Sr-isotope analysis of speleothems by LA-MC-ICP-MS: High temporal resolution and fast data acquisition

Speleothems are well established climate archives. A wide array of geochemical proxies, including stable isotopes and trace elements are present within speleothems to reconstruct past climate variability. However, each proxy is influenced by multiple factors, often hampering robust interpretation. Sr isotope ratios (87Sr/86Sr) can provide useful information about water residence time and water mixing in the host rock, as they are not fractionated during calcite precipitation. Laser ablation multi-collector-inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) has rarely been used for determination of Sr isotope signatures in speleothems, as speleothems often do not possess appropriately high concentrations of Sr to facilitate this analysis. Yet the advantages of this approach include rapid data acquisition, higher spatial resolution, larger sample throughput and the absence of chemical treatment prior to analysis. We present LA-MC-ICP-MS Sr isotope data from two speleothems from Morocco (Grotte de Piste) and India (Mawmluh Cave), and we compare linescan and spot analysis ablation techniques along speleothem growth axes. The analytical uncertainty of our LA-MC-ICP-MS Sr data is comparable to studies conducted on other carbonate materials. The results of both ablation techniques are reproducible within analytical error, implying that this technique yields robust results when applied to speleothems. In addition, several comparative measurements of different carbonate reference materials (i.e. MACS-3, JCt-1, JCp-1), including tests with standard bracketing and comparison of the 87Sr/86Sr ratios with a nanosecond laser ablation system and a state-of-the-art femtosecond laser ablation system, highlight the robustness of the method

OIB/seamount recycling as a possible process for E-MORB genesis

International audienceThis paper deals with the origin of enriched MORB independent from any hot spot activity. Indeed, MORB enrichment was readily attributed to a ridge/hot spot interaction and in absence of identified neighboring hot spot, to more questionable processes (e.g., incipient plume or plume activity residue). More recently, the existence of enriched MORB away from any identifiable hot spot was attributed to different origins (i.e., recycled oceanic crust and/or enriched mantle after subduction metasomatism). Within this frame, we present here a new set of geochemical analyses of major and trace elements and Sr, Nd and Pb isotopes on samples collected by submersible on both intersections of the 15°20′N fracture zone with the spreading axis of the Mid-Atlantic Ridge. This area is characterized by an increasing enrichment of the lava compositions from north to south through the fracture zone. Results show that the geochemical enrichment observed with a different intensity on both sides of the fracture zone is linked to the 14°N topographic and geochemical anomaly. Our modeling shows that both trace element and isotopic compositions are consistent with a binary mixing between the regional depleted MORB mantle source and a recycled OIB/seamount, as previously proposed to explain the observed enrichment at 14°N. This model can also account for other enriched MORB i.e., the 18°-20°S region of the Central Indian Ridge, illustrating that it does not represent an isolated and local process. On the basis of our results and on the DMM isotopic evolution, the age of the recycled OIB/seamount is estimated to be ∼250 Ma, suggesting a recycling within the upper mantle. Considering the huge number of ocean islands and seamounts upon the ocean floor, their recycling into the upper mantle is a plausible process to produce enriched MORB

Artifacts from manganese reduction in rock samples prepared by focused ion beam (FIB) slicing for X-ray microspectroscopic analysis

Abstract. Manganese (Mn)-rich natural rock coatings, so-called rock varnishes, are discussed controversially regarding their genesis. Biogenic and abiogenic mechanisms, as well as a combination of both, have been proposed to be responsible for the Mn oxidation and deposition process. We conducted scanning transmission X-ray microscopy - near edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS) measurements to examine the abundance and spatial distribution of the different oxidation states of Mn within these nano- to micrometer thick crusts. Such microanalytical measurements of thin and hard rock crusts require sample preparation with minimal contamination risk. Focused ion beam (FIB) slicing, a well-established technique in geosciences, was used in this study to obtain 100–200 nm thin slices of the samples for X-ray transmission spectroscopy. However, even though this preparation is suitable to investigate element distributions and structures in rock samples, we observed that, using standard parameters, modifications of the Mn oxidation states occur in the surfaces of the FIB slices. Based on our results, the preparation technique likely causes the reduction of Mn4+ to Mn2+/3+. We draw attention to this issue, since FIB slicing, SEM imaging, and other preparation and visualization techniques operating in the keV range are well-established in geosciences, but researchers are often unaware of the potential for reduction of Mn and possibly other elements in the samples’ surface layers

Elemental Inventory in Fish Otoliths Reflects Natal Origin of Atlantic Herring (Clupea harengus) From Baltic Sea Juvenile Areas

