Sulfur disproportionation in deep COHS slab fluids drives mantle wedge oxidation.

Sulfur degassed at volcanic arcs calls for dissolved sulfate ions (S6+) released by subduction-zone fluids, oxidizing (in association with carbon) the subarc mantle, but sulfur speciation in subduction fluids at subarc depths remains unclear. We apply electrolytic fluid thermodynamics to model the dissolution behavior of pyrite in metacarbonate sediments as a function of P, T and rock redox state up to 4.3 gigapascals and 730°C. At subarc depth and the redox conditions of the fayalite-magnetite-quartz oxygen buffer, pyrite dissolution releases oxidized sulfur in fluids by disproportionation into sulfate, bisulfite, and sulfide species. These findings indicate that oxidized, sulfur-rich carbon-oxygen-hydrogen-sulfur (COHS) fluids form within subducting slabs at depths greater than 100 kilometers independent from slab redox state and that sulfur can be more effective than the concomitantly dissolved carbon at oxidizing the mantle wedge, especially when carbonates are stable.

Spatially resolved CO2 carbon stable isotope analyses at the microscale using Raman spectroscopy.

Measuring the carbon stable isotope ratio (13C/12C, expressed as δ13CCO2) in geogenic CO2 fluids is a crucial geochemical tool for studying Earth's degassing. Carbon stable isotope analysis is traditionally performed by bulk mass spectrometry. Although Raman spectroscopy distinguishes 12CO2 and 13CO2 isotopologue bands in spectra, using this technique to determine CO2 isotopic signature has been challenging. Here, we report on in-situ non-destructive analyses of the C stable isotopic composition of CO2, applying a novel high-resolution Raman configuration on 42 high-density CO2 fluid inclusions in mantle rocks from the Lake Tana region (Ethiopia) and El Hierro (Canary Islands). We collected two sets of three spectra with different acquisition times at high spectral resolution in each fluid inclusion. Among the 84 sets of spectra, 58 were characterised by integrated 13CO2/12CO2 band area ratios with reproducibility better than 4‰. Our results demonstrate the determination of δ13CCO2 by Raman spectroscopy in individual fluid inclusions with an error better than 2.5 ‰, which satisfactorily matches bulk mass spectrometry analyses in the same rock samples, supporting the accuracy of the measurements. We thus show that Raman Spectroscopy can provide a fundamental methodology for non-destructive, site-specific, and spatially resolved carbon isotope labelling at the microscale.

Plastic debris in lakes and reservoirs.

Plastic debris is thought to be widespread in freshwater ecosystems globally1. However, a lack of comprehensive and comparable data makes rigorous assessment of its distribution challenging2,3. Here we present a standardized cross-national survey that assesses the abundance and type of plastic debris (>250 µm) in freshwater ecosystems. We sample surface waters of 38 lakes and reservoirs, distributed across gradients of geographical position and limnological attributes, with the aim to identify factors associated with an increased observation of plastics. We find plastic debris in all studied lakes and reservoirs, suggesting that these ecosystems play a key role in the plastic-pollution cycle. Our results indicate that two types of lakes are particularly vulnerable to plastic contamination: lakes and reservoirs in densely populated and urbanized areas and large lakes and reservoirs with elevated deposition areas, long water-retention times and high levels of anthropogenic influence. Plastic concentrations vary widely among lakes; in the most polluted, concentrations reach or even exceed those reported in the subtropical oceanic gyres, marine areas collecting large amounts of debris4. Our findings highlight the importance of including lakes and reservoirs when addressing plastic pollution, in the context of pollution management and for the continued provision of lake ecosystem services.

Raman Spectroscopy for the Analysis of Microplastics in Aquatic Systems.

Raman spectroscopy is gaining ground in the analysis of microplastics, especially due to its high spatial resolution that allows the investigation of small plastic particles, whose numeric abundance is argued to be particularly relevant in aquatic systems. Here, we aimed at outlining the status of Raman analysis of microplastics from aquatic systems, highlighting the advantages and the drawbacks of this technique and critically presenting tools and ways to effectively employ this instrument and to improve the spectra obtained and their interpretation. In particular, we summarized procedural information for the use of Raman spectroscopy, and we discussed issues linked to fluorescence interference and the analysis of weathered polymers, which may complicate the interpretation of Raman signatures. In this context, a deep understanding of the different plastic polymers and their Raman peaks and chemical fingerprints is fundamental to avoid misidentification. Therefore, we provided a catalog with detailed information about peaks of most common plastic polymers, and this represents, to the best of our knowledge, the first comprehensive resource that systematically synthesized plastic Raman peaks. Additionally, we focused on plastic additives, which are contained in the majority of plastics. These compounds are often intense in Raman scattering and may partly or completely overlie the actual material types, resulting in the identification of additives alone or misidentification issue. For these reasons, we also presented a new R package "RamanMP" that includes a database of 356 spectra (325 of which are additives). This will help to foster the use of this technique, which is becoming especially relevant in microplastic analysis.

