候变化与大气二氧化碳浓度息息相关.大陆岩石圈风化是影响大气二氧化碳浓度的重要过程.通过还原陆壳古风化信息,我们可以有效地了解地球气候条件的演化历史.传统方法上,前人曾使用锶同位素示踪大陆风化,但其解释尚有不足.例如,海水锶同位素比值会受到海洋热液的影响,而河流锶同位素比值则易受风化岩石类型的影响.此外,只有硅酸盐风化被认为在长时间尺度控制着大气碳汇,但锶的碳酸盐风化却与硅酸盐风化很难分辨.因此,我们需要一种更理想的同位素体系作为示踪大陆风化历史的介质.锂,作为微量元素,主要集中在岩石圈的硅酸盐矿物中,在碳酸盐岩含量较少.所以,硅酸盐风化可以使用锂同位素予以记录.同时,锂同位素受生物分馏效应影响较小,可以在海相碳酸盐岩中保存良好.这些优势为海相碳酸盐岩的锂同位素信号示踪大陆风化历史提供了有力支撑,但我们仍需对风化、迁移和结晶等过程的锂同位素地球化学行为有清晰的认识.为此,本文回顾不同储库的锂同位素组成以及各物相间锂元素配分和同位素分馏特征,总结了近年来锂同位素在重建大陆风化历史方面的进展,并详述了有待解决的关键问题.     

中太平洋富钴结壳的Os同位素组成及其物质来源意义

深海化学沉积物富钴结壳富含多种有用元素,是重要的海底矿产资源,其沉积速率缓慢(1～10 mm/Ma),几个毫米的厚度就经历了百万年的海洋历史,储存了丰富的古海洋信息,如富钴结壳生长的物质来源、古海洋物理化学条件、古气候变迁、重大的古海洋事件等.因此,富钴结壳是一种重要的古海洋记录(Hein,2000).由于海洋环境中Os同位素能够提供一些其它同位素如Pb、Nd、sr所无法给出的重要信息,在示踪物源、古海洋环境及古大陆风化等方面,具有明显的优势.因此,作者通过测定中太平洋一富钴结壳样品各壳层的锇同位素组成,来了解富钴结壳不同生长时期的Os同位素组成特征,揭示其所蕴含的物质来源信息和古大陆风化情况.     

200 ka以来澳大利亚西北岸外沉积物源区风化的Mg同位素记录及其对澳洲古季风的响应

本文通过对IODP 363航次于澳大利亚西北岸外陆架上钻取的U1483站岩芯进行沉积物粒度、镁同位素以及主量元素成分等分析,重建200 ka以来帝汶海西南部沉积物输入演化及其指示的源区风化和侵蚀历史,探讨海洋沉积物中细粒硅质碎屑组分镁同位素的古环境指示意义。U1483站陆源碎屑组分主要由黏土质粉砂组成,其δ²⁶Mg变化范围超过0.25‰。通过计算化学蚀变指数(chemical index of alteration, CIA)和两种物理侵蚀指标(包括陆源物质堆积速率和Ti/Ca比值),结果显示200 ka以来δ²⁶Mg指标与CIA具有非常一致的曲线形态。本文推测陆源碎屑组分的Mg同位素组成主要反映物源区大陆硅酸盐风化强度的变化,而受矿物学分选、岩性和早期成岩作用的影响较小。结合区域古气候记录,我们发现本研究中的风化和侵蚀记录与同一个站位已发表的澳洲夏季风降水和表层海水温度变化具有较好的耦合关系,而与赤道太平洋海平面变化的相关程度较低,反映了轨道时间尺度上沉积物所记录的物源区风化和侵蚀演化主要受控于澳洲古季风系统,表现为气候驱动型风化模式。本研...     

青藏高原的隆起与海洋锶同位素组成的演化

近年来,随着构造隆升驱动气候变化假说的提出,青藏高原的隆起受到越来越多的关注,并将之与大陆化学风化速率及海洋锶同位素的演化紧密联系。围绕青藏高原的隆升及其环境与气候效应,对海洋锶同位素组成的演化特征及其影响因素的较为全面而详细的论述表明:将青藏高原的隆升与全球气候变化、大陆化学风化速率及海洋锶同位素组成的演化相联系,也许是解决目前关于海洋锶同位素组成的演化及其物源问题的重要手段,根据海洋锶同位素的演化历史来研究全球气候变化规律及青藏高原的构造演化历史将是本研究领域的重点。     

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.     

