Hydrogen and oxygen stable isotope analyses of precipitation sampled at Erlangen (southern Germany) between 2010 and 2013

Shallow groundwater aquifers are often influenced by anthropogenic contaminants or increased nutrient levels. In contrast, deeper aquifers hold potentially pristine paleo-waters that are not influenced by modern recharge. They thus represent important water resources, but their recharge history is often unknown. In this study groundwater from two aquifers in southern Germany were analyzed for their hydrogen and oxygen stable isotope compositions. One sampling campaign targeted the upper aquifer that is actively recharged by modern precipitation, whereas the second campaign sampled the confined, deep Benkersandstein aquifer. The groundwater samples from both aquifers were compared to the local meteoric water line to investigate sources and conditions of groundwater recharge. In addition, the deep groundwater was dated by tritium and radiocarbon analyses. Stable and radiogenic isotope data indicate that the deep-aquifer groundwater was not part of the hydrological water cycle in the recent human history. The results show that the groundwater is older than ~20,000 years and most likely originates from isotopically depleted melt waters of the Pleistocene ice age. Today, the use of this aquifer is strictly regulated to preserve the pristine water. Clear identification of such non-renewable paleo-waters by means of isotope geochemistry will help local water authorities to enact and justify measures for conservation of these valuable resources for future generations in the context of a sustainable water management.

Geochemistry of sediment cores from METEOR cruise M76/1b

Marine sediments are the main sink in the oceanic phosphorus (P) cycle. The activity of benthic microorganisms is decisive for regeneration, reflux, or burial of inorganic phosphate (Pi), which has a strong impact on marine productivity. Recent formation of phosphorites on the continental shelf and a succession of different sedimentary environments make the Benguela upwelling system a prime region for studying the role of microbes in P biogeochemistry. The oxygen isotope signature of pore water phosphate (d18OP) carries characteristic information of microbial P cycling: Intracellular turnover of phosphorylated biomolecules results in isotopic equilibrium with ambient water, while enzymatic regeneration of Pi from organic matter produces distinct offsets from equilibrium. The balance of these two processes is the major control for d18OP. Our study assesses the importance of microbial P cycling relative to regeneration of Pi from organic matter from a transect across the Namibian continental shelf and slope by combining pore water chemistry (sulfate, sulfide, ferrous iron, Pi), steady-state turnover rate modeling, and oxygen isotope geochemistry of Pi. We found d18OP values in a range from 12.8 per mill to 26.6 per mill, both in equilibrium as well as pronounced disequilibrium with water. Our data show a trend towards regeneration signatures (disequilibrium) under low mineralization activity and low Pi concentrations, and microbial turnover signatures (equilibrium) under high mineralization activity and high Pi concentrations. These findings are opposite to observations from water column studies where regeneration signatures were found to coincide with high mineralization activity and high Pi concentrations. It appears that preferential Pi regeneration in marine sediments does not necessarily coincide with a disequilibrium d18OP signature. We propose that microbial Pi uptake strategies, which are controlled by Pi availability, are decisive for the alteration of the isotope signature. This hypothesis is supported by the observation of efficient microbial Pi turnover (equilibrium signatures) in the phosphogenic sediments of the Benguela upwelling system.

U-Pb, trace element, and Hf isotope analysis for Macquarie Island detrital zircon

Oceanic zircon trace element and Hf-isotope geochemistry offers a means to assess the magmatic evolution of a dying spreading ridge and provides an independent evaluation of the reliability of oceanic zircon as an indicator of mantle melting conditions. The Macquarie Island ophiolite in the Southern Ocean provides a unique testing ground for this approach due to its formation within a mid-ocean ridge that gradually changed into a transform plate boundary. Detrital zircon recovered from the island records this change through a progressive enrichment in incompatible trace elements. Oligocene age (33-27 Ma) paleo-detrital zircon in ophiolitic sandstones and breccias interbedded with pillow basalt have trace element compositions akin to a MORB crustal source, whereas Late Miocene age (8.5 Ma) modern-detrital zircon collected from gabbroic colluvium on the island have highly enriched compositions unlike typical oceanic zircon. This compositional disparity between age populations is not complimented by analytically equivalent eHf data that primarily ranges from 14 to 13 for sandstone and modern-detrital populations. A wider compositional range for the sandstone population reflects a multiple pluton source provenance and is augmented by a single cobble clast with eHf equivalent to the maximum observed composition in the sandstone (~17). Similar sandstone and colluvium Hf-isotope signatures indicate inheritance from a similar mantle reservoir that was enriched from the depleted MORB mantle average. The continuity in Hf-isotope signature relative to trace element enrichment in Macquarie Island zircon populations, suggests the latter formed by reduced partial melting linked to spreading-segment shortening and transform lengthening along the dying spreading ridge.

