Metal-rich organic matter and hot continental passive margin: drivers for Devonian copper-cobalt-germanium mineralization in dolomitized reef-bearing carbonate platform.

The abundance and types of reef-bearing carbonate platforms reflect the evolution of Devonian climate, with conspicuous microbial-algal reefs in the warm Early and Late Devonian and sponge-coral reefs in the cooler Middle Devonian. A dolomitized Wenlock-Lower Devonian microbial-algal reef-bearing carbonate platform hosts epigenetic copper-cobalt-germanium (Cu-Co-Ge) sulfide mineralization at Ruby Creek-Bornite in the Brooks Range, Alaska. Here, we present rhenium-osmium (Re-Os) radiometric ages and molybdenum and sulfur (δ98/95Mo = +2.04 to +5.48‰ and δ34S = -28.5 to -1.8‰) isotope variations for individual Cu-Co-Fe sulfide phases along the paragenetic sequence carrollite-bornite-pyrite. In the context of a hot, extensional passive margin, greenhouse conditions in the Early Devonian favored restriction of platform-top seawater circulation and episodic reflux of oxidized brines during growth of the carbonaceous carbonate platform. Molybdenum and sulfur isotope data signal the stepwise reduction of hot brines carrying Cu during latent reflux and geothermal circulation for at least ca. 15 million years from the Early Devonian until Cu-Co sulfide mineralization ca. 379-378 million years ago (Ma) in the Frasnian, Late Devonian (weighted mean of Re-Os model ages of carrollite at 379 ± 15 Ma [n = 4]; Re-Os isochron age of bornite at 378 ± 15 Ma [n = 6]). On the basis of petrographic relationships between sulfides and solid bitumen, and the Mo and S isotope data for sulfides, we imply that the endowment in critical metals (e.g., Co, Ge, Re) in the Ruby Creek-Bornite deposit is linked to the activity of primary producers that removed trace metals from the warm Early Devonian seawater and concentrated Co, Ge, and Re in algal-bacterial organic matter in carbonate sediments. Supplementary Information: The online version contains supplementary material available at 10.1007/s00126-022-01123-1.

Stable Isotope Analysis of Greenhouse Gases Requires Analyte Preconcentration.

Nitrous oxide (N2O) is an important trace gas contributing to global warming and depletion of ozone in the stratosphere. Its increasing abundance is caused mainly by anthropogenic sources, such as application of fertilizers in agriculture or emissions from industry. To understand the N2O global budget, its sources and sinks need to be well-described and quantified. In this project, a new method for N2O source appointment was developed that can help with this task. The method is based on analysis of the eight most abundant isotopic molecules of N2O, using quantum cascade laser absorption spectroscopy (QCLAS). The applicability of the method towards the N2O biogeochemical cycle was demonstrated on a prominent N2O source (bacterial denitrification) and the most important N2O sink (UV photolysis) on samples prepared in laboratory experiments. An extension of the QCLAS method to natural samples can be achieved by hyphenation with a preconcentration technique that increases concentration of the analyte and standardizes the sample matrix. This article provides an overview of currently applied preconcentration techniques in the field of greenhouse-gas analysis and a description of the preconcentration device TREX that will be employed in future projects with the developed QCLAS method.

First investigation and absolute calibration of clumped isotopes in N2 O by mid-infrared laser spectroscopy.