Interlaboratory Application of Raman CO2 Densimeter Equations: Experimental Procedure and Statistical Analysis Using Bootstrapped Confidence Intervals.

Raman spectroscopy has been used extensively to calculate CO2 fluid density in many geological environments, based on the measurement of the Fermi diad split (Δ; cm-1) in the CO2 spectrum. While recent research has allowed the calibration of several Raman CO2 densimeters, there is a limit to the interlaboratory application of published equations. These calculate two classes of density values for the same measured Δ, with a deviation of 0.09 ± 0.02 g/cm3 on average. To elucidate the influence of experimental parameters on the calibration of Raman CO2 densimeters, we propose a bottom-up approach beginning with the calibration of a new equation, to evaluate a possible instrument-dependent variability induced by experimental conditions. Then, we develop bootstrapped confidence intervals for density estimate of existing equations to move the statistical analysis from a sample-specific to a population level. We find that Raman densimeter equations calibrated based on spectra acquired with similar spectral resolution calculate CO2 density values lying within standard errors of equations and are suitable for the interlaboratory application. The statistical analysis confirms that equations calibrated at similar spectral resolution calculate CO2 densities equivalent at 95% confidence, and each Raman densimeter does have a limit of applicability, statistically defined by a minimum Δ value, below which the error in calculated CO2 densities is too high.

Gradual and selective trace-element enrichment in slab-released fluids at sub-arc depths.

The geochemical signature of magmas generated at convergent margins greatly depends on the nature of fluids and melts released during subduction. While major- and trace-elements transport capacity of ultrahigh pressure (UHP) hydrous-silicate melts has been investigated, little is known about solute enrichment and fractionation in UHP (>3.5-4 GPa) solute-rich aqueous fluids released along colder geothermal gradients. Here, we performed in situ LA-ICP-MS trace-element analyses on selected UHP prograde-to-peak fluid inclusions trapped in a kyanite-bearing quartzite from Sulu (China). The alkali-aluminosilicate-rich aqueous fluid released from the meta-sediments by dehydration reactions is enriched in LILE, U, Th, Sr, and REE. Inclusions trapped at increasing temperature (and pressure) preserve a gradual and selective trace-element enrichment resulting from the progressive dissolution of phengite and carbonate and the partial dissolution of allanite/monazite. We show that, at the investigated P-T conditions, aqueous fluids generated by dissolution of volatile-bearing minerals fractionate trace-element distinctly from hydrous-silicate melts, regardless of the source lithology. The orogenic/post-orogenic magmas generated in a mantle enriched by metasomatic processes involving either solute-rich aqueous fluids or hydrous-silicate melts released by the slab at UHP conditions can preserve evidence of the nature of these agents.

Diamond growth from organic compounds in hydrous fluids deep within the Earth.

At subduction zones, most diamonds form by carbon saturation in hydrous fluids released from lithospheric plates on equilibration with mantle rocks. Although organic molecules are predicted among dissolved species which are the source for carbon in diamonds, their occurrence is not demonstrated in nature, and the physical model for crustal diamond formation is debated. Here, using Raman microspectroscopy, I determine the structure of carbon-based phases inside fluid inclusions in diamond-bearing rocks from the Alps. The results provide direct evidence that diamond surfaces are coated by sp2-, and sp3-bonded amorphous carbon and functional groups of carboxylic acids (e.g., carboxyl, carboxylate, methyl, and methylene), indicating the geosynthesis of organic compounds in deep hydrous fluids. Moreover, this study suggests diamond nucleation via metastable molecular precursors. As a possible scenario, with carbon saturation by reduction of carboxylate groups, I consider tetrahedral H-terminated C groups as templates for the growth of sp3-structured carbon.

Active carbon sequestration in the Alpine mantle wedge and implications for long-term climate trends.

The long-term carbon budget has major implications for Earth's climate and biosphere, but the balance between carbon sequestration during subduction, and outgassing by volcanism is still poorly known. Although carbon-rich fluid inclusions and minerals are described in exhumed mantle rocks and xenoliths, compelling geophysical evidence of large-scale carbon storage in the upper mantle is still lacking. Here, we use a geophysical surface-wave seismic tomography model of the mantle wedge above the subducted European slab to document a prominent shear-wave low-velocity anomaly at depths greater than 180 km. We propose that this anomaly is generated by extraction of carbonate-rich melts from the asthenosphere, favoured by the breakdown of slab carbonates and hydrous minerals after cold subduction. The resulting transient network of carbon-rich melts is frozen in the mantle wedge without producing volcanism. Our results provide the first in-situ observational evidence of ongoing carbon sequestration in the upper mantle at a plate-tectonic scale. We infer that carbon sequestered during cold subduction may partly counterbalance carbon outgassed from ridges and oceanic islands. However, subducted carbon may be rapidly released during continental rifting, with global effects on long-term climate trends and the habitability of planet Earth.