Geochemistry of oceanic crust beneath Costa Rica

Resolving flow geometry in the mantle wedge is central to understanding the thermal and chemical structure of subduction zones, subducting plate dehydration, and melting that leads to arc volcanism, which can threaten large populations and alter climate through gas and particle emission. Here we show that isotope geochemistry and seismic velocity anisotropy provide strong evidence for trench-parallel flow in the mantle wedge beneath Costa Rica and Nicaragua. This finding contradicts classical models, which predict trench-normal flow owing to the overlying wedge mantle being dragged downwards by the subducting plate. The isotopic signature of central Costa Rican volcanic rocks is not consistent with its derivation from the mantle wedge (Feigenson et al., 2004, doi:10.1029/2003GC000621; Herrstom et al., 1995, doi:10.1130/0091-7613(1995)023<0617:VILCAW>2.3.CO;2; Abratis and Woerner, 2001) or eroded fore-arc complexes (Goss and Kay, 2006, doi:10.1029/2005GC001163) but instead from seamounts of the Galapagos hotspot track on the subducting Cocos plate. This isotopic signature decreases continuously from central Costa Rica to northwestern Nicaragua. As the age of the isotopic signature beneath Costa Rica can be constrained and its transport distance is known, minimum northwestward flow rates can be estimated (~63-190 mm/yr) and are comparable to the magnitude of subducting Cocos plate motion (approx85 mm/yr). Trench-parallel flow needs to be taken into account in models evaluating thermal and chemical structure and melt generation in subduction zones.

Geochemistry of metasedimentary units of the Cambro-Ordovician Ross Orogen in North Victoria Land and Oates Land, Antarctica

Metasediments in the three early Palaeozoic Ross orogenic terranes in northern Victoria Land and Oates Land (Antarctica) are geochemically classified as immature litharenites to wackes and moderately mature shales. Highly mature lithotypes with Chemical Index of Weathering values of >=95 are typically absent. Geochemical and Rb-Sr and Sm-Nd isotope results indicate that the turbiditic metasediments of the Cambro-Ordovician Robertson Bay Group in the eastern Robertson Bay Terrane represent a very homogeneous series lacking significant compositional variations. Major variations are only found in chemical parameters which reflect differences in degree of chemical weathering of their protoliths and in mechanical sorting of the detritus. Geochemical data, 87Sr/ 86Sr t=490 Ma ratios of 0.7120 - 0.7174, epsilonNd, t=490 Ma values of -7.6 to -10.3 and single-stage Nd-model ages of 1.7 - 1.9 Ga are indicative of an origin from a chemically evolved crustal source of on average late Palaeoproterozoic formation age. There is no evidence for significant sedimentary infill from primitive "ophiolitic" sources. Metasediments of the Middle Cambrian Molar Formation (Bowers Terrane) are compositionally strongly heterogeneous. Their major and trace element data and Sm-Nd isotope data (epsilonNd, t=500 Ma values of -14.3 to -1.2 and single-stage Nd-model ages of 1.7 - 2.1 Ga) can be explained by mixing of sedimentary input from an evolved crustal source of at least early Palaeoproterozoic formation age and from a primitive basaltic source. The chemical heterogeneity of metasediments from the Wilson Terrane is largely inherited from compositional variations of their precursor rocks as indicated by the Ni vs TiO2 diagram. Single-stage Nd-model ages of 1.6 -2.2 Ga for samples from more western inboard areas of the Wilson Terrane (epsilonNd, t=510 Ma -7.0 to -14.3) indicate a relatively high proportion of material derived from a crustal source with on average early Palaeoproterozoic formation age. Metasedimentary series in an eastern, more outboard position (epsilonNd, t=510 Ma -5.4 to -10.0; single-stage Nd model ages 1.4 - 1.9) on the contrary document stronger influence of a more primitive source with younger formation ages. The chemical and isotopic characteristics of metasediments from the Bowers and Wilson terranes can be explained by variable contributions from two contrasting sources: a cratonic continental crust similar to the Antarctic Shield exposed in Georg V Land and Terre Adélie some hundred kilometers west of the study area and a primitive basaltic source probably represented by the Cambrian island-arc of the Bowers Terrane. While the data for metasediments of the Robertson Bay Terrane are also compatible with an origin from an Antarctic-Shield-type source, there is no direct evidence from their geochemistry or isotope geochemistry for an island-arc component in these series.