Despite centuries of human exploitation and research on Atlantic herring (Clupea harengus) in Europe, there is still much uncertainty on where major nursery areas are located. However, understanding the quantitative contribution of particular coastal systems to adult fish populations is of utmost importance to secure sustainable fish resources. Routinely, marker elements indicating certain hydrological conditions, which are incorporated into calcified structures, the so-called otoliths, are used to trace the origin of fish. However, as in the Baltic Sea, small and large scale salinity gradients potentially masking specific salinity signals. Based on the entire elemental inventory of the otolith core region, indicating the chemical signature of the spawning area, we developed a unique elemental fingerprinting index (EFI), allowing comparisons of multi-elemental chemical signatures from within and between herring juvenile areas. Our results show significantly distinct chemical “fingerprints” on the scale of particular bays and estuaries, which were not detectable with the usual marker elements. We further demonstrate that heavy metals levels drive the potential to distinguish natal origin of herring. These findings provide an essential baseline for further studies on the impact of small scale productivity for exploited fish resources and central components of marine food webs

Late Quaternary changes in moisture availability and weathering intensity on the central Tibetan Plateau indicated by chemical signatures of ostracod shells

High-resolution multi-proxy records from two lakes on the southern Tibetan Plateau, Nam Co and Tangra Yumco, are used to infer long-term variations in the Asian monsoon system with a novel set of ostracod shell chemistry proxies. We track the moisture evolution since the Last Glacial Maximum using the trace element, rare earth element (REE) and stable isotope composition of ostracod shells. The sediment records covering the past 18.8 cal. ka BP and 17.4 cal. ka BP, respectively, demonstrate the suitability of REEs as indicators of weathering intensity and thus hydrological changes and moisture sources in the catchment. In Nam Co, high concentrations of light REEs between 14 and 13 cal. ka BP suggest an increased drainage from the glaciated Nyainqêngtanglha Mountains in the south, pointing to meltwater input. REEs in ostracod shells therefore provide additional information on water sources critical for the interpretation of stable isotope records. Mg/Ca, Sr/Ca, and Ba/Ca ratios reflect salinity and thus changes in effective moisture. Asynchronous behavior of Mg/Ca, Sr/Ca, and Ba/Ca ratios are controlled by changes in dominance of precipitating carbonate minerals in the lake. Synchronous behavior reflects calcite precipitation, indicating low-Mg/Ca warm-wet conditions. Constantly low Sr/Ca ratios reflect aragonite precipitation, indicating high-Mg dry conditions. Increased Sr/Ca and Ba/Ca relative to Mg/Ca ratios show monohydrocalcite precipitation, indicating high-Mg/Ca cold-dry conditions. Furthermore, Fe/Ca, Mn/Ca and U/Ca ratios in ostracods reflect changes in oxygen saturation in lake bottom waters controlled by lake level and microbial activity. The paleoclimate histories reconstructed from Nam Co and Tangra Yumco show high similarity throughout the late Quaternary. We identified two major dry periods, corresponding to Heinrich 1 and the Younger Dryas, followed by strengthening in Indian summer monsoon precipitation. The early Holocene is characterized by a moisture maximum, reflecting abundant water supply by a strong ISM. A time-delayed shift to dry conditions occurred at 2.6 cal. ka BP at Tangra Yumco, and at 2 cal. ka BP at Nam Co, resulting in decreasing lake levels, caused by weakened monsoon intensity due to a southeastward migration of the ISM-Westerly boundary with an estimated velocity of approximately 600 m per year

Unravelling biocultural population structure in 4th/3rd century BC Monterenzio Vecchio (Bologna, Italy) through a comparative analysis of strontium isotopes, non-metric dental evidence, and funerary practices

The 4th century BC marks the main entrance of Celtic populations in northern Italy. Their arrival has been suggested based on the presence of Celtic customs in Etruscan mortuary contexts, yet up to now few bioarchaeological data have been examined to support or reject the arrival of these newcomers. Here we use strontium isotopes, non-metric dental traits and funerary patterns to unravel the biocultural structure of the necropolis of Monterenzio Vecchio (Bologna, Italy). Subsamples of our total sample of 38 individuals were analyzed based on different criteria characterizing the following analyses: 1) strontium isotope analysis to investigate migratory patterns and provenance; 2) non-metric dental traits to establish biological relationships between Monterenzio Vecchio, 13 Italian Iron age necropolises and three continental and non-continental Celtic necropolises; 3) grave goods which were statistically explored to detect possible patterns of cultural variability. The strontium isotopes results indicate the presence of local and non-local individuals, with some revealing patterns of mobility. The dental morphology reveals an affinity between Monterenzio Vecchio and Iron Age Italian samples. However, when the Monterenzio Vecchio sample is separated by isotopic results into locals and non-locals, the latter share affinity with the sample of non-continental Celts from Yorkshire (UK). Moreover, systematic analyses demonstrate that ethnic background does not retain measurable impact on the distribution of funerary elements. Our results confirm the migration of Celtic populations in Monterenzio as archaeologically hypothesized on the basis of the grave goods, followed by a high degree of cultural admixture between exogenous and endogenous traits. This contribution shows that combining different methods offers a more comprehensive perspective for the exploration of biocultural processes in past and present populations

Unravelling biocultural population structure in 4th/3rd century BC Monterenzio Vecchio (Bologna, Italy) through a comparative analysis of strontium isotopes, non-metric dental evidence, and funerary practices.