RATIONALE: Unravelling the biogeochemical cycle of the potent greenhouse gas nitrous oxide (N2 O) is an underdetermined problem in environmental sciences due to the multiple source and sink processes involved, which complicate mitigation of its emissions. Measuring the doubly isotopically substituted molecules (isotopocules) of N2 O can add new opportunities to fingerprint and constrain its cycle. METHODS: We present a laser spectroscopic technique to selectively and simultaneously measure the eight most abundant isotopocules of N2 O, including three doubly substituted species - so called "clumped isotopes". For the absolute quantification of individual isotopocule abundances, we propose a new calibration scheme that combines thermal equilibration of a working standard gas with a direct mole fraction-based approach. RESULTS: The method is validated for a large range of isotopic composition values by comparison with other established methods (laser spectroscopy using conventional isotopic scale and isotope ratio mass spectrometry). Direct intercomparison with recently developed ultrahigh-resolution mass spectrometry shows clearly the advantages of the new laser technique, especially with respect to site specificity of isotopic substitution in the N2 O molecule. CONCLUSIONS: Our study represents a new methodological basis for the measurements of both singly substituted and clumped N2 O isotopes. It has a high potential to stimulate future research in the N2 O community by establishing a new class of reservoir-insensitive tracers and molecular-scale insights.

Quantifying Isotopic Signatures of N2O Using Quantum Cascade Laser Absorption Spectroscopy.

Nitrous oxide, N2O, is the environmentally most relevant constituent of the biogeochemical nitrogen cycle. Human activities, e.g. the agricultural use of mineral fertilizers, accelerate nitrogen transformations, leading to higher emissions of this strong greenhouse gas. Investigating the stable isotopic composition of N2O provides a better understanding of formation mechanisms to disentangle its variable source and sink processes. Mid-infrared (mid-IR) laser spectroscopy is a highly attractive technique to analyze N2O isotopocules based on their specific ro-vibrational absorption characteristics. Specifically, quantum cascade laser absorption spectroscopy (QCLAS) in combination with preconcentration has shown to be powerful for simultaneous and high-precision analysis of the main N2O isotopocules. Recently, in the scope of my PhD project, we have been advancing this analytical technique for the analysis of the very rare doubly substituted N2O isotopic species 15N14N18O, 14N15N18O, and 15N15N16O, also known as clumped isotopes. Currently, we are investigating the potential of these novel isotopic tracers to track the complex N2O production and consumption pathways. Improved understanding of the nitrogen cycle will be a major step towards N2O emission reduction.

Carbonate clumped isotope analyses with the long-integration dual-inlet (LIDI) workflow: scratching at the lower sample weight boundaries.

RATIONALE: Clumped isotope analyses (Δ47 ) of carbonates by dual inlet (DI) mass spectrometry require long integration times to reach the necessary high precision due to the low abundance of the rare isotopologue 13 C18 O16 O. Traditional DI protocols reach this only with large amounts of sample and/or a large number of replicates as a large portion of the analyte gas is wasted. We tested an improved analytical workflow that significantly reduces the sample sizes and total analysis time per sample while preserving precision and accuracy. METHODS: We implemented the LIDI (long-integration dual-inlet) protocol to measure carbonates in micro-volume mode using a Kiel IV carbonate device coupled to a Thermo Scientific 253 Plus isotope ratio mass spectrometer without the new 1013 ohm amplifier technology. The LIDI protocol includes a single measurement of the sample gas (600 s integration) followed by a single measurement of the working gas (WG) with the same integration time. RESULTS: The Δ47 measurements of four calcite standards over a period of 5 weeks demonstrate excellent long-term stability with a standard deviation of ±0.021 to ±0.025 ‰ for the final values of the individual aliquots. The Δ47 analyses of a coral, four foraminifera and a calcite precipitated in the laboratory demonstrate that 14 replicates of 90 to 120 µg are sufficient to achieve an external precision of ±0.007 ‰ (1SE) or of ±0.013 ‰ at the 95% confidence level. CONCLUSIONS: This study demonstrates that by using a Kiel IV-253 Plus system with LIDI it is possible to achieve the same analytical precision as conventional DI measurements with at least a factor of 40 less sample material. With the new 1013 ohm resistor technology there is the potential to reduce the required sample material even more. This opens new avenues of research in paleoceanography, paleoclimatology, low-temperature diagenesis and other currently sample size limited applications. Copyright © 2017 John Wiley & Sons, Ltd.