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.     

地壳风化系统中的Sr同位素地球化学

近20年来,人们利用Rb－Sr同位素体系对地表－近地表地球化学过程、尤其是水圈－岩石圈之间化学物质的循环进行了广泛而深入的研究。大陆地壳风化物质以及地表径流的Sr同位素组成变化揭示了不同流域盆地的地质背景和风化作用的特征。古海洋的Sr同位素组成变化则是地壳和地幔演化以及不同地质历史时期壳－幔相互作用的共同结果。本文对地壳风化系统Sr同位素地球化学研究的全面而详细的综述表明,Rb－Sr同位素体系仍将是研究地壳风化、水圈－岩石圈之间化学物质循环的重要手段,根据古海水及其化学沉积物的Sr同位素记录研究壳－幔演化和地球圈层演化过程中的物质循环特征以及地表古环境变化将是本研究领域的重点。     

Evolution of neodymium isotopic signature of seawater during the Late Cretaceous: Implications for intermediate and deep circulation

Neodymium isotopic compositions (ε_Nd) have been largely used for the last fifty years as a tracer of past ocean circulation, and more intensively during the last decade to investigate ocean circulation during the Cretaceous period. Despite a growing set of data, circulation patterns still remain unclear during this period. In particular, the identification of the deep-water masses and their spatial extension within the different oceanic basins are poorly constrained. In this study we present new deep-water ε_Nd data inferred from the Nd isotope composition of fish remains and Fe–Mn oxyhydroxide coatings on foraminifera tests, along with new ε_Nd data of residual (partly detrital) fraction recovered from DSDP Sites 152 (Nicaraguan Rise), 258 (Naturaliste Plateau), 323 (Bellinghausen Abyssal Plain), and ODP Sites 690 (Maud Rise) and 700 (East Georgia Basin, South Atlantic). The presence of abundant authigenic minerals in the sediments at Sites 152 and 690 detected by XRD analyses may explain both middle rare earth element enrichments in the spectra of the residual fraction and the evolution of residual fraction ε_Nd that mirror that of the bottom waters at the two sites. The results point towards a close correspondence between the bottom water ε_Nd values of Sites 258 and 700 from the late Turonian to the Santonian. Since the deep-water Nd isotope values at these two sites are also similar to those at other proto-Indian sites, we propose the existence of a common intermediate to deep-water mass as early as the mid-Cretaceous. The water mass would have extended from the central part of the South Atlantic to the eastern part of proto-Indian ocean sites, beyond the Kerguelen Plateau. Furthermore, data from south and north of the Rio Grande Rise–Walvis Ridge complex (Sites 700 and 530) are indistinguishable from the Turonian to Campanian, suggesting a common water mass since the Turonian at least. This view is supported by a reconstruction of the Rio Grande Rise–Walvis Ridge complex during the Turonian, highlighting the likely existence of a deep breach between the Rio Grande Rise and the proto-Walvis Ridge at that time. Thus deep-water circulation may have been possible between the different austral basins as early as the Turonian, despite the presence of potential oceanic barriers. Comparison of new seawater and residue ε_Nd data on Nicaraguan Rise suggests a westward circulation of intermediate waters through the Caribbean Seaway during the Maastrichtian and Palaeocene from the North Atlantic to the Pacific. This westward circulation reduced the Pacific water influence in the Atlantic, and was likely responsible for more uniform, less radiogenic ε_Nd values in the North Atlantic after 80 Ma. Additionally, our data document an increasing trend observed in several oceanic basins during the Maastrichtian and the Palaeocene, which is more pronounced in the North Pacific. Although the origin of this increase still remains unclear, it might be explained by an increase in the contribution of radiogenic material to upper ocean waters in the northern Pacific. By sinking to depth, these waters may have redistributed to some extent more radiogenic signatures to other ocean basins through deep-water exchanges.     

