Claudia Ehlert

Current transport versus continental inputs in the eastern Indian Ocean: Radiogenic isotope signatures of clay size sediments

Analyses of radiogenic neodymium (Nd), strontium (Sr), and lead (Pb) isotope compositions of clay-sized detrital sediments allow detailed tracing of source areas of sediment supply and present and past transport of particles by water masses in the eastern Indian Ocean. Isotope signatures in surface sediments range from −21.5 (ɛNd), 0.8299 (87Sr/86Sr), and 19.89 (206Pb/204Pb) off northwest Australia to +0.7 (ɛNd), 0.7069 (87Sr/86Sr), and 17.44 (206Pb/204Pb) southwest of Java. The radiogenic isotope signatures primarily reflect petrographic characteristics of the surrounding continental bedrocks but are also influenced by weathering-induced grain size effects of Pb and Sr isotope systems with superimposed features that are caused by current transport of clay-sized particles, as evidenced off Australia where a peculiar isotopic signature characterizes sediments underlying the southward flowing Leeuwin Current and the northward flowing West Australian Current (WAC). Gravity core FR10/95-GC17 off west Australia recorded a major isotopic change from Last Glacial Maximum values of −10 (ɛNd), 0.745 (87Sr/86Sr), and 18.8 (206Pb/204Pb) to Holocene values of −22 (ɛNd), 0.8 (87Sr/86Sr), and 19.3 (206Pb/204Pb), which documents major climatically driven changes of the WAC and in local riverine particle supply from Australia during the past 20 kyr. In contrast, gravity core FR10/95-GC5 located below the present-day pathway of the Indonesian throughflow (ITF) shows a much smaller isotopic variability, indicating a relatively stable ITF hydrography over most of the past 92 kyr. Only the surface sediments differ significantly in their isotopic composition, indicating substantial changes in erosional sources attributed to a change of the current regime during the past 5 kyr.

Discovery of Miocene to early Pleistocene deposits on Mayaguana, Bahamas: Evidence for recent active tectonism on the North American margin

We report here the discovery of Miocene, Pliocene, and early Pleistocene shallow-marine carbonates on Mayaguana Island (southeastern Bahamas) that have so far not been observed on any other Bahamian island. Spanning more than 17 m.y., but <12 m thick, this stratigraphic succession only occurs along the northern coast of the island, indicating that the Mayaguana Bank underwent minor subsidence throughout the late Cenozoic and was tilted toward the south during the Quaternary. In addition to considerably extending the stratigraphic record of the Bahamas Islands, our findings demonstrate that these carbonate banks were at different elevations and subsided at different rates during the Neogene. The young age of the tilting event detected on Mayaguana further shows that parts of the southeastern margin of North America have recently undergone tectonic activity a long way from its actual boundary with the Caribbean plate.

GEOTRACES Intercalibration of the Stable Silicon Isotope Composition of Dissolved Silicic Acid in Seawater

The first inter-calibration study of the stable silicon isotope composition of dissolved silicic acid in seawater, δ30Si(OH)4, is presented as a contribution to the international GEOTRACES program. Eleven laboratories from seven countries analyzed two seawater samples from the north Pacific subtropical gyre (Station ALOHA) collected at 300 m and at 1000 m water depth. Sampling depths were chosen to obtain samples with a relatively low (9 μmol L-1, 300 m) and a relatively high (113 μmol L-1, 1000 m) silicic acid concentration as sample preparation differs for low- and high- concentration samples. Data for the 1000m water sample were not normally distributed so the median is used to represent the central tendency for the two samples. Median δ30Si(OH)4 values of +1.66 ‰ for the low-concentration sample and +1.25 ‰ for the high-concentration sample were obtained. Agreement among laboratories is overall considered very good; however, small but statistically significant differences among the mean isotope values obtained by different laboratories were detected likely reflecting interlaboratory differences in chemical preparation including pre-concentration and purification methods together with different volumes of seawater volume analyzed, and the use of different mass spectrometers including the Neptune MC-ICP-MS (Thermo Fisher™, Germany), the Nu Plasma MC-ICP-MS (Nu Instruments™, Wrexham, UK), and the Finnigan™ (now Thermo Fisher™, Germany) MAT 252 IRMS. Future studies analyzing δ30Si(OH)4 in seawater should also analyze and report values for these same two reference waters in order to facilitate comparison of data generated among and within laboratories over time.

A review of the stable isotope bio-geochemistry of the global silicon cycle and its associated trace elements

Silicon (Si) is the second most abundant element in the Earth’s crust and is an important nutrient in the ocean. The global Si cycle plays a critical role in regulating primary productivity and carbon cycling on the continents and in the oceans. Development of the analytical tools used to study the sources, sinks, and fluxes of the global Si cycle (e.g., elemental and stable isotope ratio data for Ge, Si, Zn, etc.) have recently led to major advances in our understanding of the mechanisms and processes that constrain the cycling of Si in the modern environment and in the past. Here, we provide background on the geochemical tools that are available for studying the Si cycle and highlight our current understanding of the marine, freshwater and terrestrial systems. We place emphasis on the geochemistry (e.g., Al/Si, Ge/Si, Zn/Si, δ13 C, δ15 N, δ18 O, δ30 Si) of dissolved and biogenic Si, present case studies, such as the Silicic Acid Leakage Hypothesis, and discuss challenges associated with the development of these environmental proxies for the global Si cycle. We also discuss how each system within the global Si cycle might change over time (i.e., sources, sinks, and processes) and the potential technical and conceptual limitations that need to be considered for future studies.