Biosignatures in chimney structures and sediment from the Loki's Castle low-temperature hydrothermal vent field at the Arctic Mid-Ocean Ridge.

We investigated microbial life preserved in a hydrothermally inactive silica­barite chimney in comparison with an active barite chimney and sediment from the Loki's Castle low-temperature venting area at the Arctic Mid-Ocean Ridge (AMOR) using lipid biomarkers. Carbon and sulfur isotopes were used to constrain possible metabolic pathways. Multiple sulfur (dδ34S, Δ33S) isotopes on barite over a cross section of the extinct chimney range between 21.1 and 22.5 % in δ34S, and between 0.020 and 0.034 % in Δ33S, indicating direct precipitation from seawater. Biomarker distributions within two discrete zones of this silica­barite chimney indicate a considerable difference in abundance and diversity of microorganisms from the chimney exterior to the interior. Lipids in the active and inactive chimney barite and sediment were dominated by a range of 13C-depleted unsaturated and branched fatty acids with δ13C values between -39.7 and -26.7 %, indicating the presence of sulfur-oxidizing and sulfate-reducing bacteria. The majority of lipids (99.5 %) in the extinct chimney interior that experienced high temperatures were of archaeal origin. Unusual glycerol monoalkyl glycerol tetraethers (GMGT) with 0­4 rings were the dominant compounds suggesting the presence of mainly (hyper-) thermophilic archaea. Isoprenoid hydrocarbons with δ13C values as low as -46 % also indicated the presence of methanogens and possibly methanotrophs.

Long-term performance of the Kiel carbonate device with a new correction scheme for clumped isotope measurements.

RATIONALE: Carbonate clumped isotope thermometry is a powerful new technique increasingly used in many fields in earth science. Recently, it has been shown that clumped isotope measurements can be performed with a Kiel carbonate preparation device and micro-volume analyses, allowing measurements of small (1.5-2 mg) carbonate samples. However, common data correction schemes rely on measurements of gases prepared offline, potentially leading to unrecognized biases in the results. METHODS: We propose a new correction scheme for the Kiel device method including: (1) A pressure-sensitive baseline correction (PBL) of the raw beam signals; (2) Transfer of data to the absolute reference frame; (3) Correction for acid fractionation; (4) Correction for average standard offsets; (5) When necessary, correction for Δ47 scale compression based on offsets among standards with different ordering state. The long-term performance of the new scheme was tested with a large set of standard measurements (N = 432) obtained over the course of 15 months. RESULTS: The PBL correction reliably removes composition-dependent artifacts, which are commonly corrected for with gas measurements, and offsets observed in micro-volume measurements when ion beams are imbalanced. We show that the shape of the PBL can vary strongly and needs to be properly characterized. Combined PBL and standard correction resulted in long-term stability with standard deviations in Δ47 of 0.012-0.016 ‰ for the five standards over the whole period, close to the average error of 0.011 ‰ observed for individual measurements consisting of 10 replicate analyses. CONCLUSIONS: Our correction scheme eliminates the need for routine gas measurements, allowing for equal treatment of samples and standards with the Kiel device setup. While the PBL and standard data obtained over 15 months reveal variable mass spectrometer behavior, they provide a robust means of correction, yielding reproducible results from small carbonate samples in the long term.

A modified procedure for gas-source isotope ratio mass spectrometry: the long-integration dual-inlet (LIDI) methodology and implications for clumped isotope measurements.