Global occurrence of tellurium-rich ferromanganese crusts and a model for the enrichment of tellurium

Hydrogenetic ferromanganese oxyhydroxide crusts (Fe-Mn crusts) precipitate out of cold ambient ocean water onto hard-rock surfaces (seamounts, plateaus, ridges) at water depths of about 400 to 4000 m throughout the ocean basins. The slow-growing (mm/Ma) Fe-Mn crusts concentrate most elements above their mean concentration in the Earth’s crust. Tellurium is enriched more than any other element (up to about 50,000 times) relative to its Earth’s crustal mean of about 1 ppb, compared with 250 times for the next most enriched element.We analyzed the Te contents for a suite of 105 bulk hydrogenetic crusts and 140 individual crust layers from the global ocean. For comparison, we analyzed 10 hydrothermal stratabound Mn-oxide samples collected from a variety of tectonic environments in the Pacific. In the Fe-Mn crust samples, Te varies from 3 to 205 ppm, with mean contents for Pacific and Atlantic samples of about 50 ppm and a mean of 39 ppm for Indian crust samples. Hydrothermal Mn samples have Te contents that range from 0.06 to 1 ppm. Continental margin Fe-Mn crusts have lower Te contents than open-ocean crusts, which is the result of dilution by detrital phases and differences in growth rates of the hydrogenetic phases.Correlation coefficient matrices show that for hydrothermal deposits, Te has positive correlations with elements characteristic of detrital minerals. In contrast, Te in open-ocean Fe-Mn crusts usually correlates with elements characteristic of the MnO₂, carbonate fluorapatite, and residual biogenic phases. In continental margin crusts, Te also correlates with FeOOH associated elements. In addition, Te is negatively correlated with water depth of occurrence and positively correlated with crust thickness. Q-mode factor analyses support these relationships. However, sequential leaching results show that most of the Te is associated with FeOOH in Fe-Mn crusts and ≤10% is leached with the MnO₂.Thermodynamic calculations indicate that Te occurs predominantly as H₅TeO₆⁻ in ocean water. The speciation of Te in ocean water and charge balance considerations indicate that Te should be scavenged by FeOOH, which is in agreement with our leaching results. The thermodynamically more stable Te(IV) is less abundant by factors of 2 to 3.5 than Te(VI) in ocean water. This can be explained by preferential (not exclusive) scavenging of Te(IV) by FeOOH at the Fe-Mn crust surface and by Fe-Mn colloids in the water column. We propose a model in which the extreme enrichment of Te in Fe-Mn crusts is likely the result of an oxidation reaction on the surface of FeOOH. A similar oxidation process has been confirmed for Co, Ce, and Tl at the surface of MnO₂ in crusts, but has not been suggested previously to occur in association with FeOOH in Fe-Mn crusts. Mass-balance considerations indicate that ocean floor Fe-Mn deposits are the major sink for Te in the oceans. The concentration and redox chemistry of Te in the global ocean are likely controlled by scavenging on Fe-Mn colloids in the water column and Fe-Mn deposits on the ocean floor, as is also the case for Ce.     

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.     

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.     

Advection and removal of Pb and stable Pb isotopes in the oceans: a general circulation model study

