Description: The initiation of Northern Hemisphere glaciation in the subarctic North Pacific at ∼2.73 Ma was marked by an abrupt cessation of high opaline accumulation, considered to result from an increased stratification of the water column that should have led to higher utilization of nutrients in the surface ocean. We present a new stable Si isotope-based record of Si utilization that is hard to reconcile with this model. A drop in 30Si/28Si by 0.4‰ at 2.73 Ma is coincident with an increase in bulk N isotope composition. The contrasting utilization records cannot have been both caused by a hydrographic change alone. Excluding a change in the Si:N export ratio, these results either imply a relative increase in silicic acid supplied to the surface waters or a change in its Si isotope composition. While it is impossible to distinguish between these two possibilities, both imply a regional or global change in the Si biogeochemical cycle, potentially caused by an enhanced storage of Si in the underlying deep waters of the Pacific.

Description: Techniques for the purification of Si for the determination of its natural stable isotopic composition have in the past been based on the requirements for gas-source mass-spectrometry, rather than MC-ICPMS. For high precision analyses by MC-ICPMS it is essential to have very pure solutions and in this paper a new technique is presented for the separation and purification of Si from natural samples to improve the determination of isotope ratios. A method has been optimised based on alkaline fusion followed by ion-exchange chromatography. The application to natural samples, such as river water samples and silicate mineral/rock samples is demonstrated. Alkali fusion avoids the use of hydrofluoric acid (HF), which introduces difficulties for the determination of Si isotope ratios using MC-ICPMS. By eliminating HF a 30–40% increase in sensitivity is achieved as well as a marked enhancement of mass bias stability leading to a factor of 2 improvement in reproducibility. The cation-exchange method enables processing of very small samples (3.6 μg Si) and a rapid and effective separation of Si from other cationic species. The overall recovery of Si during the entire procedure is better than 98% and no Si isotope fractionation is generated. Matrix tests demonstrate that this method is suitable for silicates, and that typical sulphate and nitrate abundances of river waters have no effect on measured Si isotope composition. The latter aspect is vital for analysis of river waters since the technique does not separate dissolved Si (silicic acid) from ambient anionic species. Overall, the new method presents a faster, safer and more reliable way to measure Si isotopes via MC-ICPMS.

Description: Two Nd and Pb isotope time series of hydrogenous ferromanganese crusts, one from the Tehuantepec Ridge in the deep eastern equatorial Pacific and the other from Blake Plateau in the shallow northwestern Atlantic, which cover the past 7–8 m.y., show no variations coincident with the final closure of the Panama gateway, estimated as ca. 3.5 Ma. The record of the Atlantic crust located in the present-day Gulf Stream shows a shift in isotope composition from ca. 8 to 5 Ma that is explained by a diminishing supply of Pacific water. It is argued that the major restriction of water-mass exchange through the Panama gateway occurred before 5 Ma and thus cannot serve as a direct cause of the onset of Northern Hemisphere glaciation. The absence of a significant signature in the isotope records from the Pacific crust suggests that the volume of water exchanged with the Atlantic through shallow archipelagic straits of the gateway during the 3–4 m.y. prior to closure was too small to influence the radiogenic isotope composition of Pacific deep water.

Description: New time series of Nd and Pb isotopes were generated from two hydrogenous ferromanganese crusts from the eastern Indian Ocean, which were dated by 10Be / 9Be profiles and Co chronometry. The goal was to gain information on the nature and timing of variations of the deep water radiogenic isotope composition as a function of the evolution of the Indonesian Island Arcs since the Early Miocene, changes in ocean circulation related to the different stages of the closing of the Indonesian seaway for deep and intermediate water mass exchange since the Mid-Miocene, and enhanced Himalayan weathering since the Late Oligocene. A crust from 4119 m water depth in the Wharton Basin adjacent to Sumatra and the Java Trench (DODO 232D) has recorded a small variability in Nd isotope, but pronounced variations in Pb isotope composition over the past 17 Myr. Patterns and absolute values of the Nd and Pb isotope time series closely resemble the record of previously published crust SS663 from the central Indian Ocean, located some 2500 km SW of crust DODO 232D in the northern central Indian Ocean. In accordance with the interpretation derived from crust SS663, the Pb isotope composition of deep water in the Wharton Basin has apparently been mainly controlled by products of Himalayan erosion and weathering and to a lesser extent by the evolution of the Indonesian Island Arcs. The location of a second crust (VA16 13KD-1) from 2100 m water depth on the Scott Plateau off NW Australia is beneath the present day outflow of Pacific-derived surface and thermocline water masses into the eastern Indian Ocean. The pattern of the Pb isotope time series of this crust and the observed changes in Pb isotope mixing relationships, which occurred at ∼ 11.5 and ∼ 3.5 Ma, reflect the combined influence of advection and mixing of water masses through the Indonesian Seaway and weathering of volcanic source rocks within the emerging Indonesian Island Arcs over the past 33 Myr. The Nd isotope time series shows a pattern similar to central and southwest Pacific crusts and is best explained by a mixture between Nd from water masses advected from the Indian and Southern Ocean and Nd released by weathering from the emerging Indonesian Island Arcs.

Description: 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 εNd and εHf both decrease with water depth. Similarly, εNd and εHf 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.

Description: The possible sources of pre-anthropogenic Pb contributed to the world's oceans have been the focus of considerable study. The role of eolian dust versus riverine inputs has been of particular interest. With better calibration of isotopic records from central Pacific ferromanganese crusts using Os isotope stratigraphy it now appears that deep water Pb isotopic compositions were effectively homogeneous over a distance of 5000 km for the past 80 Myr. The composition shifted slightly from high 206Pb/204Pb ratios in the range of 18.87 ± 0.02 before 65 Ma to lower values of 18.62 ± 0.02 by 45 Ma and then gradually increased again very slightly to the present day ratio of 18.67 ± 0.02. The regional homogeneity provides evidence of a dominant well-mixed atmospheric source the most likely candidate for which is volcanic aerosols contributed either directly or as soluble condensates on eolian dust. The slight shift in Pb isotope composition of deep waters in the central Pacific between 65 and 45 Ma may be the result of a regional- or perhaps global-scale change in the sources of volcanic exhalations and volcanic activity caused by an increase in the importance of melting and assimilation of older continental crustal components over the Cenozoic