RATIONALE: High-precision stable isotope measurements in gas-source isotope ratio mass spectrometry are generally carried out by repeated comparison of the composition of an unknown sample with that of a working gas (WG) through a dual-inlet (DI). Due to the established DI protocols, however, most of the sample gas is wasted rather than measured, which is a major problem when sample size is limited. Here we propose a new methodology allowing the measurement of a much larger portion of the available sample. METHODS: We tested a new measurement protocol, the long-integration dual-inlet (LIDI) method, which consists of a single measurement of the sample for 200 to 600 seconds followed by a single measurement of the WG. The isotope ratios of the sample are calculated by comparison of the beam ratios of the WG and sample at equivalent intensities of the major ion beam. RESULTS: Three isotopically very different CO2 samples were analyzed. The LIDI measurements of large samples (50 to 100 µmol of CO2) measured at quasi-constant beam sizes, and of small samples (1.5 to 2 µmol of CO2) measured in micro-volume mode, generated results that are indistinguishable from the standard DI measurements for carbon, oxygen and clumped isotope compositions. The external precision of Δ47 using the LIDI protocol (~±0.007‰) is similar to that of the state of the art DI measurements. CONCLUSIONS: For traditional and clumped isotope measurements of CO2, the LIDI protocol allows the measurement of a much larger portion of the sample gas rather than only ~20% of it. In addition, the sample can be measured at higher signal intensity and for longer time, allowing the measurement of smaller samples while preserving precision. We suggest that other gases commonly used for stable isotope measurements with gas-source mass spectrometry would also benefit from this new protocol.

An archaeobotanical and stable isotope approach to changing agricultural practices in the NW Mediterranean region around 4000 BC.

It has recently been observed, that a change in the crop spectrum happened during the so-called Middle Neolithic in France at ca. 4000 BC. An agricultural system based on free-threshing cereals (naked wheat and naked barley) seems to shift to one based on glume wheats. This is a major change for traditional farmers and this paper aims to shed light on its possible causes. Here we describe the results of new investigations in a key area for the understanding of this process: the NW Mediterranean arch, where free-threshing cereals are the main cultivars since ca. 5100 BC. New data confirm that the shift towards glume wheats is also observed in some sites of the NE of the Iberian Peninsula and that among the glume wheats that spread at ca. 4000 BC we should not only consider emmer and einkorn but also Timopheevi's wheat. Stable isotope analyses indicate no major decrease in soil fertility or alterations in local precipitation regimes. The agricultural change may be the result of a combination of the spread of damaging pests for free-threshing cereals and presumably new networks being developed with the North-eastern part of Italy and the Balkans.

Anthropogenic Eutrophication Drives Major Food Web Changes in Mwanza Gulf, Lake Victoria.

Discerning ecosystem change and food web dynamics underlying anthropogenic eutrophication and the introduction of non-native species is necessary for ensuring the long-term sustainability of fisheries and lake biodiversity. Previous studies of eutrophication in Lake Victoria, eastern Africa, have focused on the loss of endemic fish biodiversity over the past several decades, but changes in the plankton communities over this same time remain unclear. To fill this gap, we examined sediment cores from a eutrophic embayment, Mwanza Gulf, to determine the timing and magnitude of changes in the phytoplankton and zooplankton assemblages over the past century. Biogeochemical proxies indicate nutrient enrichment began around ~ 1920 CE and led to rapid increases in primary production, and our analysis of photosynthetic pigments revealed three zones: pre-eutrophication (prior to 1920 CE), onset of eutrophication with increases in all pigments (1920-1990 CE), and sustained eutrophication with cyanobacterial dominance (1990 CE-present). Cladoceran remains indicate an abrupt decline in biomass in ~ 1960 CE, in response to the cumulative effects of eutrophication and lake-level rise, preceding the collapse of haplochromine cichlids in the 1980s. Alona and Chydorus, typically benthic littoral taxa, have remained at relatively low abundances since the 1960s, whereas the abundance of Bosmina, typically a planktonic taxon, increased in the 1990s concurrently with the biomass recovery of haplochromine cichlid fishes. Overall, our results demonstrate substantial changes over the past century in the biomass structure and taxonomic composition of Mwanza Gulf phytoplankton and zooplankton communities, providing a historical food web perspective that can help understand the recent changes and inform future resource management decisions in the Lake Victoria ecosystem. Supplementary Information: The online version contains supplementary material available at 10.1007/s10021-024-00908-x.