Natural Pb-isotope variability in the oceans encodes information about the sources of continental material to the oceans, about ocean circulation, and about Pb removal. In order to use this information, we must understand the natural cycle of Pb in the oceans, which is overprinted by large anthropogenic input. In this study we use ²¹⁰Pb, which has not been significantly anthropogenically perturbed, to investigate oceanic Pb. GEOSECS ²²⁶Ra and model-derived atmospheric fluxes of ²¹⁰Pb are used to input ²¹⁰Pb into an ocean general circulation model. Irreversible scavenging of this ²¹⁰Pb onto settling biogenic particles and at the seafloor are tuned so that the model replicates the observed pattern of ²¹⁰Pb in the oceans. The best-fit model run provides a map of the variability of residence time for Pb. The global average residence time of Pb in this model is 48 yr, but there is over an order of magnitude variation between areas of high and low productivity. This is expected to enhance provinciality of Pb isotope ratios in the oceans. Because stable Pb isotopes are expected to behave in seawater in a similar fashion to ²¹⁰Pb, the pattern of removal of ²¹⁰Pb derived by the model can be used to investigate the behavior of stable Pb isotopes. We use a simplified input of Pb consisting of five point sources representing major rivers and a disseminated dust input. Although this simplified input scheme does not allow precise reconstruction of Pb concentration and isotopes in the oceans, it allows us to answer some first-order questions about the behavior of Pb as an ocean tracer. With a total Pb input of 6.3 × 10⁷ mol/yr (Chow T. J. and Patterson C. C., “The occurrence and significance of Pb isotopes in pelagic sediments,” Geochim. Cosmochim. Acta26, 263-308, 1962), the model predicts natural seawater Pb concentrations averaging 2.2 pmol/kg. Even in the absence of anthropogenic input, the model ocean exhibits a near-surface maximum in Pb concentration. And the model suggests natural Pb concentrations in the Northern Hemisphere an order of magnitude higher than in the Southern Hemisphere. A point source of Pb is suggested to dominate the seawater Pb inventory close to the source but is reduced to typically less than 10% of the inventory by the time that Pb is advected out of the originating ocean. This length scale of advection for Pb isotope signals confirms their potential as tracers of ocean circulation. Assuming an 8% dissolution of dust, their input to the open ocean are seen to be a significant portion of Pb inventory throughout the oceans and make up >50% of the Pb inventory in the model’s Southern Ocean. Finally, a preliminary investigation of the response of Pb-isotope distributions to changes in boundary conditions between glacial and interglacial times illustrates that significant variation in the Pb isotopes are expected in some regions, even for reasonably small changes in climate conditions.     

Hafnium and neodymium isotopes in surface waters of the eastern Atlantic Ocean: Implications for sources and inputs of trace metals to the ocean

We present hafnium (Hf) and neodymium (Nd) isotopic compositions and concentrations in surface waters of the eastern Atlantic Ocean between the coast of Spain and South-Africa. These data are complemented by Hf and Nd isotopic and concentration data, as well as rare earth element (REE) concentrations, in Saharan dust.Hafnium concentrations range between a maximum of 0.52 pmol/kg in the area of the Canary Islands and a minimum value of 0.08 pmol/kg in the southern Angola Basin. Neodymium concentrations also show a local maximum in the area of the Canary Islands (26 pmol/kg) but are even higher between ∼20°N and ∼4°N reaching maximum concentrations of 35 pmol/kg. These elevated concentrations provide evidence of inputs from weathering of the Canary Islands and from the partial dissolution of dust from the Sahara/Sahel region. The inputs from ocean island weathering are also reflected in radiogenic Hf and Nd isotopes.The Hf isotopic compositions of dust samples themselves are highly variable, ranging between ε_Hf = −20 and −0.6. The combined Hf and Nd isotopic compositions of dust plot close to the “terrestrial array” during periods of appreciable dust load in the atmosphere. During low atmospheric dust loading combined Hf and Nd isotopic compositions similar to seawater are observed. Most of the variability can be explained in terms of variable degrees of zircon loss from the dust samples, which in turn is linked to sorting during atmospheric transport to the eastern Atlantic Ocean and possibly presorting by sedimentary redistribution on the continent. In addition, increasing relative proportions of radiogenic clay minerals with decreasing grain size may contribute to the radiogenic Hf isotopic compositions observed.While the Nd isotopic composition in the surface ocean reflects the Nd isotopic composition of the Saharan dust adjacent to the Sahara/Sahel region, the release of Hf from that dust appears to be incongruent and results in surface ocean Hf isotopic compositions which are ∼10 ε_Hf more radiogenic than the bulk dust. Radiogenic Hf appears to be released from clays and possibly from trace apatite. Rare earth element patterns of dust samples indicate the presence of apatite but provide no evidence for ferromanganese grain coatings, suggesting that such coatings are insignificant in the release of Hf and Nd from Saharan dust to the surface ocean.The Nd isotopic composition of the surface waters becomes less radiogenic south of the equator, most likely reflecting the release of Nd from Congo river sediments. The release of Hf from Saharan dust and the Congo river sediments, however, does not produce distinct Hf isotopic signatures in the surface ocean, implying that the mobile fraction of Hf integrated over large continental areas is isotopically uniform. The Hf isotopic uniformity in the surface ocean means that the limited variability in deep water isotopic compositions is consistent with a short deep water residence time and reflects homogenous continental inputs rather than efficient deep water homogenization.