Constraining Holocene hydrological changes in the Carpathian–Balkan region using speleothem δ18O and pollen-based temperature reconstructions

Here we present a speleothem isotope record (POM2) from Ascunsă Cave (Romania) that provides new data on past climate changes in the Carpathian–Balkan region from 8.2 ka until the present. This paper describes an approach to constrain the effect of temperature changes on calcite δ18O values in stalagmite POM2 over the course of the middle Holocene (6–4 ka), and across the 8.2 and 3.2 ka rapid climate change events. Independent pollen temperature reconstructions are used to this purpose. The approach combines the temperature-dependent isotope fractionation of rain water during condensation and fractionation resulting from calcite precipitation at the given cave temperature. The only prior assumptions are that pollen-derived average annual temperature reflects average cave temperature, and that pollen-derived coldest and warmest month temperatures reflect the range of condensation temperatures of rain above the cave site. This approach constrains a range of values between which speleothem δ18O changes should be found if controlled only by surface temperature variations at the cave site. Deviations of the change in δ18Ocspel values from the calculated temperature-constrained range of change are interpreted towards large-scale variability of climate–hydrology. Following this approach, we show that an additional ∼0.6‰ enrichment of δ18Oc in the POM2 stalagmite was caused by changing hydrological patterns in SW Romania across the middle Holocene, most likely comprising local evaporation from the soil and an increase in Mediterranean moisture δ18O. Further, by extending the calculations to other speleothem records from around the entire Mediterranean basin, it appears that all eastern Mediterranean speleothems recorded a similar isotopic enrichment due to changing hydrology, whereas all changes recorded in speleothems from the western Mediterranean are fully explained by temperature variation alone. This highlights a different hydrological evolution between the two sides of the Mediterranean. Our results also demonstrate that during the 8.2 ka event, POM2 stable isotope data essentially fit the temperature-constrained isotopic variability. In the case of the 3.2 ka event, an additional climate-related hydrological factor is more evident. This implies a different rainfall pattern in the Southern Carpathian region during this event at the end of the Bronze Age

Fe isotopes revealing mineral-specific redox cycling in sediments

Reactive Fe (oxyhydr)oxides preferentially undergo early diagenetic cycling and cause a diffusive flux of dissolved Fe2+ towards the sediment-water interface. The partitioning of sedimentary Fe has traditionally been studied by applying sequential extractions. We modified an existing leaching method [1] in order to enable δ56Fe measurements on specific Fe mineral fractions. Those are siderite/sorbed Fe, ferrihydrite/lepidocrocite, goethite/hematite, and magnetite. The selectivity of extractions was tested by leaching pairs of 58Fe-spiked and unspiked synthetic minerals. Insignificant amounts of goethite and hematite are dissolved in hydroxylamine-HCl targetting ferrihydrite/lepidocrocite. The determination of reducible oxides leached by dithionite was found to be slightly compromised in presence of magnetite. Removal of extraction matrix was achieved by repetitive oxidation, heating, Fe precipitation, and column separation. The new method was applied to a short sediment core from the North Sea. Downcore mineral-specific variations in δ56Fe revealed differing contributions of Fe oxides to redox cycling. Acetic acid soluble Fe and ferrihydrite/lepidocrocite-Fe showed increasing δ56Fe values with depth in accordance with progressive dissimilatory iron reduction (DIR). Low δ56Fe in acetic acid soluble Fe relative to ferric hydrous oxide-Fe is consistent with the fractionation pattern between sorbed Fe(II) and ferric substrate during DIR experiments [2]. Goethite/hematite-and magnetite-Fe do not show δ56Fe trends with depth. The results demonstrate the importance of δ56Fe analysis on individual Fe fractions that differ in origin and reactivity. The developed procedure provides a basis for specific Fe isotope studies in past and present environments that undergo or underwent redox changes. [1] Poulton and Canfield (2005), Chemical Geology 214, 209-221. [2] Crosby et al., Geobiology 5 (2007), 169-189

Iron cycling and stable Fe isotope fractionation in Antarctic shelf sediments, King George Island