Background effects on Faraday collectors in gas-source mass spectrometry and implications for clumped isotope measurements.

RATIONALE: The measurement of the abundances of minor isotopologues by mass spectrometry requires correction of subtle non-linearities in the mass spectrometer that cause deviations in the relationship between actual and measured isotope ratios. Here we show that negative backgrounds on the Faraday cups recording the minor ion beams are the cause of the observed non-linearities in the measurement of CO(2) isotopologues, and propose a new correction procedure for clumped isotope measurements. METHODS: We carefully investigated the cause of non-linearity effects in the measurement of the abundance of (13)C(18)O(16)O, a minor isotopologue of CO(2) with m/z 47, on two different mass spectrometers. By using gases of different composition with close to stochastic and with non-random distribution of isotopes we demonstrate that the apparent dependence of the excess abundance of the isotopologue of m/z 47 on the bulk isotopic composition of CO(2) is due to a background interference that is linearly dependent on the partial pressure of the gas in the source of the mass spectrometer. CONCLUSIONS: Background determination with gas flowing into the source of the mass spectrometer is necessary for accurate clumped isotope measurements of CO(2). Background corrections can be performed accurately if the slit width of the m/z 44 Faraday cup significantly exceeds that of the one for m/z 47, using a correlation between m/z 44 signal intensity and the corresponding minimum in m/z 47 background. We propose two new correction schemes that reduce the time-consuming measurement of gases of different bulk isotopic compositions. These findings may also be relevant for the measurement of other rare isotopologues by mass spectrometry.

In-situ experiment reveals CO2 enriched fluid migration in faulted caprock.

The sealing characteristics of the geological formation located above a CO2 storage reservoir, the so-called caprock, are essential to ensure efficient geological carbon storage. If CO2 were to leak through the caprock, temporal changes in fluid geochemistry can reveal fundamental information on migration mechanisms and induced fluid-rock interactions. Here, we present the results from a unique in-situ injection experiment, where CO2-enriched fluid was continuously injected in a faulted caprock analogue. Our results show that the CO2 migration follows complex pathways within the fault structure. The joint analysis of noble gases, ion concentrations and carbon isotopes allow us to quantify mixing between injected CO2-enriched fluid and resident formation water and to describe the temporal evolution of water-rock interaction processes. The results presented here are a crucial complement to the geophysical monitoring at the fracture scale highlighting a unique migration of CO2 in fault zones.

Deciphering local and regional hydroclimate resolves contradicting evidence on the Asian monsoon evolution.

The winter and summer monsoons in Southeast Asia are important but highly variable sources of rainfall. Current understanding of the winter monsoon is limited by conflicting proxy observations, resulting from the decoupling of regional atmospheric circulation patterns and local rainfall dynamics. These signals are difficult to decipher in paleoclimate reconstructions. Here, we present a winter monsoon speleothem record from Southeast Asia covering the Holocene and find that winter and summer rainfall changed synchronously, forced by changes in the Pacific and Indian Oceans. In contrast, regional atmospheric circulation shows an inverse relation between winter and summer controlled by seasonal insolation over the Northern Hemisphere. We show that disentangling the local and regional signal in paleoclimate reconstructions is crucial in understanding and projecting winter and summer monsoon variability in Southeast Asia.

Stable isotope analysis of organic carbon in small (µg C) samples and dissolved organic matter using a GasBench preparation device.

