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Oxic lake surface waters are frequently oversaturated with methane (C H4). The contribution to the global CH4 cycle is significant, thus leading to an increasing number of studies and stimulating debates. Here we show, using a mass balance, on a temperate, mesotrophic lake, that ~90% of CH4 emissions to the atmosphere is due to CH4 produced within the oxic surface mixed layer (SML) during the stratified period, while the often observed CH4 maximum at the thermocline represents only a physically driven accumulation. Negligible surface CH4 oxidation suggests that the produced 110 ± 60 nmol CH4 L-1 d-1 efficiently escapes to the atmosphere. Stable carbon isotope ratios indicate that CH4 in the SML is distinct from sedimentary CH4 production, suggesting alternative pathways and precursors. Our approach reveals CH4 production in the epilimnion that is currently overlooked, and that research on possible mechanisms behind the methane paradox should additionally focus on the lake surface layer. [ABSTRACT FROM AUTHOR]

Gold production from the northern Pataz district in the eastern Andean Cordillera of Peru has been sourced mainly from mesothermal quartz-carbonate-sulfide veins hosted by the Mississippian Pataz batholith. Gold is also found in basement-hosted veins underlying the batholith, in the Vijus-Santa Filomena area of the district. Both are located within a central horst; similar vein mineralogy and proximal phengitic white mica alteration are common to both. However, comb-textured quartz, the chemical compositions of bulk ore and sulfide minerals, and the presence of barite and siderite veins suggest that the basement-hosted veins formed at a shallower crustal level. Similar expressions of hydrothermal alteration associated with anomalous gold, As, Sb, and Tl are also present in the adjacent Lavasen graben, where alteration is intimately associated with volcanic processes that deposited the Mississippian Lavasen Volcanics. K-Ar and 40Ar-39Ar ages for hydrothermal illite from all three locations range between Mississippian and Late Triassic but are consistent with a single Mississippian hydrothermal event, if the data record a minimum age for original illite formation. The geologic setting, mineralization styles, and chemical data suggest a range of crustal depths, ranging from mesothermal batholith-hosted veins through shallow to intermediate depths for the Vijus-Santa Filomena area to a near-surface epithermal setting for the Misquichilca area. Telescoping of this 10- to 13-km crustal range into a 3-km topographic section of the Andes is attributed to syn- and postmineralization uplift and erosion. Sulfide-rich high-grade ore shoots and moderately saline fluid inclusions in the batholith-hosted veins are inconsistent with the original orogenic gold model and suggest a magmatic source component for the ore fluid, consistent with stable isotope (O, H, C, and S) compositions of quartz, illite, carbonates, and sulfides. The isotopic data suggest a mixed magmatic-meteoric ore fluid in the basement-hosted deposits of the Vijus-Santa Filomena area and the volcanic-hosted Misquichilca area. Both the Pataz batholith and the Esperanza Subvolcanic Complex are of the same Mississippian age as the hydrothermal alteration and mineralization. The Esperanza Subvolcanic Complex, comagmatic with the Lavasen Volcanics, contains cognate mineral clots from which a subjacent magma chamber can be inferred. It exhibits potassic, calc-silicate, and argillic alteration, and evidence for the evolution of an Fe-rich volatile phase. The Lavasen-Esperanza magma suite is ferroan and weakly alkaline, with A-type affinities. These features provide a conceptual genetic link with hydrothermal alteration associated with gold mineralization, including Fe (±As) sulfides, phengitic white mica, celadonite, Fe-rich carbonates, and less common Fe oxides. An oxidized intrusion-related model is proposed for gold and hydrothermal alteration in the northern Pataz district. [ABSTRACT FROM AUTHOR]