Iron (Fe) fluxes from reducing sediments and subglacial environments are potential sources of bioavailable Fe into the Southern Ocean. Stable Fe isotopes (δ56Fe ) are considered a proxy for Fe sources and reaction pathways, but respective data are scarce and Fe cycling in complex natural environments is not understood sufficiently to constrain respective δ56Fe “endmembers” for different types of sediments, environmental conditions, and biogeochemical processes. We present δ56Fe data from pore waters and sequentially extracted sedimentary Fe phases of two contrasting sites in Potter Cove (King George Island, Antarctic Peninsula), a bay that is affected by fast glacier retreat. Sediments close to the glacier front contain more easily reducible Fe oxides and pyrite and show a broader ferruginous zone, compared to sediments close to the icefree coast, where surficial oxic meltwater streams discharge into the bay. Pyrite in sediments close to the glacier front predominantly derives from eroded bedrock. For the high amount of easily reducible Fe oxides proximal to the glacier we suggest mainly subglacial sources, where Fe liberation from comminuted material beneath the glacier is coupled to biogeochemical weathering processes (likely pyrite oxidation or dissimilatory iron reduction, DIR). Our strongest argument for a subglacial source of the highly reactive Fe pool in sediments close to the glacier front is its predominantly negative δ56Fe signature that remains constant over the whole ferruginous zone. This implies in situ DIR does not significantly alter the stable Fe isotope composition of the accumulated Fe oxides. The nonetheless overall light δ56Fe signature of easily reducible Fe oxides suggests pre-depositional microbial cycling as it occurs in potentially anoxic subglacial environments. The strongest 56Fe-depletion in pore water and most reactive Fe oxides was observed in sediments influenced by oxic meltwater discharge. The respective site showed a condensed redox zonation and a pore water δ56Fe profile typical for in-situ Fe cycling. We demonstrate that the potential of pore water δ56Fe as a proxy for benthic Fe fluxes is not straight-forward due to its large variability in marine shelf sediments at small spatial scales (- 2.4‰ at the site proximal to oxic meltwater discharge vs. -0.9‰ at the site proximal to the marine glacier terminus, both at 2 cm sediment depth). The controlling factors are multifold and include the amount and reactivity of reducible Fe oxides and organic matter, the isotopic composition of the primary and secondary ferric substrates, sedimentation rates, and physical reworking (bioturbation, ice scraping). The application of δ56Fe geochemistry may prove valuable in investigating biogeochemical weathering and Fe cycling in subglacial environments. This requires, however (similarly to the use of δ56Fe for the quantification of benthic fluxes), that the spatial and temporal variability of the isotopic endmember is known and accounted for. Since geochemical data from subglacial environments are very limited, further studies are needed in order to sufficiently assess Fe cycling and fractionation at glacier beds and the composition of discharges from those areas

Insight into contributions of different iron sources to the ocean from a model of the Fe stable isotopes

It has been widely accepted that iron is an essential micronutrient for ocean biota, and its distribution strongly affects the magnitude of phytoplankton primary productivity and thus the carbon uptake in the ocean. Yet there is still no consensus on the mechanisms behind the distribution of iron and especially on the relative role of different external iron sources to the ocean (e.g. aeolian dust, marine sediments, hydrothermal and riverine inputs). In recent years, the analysis of the stable isotopic composition of dissolved iron in sea water has been increasingly used to constrain the relative role of different iron sources. To take into account processes in the ocean interior to fractionate between iron isotopes and physical processes (transport and diffusion) to mix water masses with different isotopic compositions, we have extended a global biogeochemical model of iron with an explicit representation of isotopic effects and present here some insight from the modelling perspective into contributions of different iron sources to the ocean

Indian winter and summer monsoon strength over the 4.2 ka BP event in foraminifer isotope records from the Indus River delta in the Arabian Sea