The stable isotopes of organic matter can provide valuable information on carbon cycling dynamics, microbial metabolisms, and past climates. Since bulk measurements may mask dynamic changes to critical portions of the organic pool, researchers are increasingly isolating individual compounds for isotopic analysis. The amount of carbon isolated is frequently small, requiring specialized equipment for its analysis. We present a simple and accurate method to measure the δ(13)C values of µg-amounts of organic compounds and dissolved organic matter in freshwaters using wet oxidation and a GasBench II preparation device. Samples containing 3 µg C can be analyzed with a precision of <0.4‰. For samples containing 1.2 µg C, the precision is <0.8‰. The blank is estimated to be ~0.2 µg C. The accuracy of the method is demonstrated for a wide range of compounds including those that are difficult to oxidize such as humic acid and phthalic acid. The δ(13)C values of DOC from river and riparian ground water determined by this method are comparable with those determined with an elemental analyzer on freeze-dried samples of DOC. The low detection limit and the ease with which it can be combined with isolation techniques such as liquid chromatography make this technique attractive for the off-line analysis of organic compounds, and open new possibilities for the development of methodologies for compound-specific carbon isotope analysis of complex mixtures separated by HPLC.

A simple method for the removal of dissolved organic matter and δ15N analysis of NO3(-) from freshwater.

RATIONALE: Stable isotopes of nitrogen in nitrate (NO(3)(-)) are frequently used to identify nitrate sources and to study nitrogen (N) transformation processes, but the measurement methods available are generally rather labor intensive and/or costly, and dissolved organic matter (DOM) can interfere with the δ(15)N signature of nitrate. We therefore have developed a simple cleanup procedure for freshwater samples with low nitrate and high DOM concentrations. METHODS: Nitrate and DOM are extracted from a freeze-dried water sample by using a concentrated sodium hydroxide solution. By the subsequent addition of acetone, two liquid layers are formed, and nitrate migrates into the acetone while DOM remains in the concentrated NaOH solution, thus separating the nitrate from the DOM. For nitrogen isotope analysis, purified nitrate salts are combusted at 1030 °C to produce N(2) gas in an elemental analyzer (EA) coupled to an isotope ratio mass spectrometer (IRMS). RESULTS: With this novel technique up to 99% of DOM could be removed from river water and soil solutions. The method has been tested for sample amounts as small as 4 µmol NO(3)(-) with a precision of <0.1‰ (1SD). Nitrate standards are reproduced accurately without any blank correction. CONCLUSIONS: The benefits of this method are the lack of interferences derived from DOM on the δ(15)N signature and the ease of sample preparation.

Bacterial, archaeal and fungal succession in the forefield of a receding glacier.

Glacier forefield chronosequences, initially composed of barren substrate after glacier retreat, are ideal locations to study primary microbial colonization and succession in a natural environment. We characterized the structure and composition of bacterial, archaeal and fungal communities in exposed rock substrates along the Damma glacier forefield in central Switzerland. Soil samples were taken along the forefield from sites ranging from fine granite sand devoid of vegetation near the glacier terminus to well-developed soils covered with vegetation. The microbial communities were studied with genetic profiling (T-RFLP) and sequencing of clone libraries. According to the T-RFLP profiles, bacteria showed a high Shannon diversity index (H) (ranging from 2.3 to 3.4) with no trend along the forefield. The major bacterial lineages were Proteobacteria, Actinobacteria, Acidobacteria, Firmicutes and Cyanobacteria. An interesting finding was that Euryarchaeota were predominantly colonizing young soils and Crenarchaeota mainly mature soils. Fungi shifted from an Ascomycota-dominated community in young soils to a more Basidiomycota-dominated community in old soils. Redundancy analysis indicated that base saturation, pH, soil C and N contents and plant coverage, all related to soil age, correlated with the microbial succession along the forefield.

Oxygen isotopes unravel the role of microorganisms in phosphate cycling in soils.