Changes in diatom productivity and upwelling intensity off Peru since the Last Glacial Maximum: Response to basin‐scale atmospheric and oceanic forcing

New records of stable silicon isotope signatures (δ30Si) together with concentrations of biogenic opal and organic carbon from the central (9° S) and northern (5° S) Peruvian margin reveal changes in diatom productivity and nutrient utilization during the past 20,000 years. The findings are based on a new approach using the difference between the δ30Si signatures of small (11-32μm) and large (>150μm) diatom fractions (Δ30Sicoscino-bSi) in combination with the variance in diatom assemblages for reconstruction of past upwelling intensity. Combination of our records with two previously published records from the southern upwelling area off Peru (12-15° S) shows a general decoupling of the environmental conditions at the central and southern shelf mainly caused by a northward shift of the main upwelling cell from its modern position (12-15° S) towards 9° S during Termination 1. At this time only moderate upwelling intensity and productivity levels prevailed between 9° S and 12° S interpreted by a more northerly position of Southern Westerly Winds and the South Pacific Subtropical High. Furthermore, a marked decrease in productivity at 12-15° S during Heinrich Stadial 1 coincided with enhanced biogenic opal production in the Eastern Equatorial Pacific, which was induced by a southward shift of the Intertropical Convergence zone and enhanced northeasterly trade winds. Modern conditions were only established at the onset of the Holocene. Past changes in preformed δ30Si signatures of subsurface waters reaching the Peruvian Upwelling System did not significantly affect the preserved δ30Si signatures.

Latitudinal variations of δ 30 Si and δ 15 N signatures along the Peruvian shelf: quantifying the effects of nutrient utilization versus denitrification over the past 600 years

The stable sedimentary nitrogen isotope compositions of bulk organic matter (δNbulk) and the silicon isotope composition of diatoms (δSiBSi) both mainly reflect the degree of past nutrient utilization by primary producers. However, in ocean areas where anoxic and suboxic conditions prevail, the δNbulk signal ultimately recorded within the sediments is also influenced by water column denitrification, causing an increase in the subsurface δ15N signature of dissolved nitrate (δNO3 ) upwelled to the surface. Such conditions are found in the oxygen minimum zone off the coast of Peru, where, at present, an increase in subsurface δNO3 from north to south along the shelf is observed due to ongoing denitrification within the poleward-flowing subsurface waters, while the δ30Si signature of silicic acid (δSi(OH)4) at the same time remains unchanged. Here, we present three new δSiBSi records between 11 and 15 S and compare these to previously published δSiBSi and δNbulk records from Peru covering the past 600 years. We present a new approach to calculate past subsurface δNO3 signatures based on the direct comparison of δSiBSi and δNbulk signatures at a latitudinal resolution for different time periods. Our results show that, during the Current Warm Period (CWP, since 1800 CE) and prior shortterm arid events, source water δNO3 compositions have been close to modern values, increasing southward from 7 to 10 ‰ (between 11 and 15 S). In contrast, during the Little Ice Age (LIA) we calculate low δNO3 values between 6 ‰ and 7.5 ‰. Furthermore, the direct δSiBSi versus δNbulk comparison also enables us to relate the short-term variability in both isotope compositions to changes in the ratio of nutrients (NO−3 : Si(OH)4) taken up by different dominating phytoplankton groups (diatoms and non-siliceous phytoplankton) under the variable climatic conditions of the past 600 years. Accordingly, we estimate a shift from a 1 : 1 (or 1 : 2) ratio during the CWP and a 2 : 1 (up to 15 : 1) ratio during the LIA, associated with a shift from overall high nutrient utilization to NO−3 -dominated (and thus non-siliceous phytoplankton) utilization.

Silicon analysis and dissolved cation concentrations in the sandy beach ecosystem Spiekeroog, German North Sea

Dissolved silicon isotope compositions (d30Si) have been analysed for the first time in groundwaters of beach sediments, which represent a subterranean estuary with fresh groundwater discharge from a freshwater reservoir and mixing with recirculated seawater. The fresh groundwater reservoir has high and variable dissolved silica concentrations between 136 and 736 µM, but homogeneous d30Si of +1.0 ± 0.15 per mil. By contrast, the seawater is strongly depleted in dissolved silica with concentrations of 3 µM, and consequently characterised by high d30Si of +3.0 per mil. The beach groundwaters are variably enriched in dissolved silica compared to seawater (23-192 µM), and concentrations increase with depth at all sampling sites. The corresponding d30Si values are highly variable (+0.3 per mil to +2.2 per mil) and decrease with depth at each site. All groundwater d30Si values are lower than seawater and most values are lower than dissolved d30Si of freshwater discharge indicating a significant amount of lithogenic silica dissolution in beach sediments. In contrast to open North Sea sediments, diatom dissolution or formation of authigenic silica in beach sediments is very low (ca. 5 µmol Si g). Silica discharge from the beach to the coastal ocean is estimated as approximately 210 mol Si yr per meter shoreline. Considering the extent of coastline this is, at least for the study area, a significant amount of the total Si budget and amounts to ca. 1% of river and 3.5% of backbarrier tidal flat area Si input.