Abstract. The plains of northwest South Asia receive rainfall during both the Indian summer (June–September) and winter (December–March) monsoon. Researchers have long attempted to deconstruct the influence of these precipitation regimes in paleoclimate records, in order to better understand regional climatic drivers and their potential impact on human populations. The mid–late Holocene transition between 5.3 and 3.3 ka is of particular interest in this region because it spans the period of the Indus Civilization from its early development, through its urbanization, and onto eventual transformation into a rural society. An oxygen isotope record of the surface-dwelling planktonic foraminifer Globigerinoides ruber from the northeast Arabian Sea provided evidence for an abrupt decrease in rainfall and reduction in Indus River discharge at 4.2 ka, which the authors linked to the decline in the urban phase of the Indus Civilization (Staubwasser et al., 2003). Given the importance of this study, we used the same core (63KA) to measure the oxygen isotope profiles of two other foraminifer species at decadal resolution over the interval from 5.4 to 3.0 ka and to replicate a larger size fraction of G. ruber than measured previously. By selecting both thermocline-dwelling (Neogloboquadrina dutertrei) and shallow-dwelling (Globigerinoides sacculifer) species, we provide enhanced detail of the climatic changes that occurred over this crucial time interval. We found evidence for a period of increased surface water mixing, which we suggest was related to a strengthened winter monsoon with a peak intensity over 200 years from 4.5 to 4.3 ka. The time of greatest change occurred at 4.1 ka when both the summer and winter monsoon weakened, resulting in a reduction in rainfall in the Indus region. The earliest phase of the urban Mature Harappan period coincided with the period of inferred stronger winter monsoon between 4.5 and 4.3 ka, whereas the end of the urbanized phase occurred some time after the decrease in both the summer and winter monsoon strength by 4.1 ka. Our findings provide evidence that the initial growth of large Indus urban centers coincided with increased winter rainfall, whereas the contraction of urbanism and change in subsistence strategies followed a reduction in rainfall of both seasons. ER

Iron isotope signals: Use and limitations in natural marine sediments

Oral presentatio

Indian winter and summer monsoon strength over the 4.2 ka BP event in foraminifer isotope records from the Indus River delta in the Arabian Sea

The plains of northwest South Asia receive rainfall during both the Indian summer (June–September) and winter (December–March) monsoon. Researchers have long attempted to deconstruct the influence of these precipitation regimes in paleoclimate records, in order to better understand regional climatic drivers and their potential impact on human populations. The mid–late Holocene transition between 5.3 and 3.3 ka is of particular interest in this region because it spans the period of the Indus Civilization from its early development, through its urbanization, and onto eventual transformation into a rural society. An oxygen isotope record of the surface-dwelling planktonic foraminifer Globigerinoides ruber from the northeast Arabian Sea provided evidence for an abrupt decrease in rainfall and reduction in Indus River discharge at 4.2 ka, which the authors linked to the decline in the urban phase of the Indus Civilization (Staubwasser et al., 2003). Given the importance of this study, we used the same core (63KA) to measure the oxygen isotope profiles of two other foraminifer species at decadal resolution over the interval from 5.4 to 3.0 ka and to replicate a larger size fraction of G. ruber than measured previously. By selecting both thermocline-dwelling (Neogloboquadrina dutertrei) and shallow-dwelling (Globigerinoides sacculifer) species, we provide enhanced detail of the climatic changes that occurred over this crucial time interval. We found evidence for a period of increased surface water mixing, which we suggest was related to a strengthened winter monsoon with a peak intensity over 200 years from 4.5 to 4.3 ka. The time of greatest change occurred at 4.1 ka when both the summer and winter monsoon weakened, resulting in a reduction in rainfall in the Indus region. The earliest phase of the urban Mature Harappan period coincided with the period of inferred stronger winter monsoon between 4.5 and 4.3 ka, whereas the end of the urbanized phase occurred some time after the decrease in both the summer and winter monsoon strength by 4.1 ka. Our findings provide evidence that the initial growth of large Indus urban centers coincided with increased winter rainfall, whereas the contraction of urbanism and change in subsistence strategies followed a reduction in rainfall of both seasons

Iron Transport by Subglacial Meltwater Indicated by δ56Fe in Coastal Sediments of King George Island, Antarctica

