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: 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 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

Description: Many marine radiogenic isotope records show both spatial and temporal variations, reflecting both the degree of mixing of distinct sources in the oceans and changes in the distribution of chemical weathering on the continents. However, changes in weathering and transport processes may themselves affect the composition of radiogenic isotopes released into seawater. The provenance of physically weathered material in the Labrador Sea, constrained through the use of Ar–Ar ages of individual detrital minerals, has been used to estimate the relative contributions of chemically weathered terranes releasing radiogenic isotopes into the Labrador Sea. A simple box-model approach for balancing observed Nd-isotope variations has been used to constrain the relative importance of localised input in the Labrador Sea, and the subsequent mixing of Labrador Sea Water into North Atlantic Deep-Water. The long-term pattern of erosion and deep-water formation around the North Atlantic seems to have been a relatively stable feature since 1.5 Ma, although there has been a dramatic shift in the nature of physical and chemical weathering affecting the release of Hf and Pb isotopes. The modelled Nd isotopes imply a relative decrease in water mass advection into the Labrador Sea between 2.4 and 1.5 Ma, accompanied by a decrease in the rate of overturning, possibly caused by an increased freshwater input into the Labrador Sea.

Description: It has been proposed that silicon (Si) isotopes are fractionated during weathering and biological activity leading to heavy dissolved riverine compositions. In this study, the first seasonal variations of stable isotope compositions of dissolved riverine Si are reported and compared with concomitant changes in water chemistry. Four different rivers in Switzerland were sampled between March 2004 and July 2005. The unique high-resolution multi-collector ICP-MS Nu1700, has been used to provide simultaneous interference-free measurements of 28Si, 29Si and 30Si abundances with an average limiting precision of ± 0.04‰ on δ30Si. This precision facilitates the clarification of small temporal variations in isotope composition. The average of all the data for the 40 samples is δ30Si = + 0.84 ± 0.19‰ (± 1σSD). Despite significant differences in catchment lithologies, biomass, climate, total dissolved solids and weathering fluxes the averaged isotopic composition of dissolved Si in each river is strikingly similar with means of + 0.70 ± 0.12‰ for the Birs,+ 0.95 ± 0.22‰ for the Saane,+ 0.93 ± 0.12‰ for the Ticino and + 0.79 ± 0.19‰ for the Verzasca. However, the δ30Si undergoes seasonal variations of up to 0.6‰. Comparisons between δ30Si and physico–chemical parameters, such as the concentration of dissolved Si and other cations, the discharge of the rivers, and the resulting weathering fluxes, permits an understanding of the processes that control the Si budget and the fate of dissolved Si within these rivers. The main mechanism controlling the Si isotope composition of the mountainous Verzasca River appears to be a two component mixing between the seepage of soil/ground waters, with heavier Si produced by clay formation and superficial runoff associated with lighter Si during high discharge events. A biologically-mediated fractionation can be excluded in this particular river system. The other rivers display increasing complexity with increases in the proportion of forested and cultivated landscapes as well as carbonate rocks in the catchment. In these instances it is impossible to resolve the extent of the isotopic fractionation and contributed flux of Si contributed by biological processes as opposed to abiotic weathering. The presence of seasonal variations in Si isotope composition in mountainous rivers provides evidence that extreme changes in climate affect the overall composition of dissolved Si delivered to the oceans. The oceanic Si isotope composition is very sensitive to even small changes in the riverine Si isotope composition and this parameter appears to be more critical than plausible changes in the Si flux. Therefore, concurrent changes in weathering style may need to be considered when using the Si isotopic compositions of diatoms, sponges and radiolaria as paleoproductivity proxies.