Boron contents and boron, carbon, and oxygen isotope data for ODP Sites 160-970 and 160-971

Products of two mud volcanoes from the distal part of the Mediterranean Ridge accretionary complex have been investigated regarding their B, C, and O stable isotope signatures. The mud breccias have been divided into mud matrix, lithified clasts, biogenic deposits, and authigenic cements and crusts related to fluid flow and cementation. Isotope geochemistry is used to evaluate the depth of mobilization of each phase in the subduction zone. B contents and isotope ratios of the mud and mud clasts show a general trend of B enrichment and decreasing d11B values with increasing consolidation (i.e., depth). However, the majority of the clast and matrix samples relate to moderate depths of mobilization within the wedge (1-2 km below seafloor). The carbonate cements of most of these clasts as well as the authigenic crusts, however, provide evidence for a deep fluid influence, probably associated with the décollement at 5-6 km depth. This interpretation is supported by d13C ratios of the crust, which indicate precipitation of C from thermogenic methane, and by the d11B ratios of pore-water samples of mud-breccia drill cores. Clams (Vesicomya sp.) living adjacent to fluid vents have d11B and d18O values corresponding to brines known in the area, which acted as the parent solution for shell precipitation. Such brines are most likely Miocene pore waters trapped at deep levels within the backstop to the accretionary prism, probably prior to desiccation of the Mediterranean in the Messinian (6-5 Ma). Combining all results, deep fluid circulation and expulsion are identified as the main processes triggering mud liquefaction and extrusion, whereas brines contribute only locally. Given the high B contents, mud extrusion has to be considered a major backflux mechanism of B into the hydrosphere.

Strontium, oxygen and hydrogen isotope ratios of basalts from DSDP Hole 504B

DSDP Hole 504B was drilled into 6 Ma crust, about 200 km south of the Costa Rica Rift, Galapagos Spreading Center, penetrating 1.35 km into a section that can be divided into four zones-Zone I: oxic submarine weathering; Zone II: anoxic alteration; Zones III and IV: hydrothermal alteration to greenschist facies. In Zone III there is intense veining of pillow basalts. Zone IV consists of altered sheeted dikes. Isotopic geochemical signatures in relation to the alteration zones are recorded in Hole 504B, as follows: Zone Depth(m) Average87Sr/86Sr Average delta18O (?) Average deltaD (?) I 275-550 0.7032 7.3 -63 II 550-890 0.7029 6.5 -45 III 890-1050 0.7035 5.6 -31 IV 1050-1350 0.7032 5.5 -36 Alteration temperatures are as low as 10°C in Zones I and II based on oxygen isotope fractionation. Strontium isotopic data indicate that a circulation of seawater is much more restricted in Zone II than in Zone I. Fluid inclusion measurements of vein quartz indicate the alteration temperature was mainly 300 +/- 20°C in Zones III and IV, which is consistent with secondary mineral assemblages. The strontium, oxygen, and hydrogen isotopic compositions of hydrothermal fluids which were responsible for the greenschist facies alteration in Zones III and IV are estimated to be 0.7037, 2?, and 3?, respectively. Strontium and oxygen isotope data indicate that completely altered portions of greenstones and vein minerals were in equilibrium with modified seawater under low water/rock ratios (in weight) of about 1.6. This value is close to that of the end-member hydrothermal fluids issuing at 21°N EPR. Basement rocks are not completely hydrothermally altered. About 32% of the greenstones in Zones III and IV have escaped alteration. Thus 1 g of fresh basalt including the 32% unaltered portion are required in order to make 1 g of end-member solution from fresh seawater in water-rock reactions.