Iron (Fe) fluxes from reducing sediments and subglacial environments potentially contribute to bioavailable Fe in the Southern Ocean. Stable Fe isotopes (δ56Fe) may be used to trace Fe sources and reactions, but data are scarce and Fe cycling in natural environments is not understood sufficiently to constrain δ56Fe endmembers for different types of sediments, environments, and biogeochemical processes. δ56Fe data from pore waters and sequentially extracted solid Fe phases at two sites in Potter Cove (King George Island, Antarctica), a bay affected by fast glacier retreat, are presented. Close to the glacier front, sediments contain high amounts of easily reducible Fe oxides and show a dominance of ferruginous conditions compared to sediments close to the ice-free coast, where surficial oxic meltwater discharges and sulfate reduction dominates. We suggest that high amounts of reducible Fe oxides close to the glacier mainly derive from subglacial sources, where Fe liberation from comminuted material beneath the glacier is coupled to biogeochemical weathering. A strong argument for a subglacial source is the predominantly negative δ56Fe signature of reducible Fe oxides that remains constant throughout the ferruginous zone. In situ dissimilatory iron reduction (DIR) does not significantly alter the isotopic composition of the oxides. The composition of the easily reducible Fe fraction therefore suggests pre-depositional microbial cycling as it occurs in subglacial environments. Sediments influenced by oxic meltwater discharge show downcore trends towards positive δ56Fe signals in pore water and reactive Fe oxides, typical for in situ DIR as 54Fe becomes less available with increasing depth. Henkel et al. (2018) Diagenetic iron cycling and stable Fe isotope fractionation in Antarctic shelf sediments, King George Island. GCA 237, 320-338

Fraction-specific controls on the trace element distribution in iron formations: Implications for trace metal stable isotope proxies

Iron formations (IFs) are important geochemical repositories that provide constraints on atmospheric and ocean chemistry, prior to and during the onset of the Great Oxidation Event. Trace metal abundances and their Mo-Cr-U isotopic ratios have been widely used for investigating ocean redox processes through the Archean and Paleoproterozoic. Mineralogically, IFs consist of three main Fe-bearing fractions: (1) Fe-Ca-Mg-Mn carbonates, (2) magnetite and/or hematite and (3) Fe-silicates. These fractions are typically fine-grained on a sub-μm scale and their co-occurrence in varying amounts means that bulk-rock or microanalytical geochemical and stable isotope data can be influenced by cryptic changes in mineralogy. Fraction specific geochemical analysis has the potential to resolve mineralogical controls and reveal diagenetic versus primary precipitative controls on IF mineralogy. Here we adapt an existing sequential extraction scheme for Fe-phases (Poulton and Canfield, 2005) to the high Fe-content in IF and the specific three-fraction mineralogy. We optimized the scheme for magnetite-dominated Archean IFs using samples from the hematite-poor Asbestos Hills Subgroup IF, Transvaal Supergroup, South Africa. Previously commonly-used hydroxylamine-HCl and dithionite leaches were omitted since ferric oxides are quantitatively insignificant in these IF samples. The acetate leach was tested at variable temperatures, reaction times and under different atmospheres in order to ensure that all micro-crystalline Fe-carbonates were effectively dissolved, resulting in an optimum extraction for 48 h at 50 °C under anoxic conditions. The dissolution of magnetite by NH4-oxalate was also tested, resulting in an optimum extraction for 24 h under an ambient atmosphere. Finally, a HF-HClO4-HNO3 leach was used to dissolve the residual silicate fraction which has to date not been considered in detail in IF. Accuracy of the extraction technique was generally excellent, as verified using 1) elemental recoveries, 2) comparison of major and trace element distributions against mineralogy and 3) comparison to results from microanalytical techniques. This study focuses on the distribution of three frequently used geochemical proxies in IF; U, Mo and Cr. Molybdenum abundances in the Kuruman and Griquatown IF are low and show an apparent correlation with mineralogical variability, as determined by the sequential extraction. This suggests that changes in bulk-rock mineralogy, rather than redox chemistry might significantly affect Mo stable isotopes. For Cr, a minor bulk-rock stratigraphic increase can be related to the oxide and silicate fraction. However, a positive relationship with Zr indicates that this was also controlled by detrital or volcanic ash input. Uranium is predominantly bound to the silicate fraction and shows clear correlations with Zr and Sc implying detrital reworking under anoxic conditions. The discrepant behaviour of these three proxies indicate that mineralogy should be taken into account when interpreting heterogeneous bulk-rock samples and that fraction specific techniques will provide new insights into the evolution of atmosphere and ocean chemistry

Simultaneous analysis of17O/16O,18O/16O and2H/1H of gypsum hydration water by cavity ring-down laser spectroscopy

The recent development of cavity ring-down laser spectroscopy (CRDS) instruments capable of measuring 17O-excess in water has created new opportunities for studying the hydrologic cycle. Here we apply this new method to studying the triple oxygen (17O/16O, 18O/16O) and hydrogen (2H/1H) isotope ratios of gypsum hydration water (GHW), which can provide information about the conditions under which the mineral formed and subsequent post-depositional interaction with other fluids