The 4th century BC marks the main entrance of Celtic populations in northern Italy. Their arrival has been suggested based on the presence of Celtic customs in Etruscan mortuary contexts, yet up to now few bioarchaeological data have been examined to support or reject the arrival of these newcomers. Here we use strontium isotopes, non-metric dental traits and funerary patterns to unravel the biocultural structure of the necropolis of Monterenzio Vecchio (Bologna, Italy). Subsamples of our total sample of 38 individuals were analyzed based on different criteria characterizing the following analyses: 1) strontium isotope analysis to investigate migratory patterns and provenance; 2) non-metric dental traits to establish biological relationships between Monterenzio Vecchio, 13 Italian Iron age necropolises and three continental and non-continental Celtic necropolises; 3) grave goods which were statistically explored to detect possible patterns of cultural variability. The strontium isotopes results indicate the presence of local and non-local individuals, with some revealing patterns of mobility. The dental morphology reveals an affinity between Monterenzio Vecchio and Iron Age Italian samples. However, when the Monterenzio Vecchio sample is separated by isotopic results into locals and non-locals, the latter share affinity with the sample of noncontinental Celts from Yorkshire (UK). Moreover, systematic analyses demonstrate that ethnic background does not retain measurable impact on the distribution of funerary elements. Our results confirm the migration of Celtic populations in Monterenzio as archaeologically hypothesized on the basis of the grave goods, followed by a high degree of cultural admixture between exogenous and endogenous traits. This contribution shows that combining different methods offers a more comprehensive perspective for the exploration of biocultural processes in past and present populations

Above- and belowground biodiversity jointly tighten the P cycle in agricultural grasslands

Experiments showed that biodiversity increases grassland productivity and nutrient exploitation, potentially reducing fertiliser needs. Enhancing biodiversity could improve P-use efficiency of grasslands, which is beneficial given that rock-derived P fertilisers are expected to become scarce in the future. Here, we show in a biodiversity experiment that more diverse plant communities were able to exploit P resources more completely than less diverse ones. In the agricultural grasslands that we studied, management effects either overruled or modified the driving role of plant diversity observed in the biodiversity experiment. Nevertheless, we show that greater above- (plants) and belowground (mycorrhizal fungi) biodiversity contributed to tightening the P cycle in agricultural grasslands, as reduced management intensity and the associated increased biodiversity fostered the exploitation of P resources. Our results demonstrate that promoting a high above- and belowground biodiversity has ecological (biodiversity protection) and economical (fertiliser savings) benefits. Such win-win situations for farmers and biodiversity are crucial to convince farmers of the benefits of biodiversity and thus counteract global biodiversity loss

MPI-DING reference glasses for in situ microanalysis: New reference values for element concentrations and isotope ratios

We present new analytical data of major and trace elements for the geological MPI-DING glasses KL2-G, ML3B-G, StHs6/80-G, GOR128-G, GOR132-G, BM90/21-G, T1-G, and ATHO-G. Different analytical methods were used to obtain a large spectrum of major and trace element data, in particular, EPMA, SIMS, LA-ICPMS, and isotope dilution by TIMS and ICPMS. Altogether, more than 60 qualified geochemical laboratories worldwide contributed to the analyses, allowing us to present new reference and information values and their uncertainties (at 95% confidence level) for up to 74 elements. We complied with the recommendations for the certification of geological reference materials by the International Association of Geoanalysts (IAG). The reference values were derived from the results of 16 independent techniques, including definitive (isotope dilution) and comparative bulk (e.g., INAA, ICPMS, SSMS) and microanalytical (e.g., LA-ICPMS, SIMS, EPMA) methods. Agreement between two or more independent methods and the use of definitive methods provided traceability to the fullest extent possible. We also present new and recently published data for the isotopic compositions of H, B, Li, O, Ca, Sr, Nd, Hf, and Pb. The results were mainly obtained by high-precision bulk techniques, such as TIMS and MC-ICPMS. In addition, LA-ICPMS and SIMS isotope data of B, Li, and Pb are presented. Copyright 2006 by the American Geophysical Union