Phosphorus (P) is considered the ultimate limiting nutrient for plants in most natural systems and changes in the distribution of inorganic and organic P forms during soil development have been well documented. In particular, microbial activity has been shown to be an important control on P cycling but its contribution in building up the pool of plant-available P during soil development is still poorly quantified. To determine the importance of different biological processes on P cycling, we analyzed the isotopic composition of oxygen in phosphate (δ(18)O-Pi) from the parent material, soil microorganisms, the available P pool, and from the vegetation along a 150-year soil chronosequence of a glacier forefield. Our results show that at all sites, δ(18)O-Pi of microbial Pi is within the range expected for the temperature-dependent equilibrium between phosphate and water. In addition, the isotopic signature of available Pi is close to the signature of microbial Pi, independently of the contribution of parent material Pi, vegetation Pi or Pi released from organic matter mineralization. Thus, we show that phosphate is cycled through soil microorganisms before being released to the available pool. This isotopic approach demonstrates for the first time in the field and over long time scales, and not only through controlled experiments, the role of the microbial activity in cycling of P in soils.

Archaeobotanical and isotopic analyses of waterlogged remains from the Neolithic pile-dwelling site of Zug-Riedmatt (Switzerland): Resilience strategies of a plant economy in a changing local environment.

The excellent preservation of the waterlogged botanical remains of the multiphase Neolithic pile-dwelling site of Zug-Riedmatt (Central Switzerland) yielded an ideal dataset to delve into the issue of plant economy of a community spanning several decades. The study identified a major change in crops where oil plants played a key role in the site's initial phase before being supplanted over the course of a few decades by naked wheat, barley and pea. Wild plants continued to be gathered albeit in different proportions. In the latest settlement phase, the changes in the local vegetation and in the values of the analyses of carbon stable isotopes suggest a less humid environment. The hypothesis is that the changes perceived in the plant economy represent a resilience strategy adopted by the inhabitants in reaction to short term local climatic alterations. The two types of soil sampling techniques (monolith and bulk) allowed comparing these results. While the density of plant remains appears to be underestimated among the samples collected by the monolith technique, the proportions of economic taxa remain unaffected. The findings thus reveal that when the bulk samplings are distributed carefully throughout multiphase sites and avoid mixing stratigraphical units, and if the samplings are representative of all archaeological features from a whole area, then each of the two techniques offer analogous results.

Deposit-feeding worms control subsurface ecosystem functioning in intertidal sediment with strong physical forcing.

Intertidal sands are global hotspots of terrestrial and marine carbon cycling with strong hydrodynamic forcing by waves and tides and high macrofaunal activity. Yet, the relative importance of hydrodynamics and macrofauna in controlling these ecosystems remains unclear. Here, we compare geochemical gradients and bacterial, archaeal, and eukaryotic gene sequences in intertidal sands dominated by subsurface deposit-feeding worms (Abarenicola pacifica) to adjacent worm-free areas. We show that hydrodynamic forcing controls organismal assemblages in surface sediments, while in deeper layers selective feeding by worms on fine, algae-rich particles strongly decreases the abundance and richness of all three domains. In these deeper layers, bacterial and eukaryotic network connectivity decreases, while percentages of clades involved in degradation of refractory organic matter, oxidative nitrogen, and sulfur cycling increase. Our findings reveal macrofaunal activity as the key driver of biological community structure and functioning, that in turn influence carbon cycling in intertidal sands below the mainly physically controlled surface layer.

Building an isoscape based on tooth enamel for human provenance estimation in Brazil.

In this study, we present a correlation between δ18OC values of carbonate in tooth enamel samples from the modern Brazilian population and the available δ18ODW data for the meteoric water from the Global Network of Isotopes in Precipitation (GNIP). Tooth enamel from 119 Brazilian individuals from five different regions of the country were analyzed. The δ18OC isoscape obtained is in good agreement with the isoscape based on regional meteoric and drinking water. The regression matrix obtained for the δ18O values of the carbonate tooth enamel and meteoric water was used to build an isoscape using the regression-kriging approach. Our data show that Brazil can be divided in two main regions with respect to the δ18O values of the carbonate tooth enamel: (1) the most easterly part of the northeast region, which is characterized by a warm and dry climate and (2) the remainder of the country, stretching from the Amazon rain forest to the more southernly regions. The data herein reported can be used for forensic purposes related to human identification.