A detailed stratigraphical and geochemical analysis was performed on the upper part of the Maiolica Formation outcropping in the Breggia (southern Switzerland) and Capriolo sections (northern Italy). In these localities, the Maiolica Formation consists of well-bedded, partly siliceous, pelagic, micritic carbonate, which lodges numerous thin, dark and organic-rich layers. Stable-isotope, phosphorus, organic-carbon and a suite of redox-sensitive trace-metal contents (RSTE: Mo, U, Co, V and As) were measured. Higher densities of organic-rich layers were identified in the uppermost Hauterivian, lower Barremian and the Barremian-Aptian boundary intervals, whereas the upper Barremian interval and the interval immediately following the Barremian-Aptian boundary interval are characterized by lower densities of organic-rich layers. TOC contents, RSTE pattern and Corg:Ptot ratios indicate that most layers were deposited under dysaerobic rather than anaerobic conditions and that latter conditions were likely restricted to short intervals in the latest Hauterivian, the early Barremian and the pre-Selli early Aptian. Correlations are possible with organic-rich intervals in central Italy (the Gorgo a Cerbara section) and the Boreal northwest German Basin, and with the facies and drowning pattern in the evolution of the Helvetic segment of the northern Tethyan carbonate platform. Our data and correlations suggest that the latest Hauterivian witnessed the progressive installation of dysaerobic conditions in the Tethys, which went along with the onset in sediment condensation, phosphogenesis and platform drowning on the northern Tethyan margin, and which culminated in the Faraoni anoxic episode. This brief episode is followed by further episodes of dysaerobic conditions in the Tethys and the northwest German Basin, which became more frequent and progressively stronger in the late early Barremian. Platform drowning persisted and did not halt before the latest early Barremian. The late Barremian witnessed diminishing frequencies and intensities in dysaerobic conditions, which went along with the progressive installation of the Urgonian carbonate platform. Near the Barremian-Aptian boundary, the increasing density in dysaerobic episodes in the Tethyan and northwest German Basins is paralleled by a change towards heterozoan carbonate production on the northern Tethyan shelf. The following return to more oxygenated conditions is correlated with the second phase of Urgonian platform growth and the period immediately preceding and corresponding to the Selli anoxic episode is characterized by renewed platform drowning and the change to heterozoan carbonate production. Changes towards more humid climate conditions were likely the cause for the repetitive installation of dys- to anaerobic conditions in the Tethyan and Boreal basins and the accompanying changes in the evolution of the carbonate platform towards heterozoan carbonate-producing ecosystems and platform drowning. [ABSTRACT FROM AUTHOR]

Peatlands are permanent wetlands recognized for ecosystem services such as biodiversity conservation and carbon storage capacity. Little information is available about their response to global change, the reason why most Earth system climate models consider a linear increase in the release of greenhouse gases (GHG), such as CO 2 , with increasing temperatures. Nevertheless, numerous studies suggest that an increase in the temperature may not imply a decrease in photosynthesis and carbon storage rates if water availability is sufficient, the latter being under the control of local hydrology mechanisms. Mediterranean peatlands well illustrate this fact. Since they are groundwater-dependent, they are hydrologically resilient to the strong seasonality of hydroclimatic conditions, especially during the summer drought. In the present study, we demonstrate that, even if such peatlands release CO 2 into the atmosphere, they can maintain a carbon storage capacity. To this end, a geochemical study disentangles the origin and fate of carbon within a Mediterranean peatland at the watershed scale. Field parameters, major ions, dissolved organic and inorganic carbon content and associated δ 13 C values allow for characterizing the seasonality of hydrochemical mechanisms and carbon input from an alluvial aquifer (where rain, river, shallow, and deep groundwater flows are mixing) to the peatland. The inorganic and organic content of peat soil and δ 13 C values of total organic matter and CO 2 complete the dataset, making it possible to provide arguments in favour of lower organic matter oxidation compared to primary production. Overall, this study highlights the groundwater role in the fluxes of CO 2 at the peatland-atmosphere interface, and more broadly the need to understand the interactions between the water and carbon cycles to build better models of the future evolution of the global climate., Competing Interests: Declaration of competing interest S. Santoni reports financial support was provided by Cullettività di Corsica., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The fatty acids from cocoa butters of different origins, varieties, and suppliers and a number of cocoa butter equivalents (Illexao 30-61, Illexao 30-71, Illexao 30-96, Choclin, Coberine, Chocosine-Illipé, Chocosine-Shea, Shokao, Akomax, Akonord, and Ertina) were investigated by bulk stable carbon isotope analysis and compound specific isotope analysis. The interpretation is based on principal component analysis combining the fatty acid concentrations and the bulk and molecular isotopic data. The scatterplot of the two first principal components allowed detection of the addition of vegetable fats to cocoa butters. Enrichment in heavy carbon isotope ((13)C) of the bulk cocoa butter and of the individual fatty acids is related to mixing with other vegetable fats and possibly to thermally or oxidatively induced degradation during processing (e.g., drying and roasting of the cocoa beans or deodorization of the pressed fat) or storage. The feasibility of the analytical approach for authenticity assessment is discussed.

The authenticity of vegetable oils consumed in Slovenia and Croatia was investigated by carbon isotope analysis of the individual fatty acids by the use of gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS), and through carbon isotope analysis of the bulk oil. The fatty acids from samples of olive, pumpkin, sunflower, maize, rape, soybean, and sesame oils were separated by alkaline hydrolysis and derivatized to methyl esters for chemical characterization by capillary gas chromatography/mass spectrometry (GC/MS) prior to isotopic analysis. Enrichment in heavy carbon isotope ((13)C) of the bulk oil and of the individual fatty acids are related to (1) a thermally induced degradation during processing (deodorization, steam washing, or bleaching), (2) hydrolytic rancidity (lipolysis) and oxidative rancidity of the vegetable oils during storage, and (3) the potential blend with refined oil or other vegetable oils. The impurity or admixture of different oils may be assessed from the delta(13)C(16:0) vs. delta(13)C(18:1) covariations. The fatty acid compositions of Slovenian and Croatian olive oils are compared with those from the most important Mediterranean producer countries (Spain, Italy, Greece, and France).