Second-order Raman modes correlate with the electrical properties of reduced graphene oxide measured at the nanoscale by atomic force microscopy.

Abstract. The East Siberian Arctic Shelf (ESAS) is the broadest and shallowest continental shelf in the world. It is characterized by both the highest rate of coastal erosion in the world and a large riverine input of terrigenous dissolved organic matter (DOM). DOM plays a significant role in marine aquatic ecosystems. The chromophoric fraction of DOM (CDOM) directly affects the quantity and spectral quality of available light, thereby impacting both primary production and ultraviolet (UV) exposure in aquatic ecosystems. A multiyear study of CDOM absorption, fluorescence, and spectral characteristics was carried out over the vast ESAS in the summer–fall seasons. The paper describes observations accomplished at 286 stations and 1766 in situ high-resolution optical measurements distributed along the nearshore zone. Spatial and interannual CDOM dynamics over the ESAS were investigated, and driving factors were identified. It was shown that the atmospheric circulation regime is the dominant factor controlling CDOM distribution on the ESAS. This paper explores the possibility of using CDOM and its spectral parameters to identify the different biogeochemical regimes in the surveyed area. The analysis of CDOM spectral characteristics showed that the major part of the Laptev and East Siberian seas shelf is influenced by terrigenous DOM carried in riverine discharge. Western and eastern provinces of the ESAS with distinctly different DOM optical properties were also identified; a transition between the two provinces at around 165–170° E, also consistent with hydrological and hydrochemical data, is shown. In the western ESAS, a region of substantial river impact, the content of aromatic carbon within DOM remains almost constant. In the eastern ESAS, a gradual decrease in aromaticity percentage was observed, indicating contribution of Pacific-origin waters, where allochthonous DOM with predominantly aliphatic character and much smaller absorption capacity predominates. In addition, we found a stable tendency towards reduced concentrations of CDOM and dissolved lignin and an increase in spectral slope and slope ratio values eastward from the Lena River delta; the Lena is the main supplier of DOM to the eastern Arctic shelf. The strong positive correlation (r  =  0.97) between dissolved organic carbon (DOC) and CDOM values in the surface shelf waters influenced by terrigenous discharge indicates that it is feasible to estimate DOC content from CDOM fluorescence assessed in situ using a WETStar fluorometer. This approach is reliable over the salinity range of 3 to 24.5. The fact that there is little difference between predicted and observed parameters indicates that the approach is justified. The direct estimation of DOM optical characteristics in the surface ESAS waters provided by this multiyear study will also be useful for validating and calibrating remote sensing data.

Abstract. It has been suggested that increasing terrestrial water discharge to the Arctic Ocean may partly occur as submarine groundwater discharge (SGD), yet there are no direct observations of this phenomenon in the Arctic shelf seas. This study tests the hypothesis that SGD does exist in the Siberian Arctic Shelf seas, but its dynamics may be largely controlled by complicated geocryological conditions such as permafrost. The field-observational approach in the southeastern Laptev Sea used a combination of hydrological (temperature, salinity), geological (bottom sediment drilling, geoelectric surveys), and geochemical ( 224 Ra, 223 Ra, 228 Ra, and 226 Ra) techniques. Active SGD was documented in the vicinity of the Lena River delta with two different operational modes. In the first system, groundwater discharges through tectonogenic permafrost talik zones was registered in both winter and summer. The second SGD mechanism was cryogenic squeezing out of brine and watersoluble salts detected on the periphery of ice hummocks in the winter. The proposed mechanisms of groundwater transport and discharge in the Arctic land-shelf system is elaborated. Through salinity vs. 224 Ra and 224 Ra/ 223 Ra diagrams, the three main SGD-influenced water masses were identified and their end-member composition was constrained. Based on simple mass-balance box models, discharge rates at sites in the submarine permafrost talik zone were 1.7×10 6 m 3 d −1 or 19.9 m 3 s −1 , which is much higher than the April discharge of the Yana River. Further studies should apply these techniques on a broader scale with the objective of elucidating the relative importance of the SGD transport vector relative to surface freshwater discharge for both water balance and aquatic components such as dissolved organic carbon, carbon dioxide, methane, and nutrients.

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We investigated the mechanochemical synthesis of complex slow release fertilizers (SRF) derived from glauconite. We studied the effectiveness of the mechanical intercalation of urea into glauconite using planetary and ring mills. The potassium-nitric complex SRFs were synthesized via a mechanochemical method mixing glauconite with urea in a 3:1 ratio. The obtained composites were analyzed using X-ray diffraction analysis, scanning electron microscopy, X-ray fluorescence analysis, and infrared spectroscopy. The results show that as duration of mechanochemical activation increases, the mineralogical, chemical, and structural characteristics of composites change. Essential modifications associated with a decrease in absorbed urea and the formation of microcrystallites were observed when the planetary milling time increased from 5 to 10 min and the ring milling from 15 to 30 min. Complete intercalation of urea into glauconite was achieved by 20 min grinding in a planetary mill or 60 min in a ring mill. Urea intercalation in glauconite occurs much faster when using a planetary mill compared to a ring mill.

Subsea permafrost represents a large carbon pool that might be or become a significant greenhouse gas source. Scarcity of observational data causes large uncertainties. We here use five 21-56 m long subsea permafrost cores from the Laptev Sea to constrain organic carbon (OC) storage and sources, degradation state and potential greenhouse gas production upon thaw. Grain sizes, optically-stimulated luminescence and biomarkers suggest deposition of aeolian silt and fluvial sand over 160 000 years, with dominant fluvial/alluvial deposition of forest- and tundra-derived organic matter. We estimate an annual thaw rate of 1.3 ± 0.6 kg OC m−2 in subsea permafrost in the area, nine-fold exceeding organic carbon thaw rates for terrestrial permafrost. During 20-month incubations, CH4 and CO2 production averaged 1.7 nmol and 2.4 µmol g−1 OC d−1, providing a baseline to assess the contribution of subsea permafrost to the high CH4 fluxes and strong ocean acidification observed in the region.

Studies of mineral-forming processes in modern peat bogs can shed light on metal concentrations and their cycling in similar environments, especially in geological paleoanalogs. In terms of the mineralogical and geochemical evolution of peat bog environments, the Vasyugan Swamp in Western Siberia is a unique scientific object. Twelve peat samples were collected from the Vasyugan Swamp up to the depth of 275 cm at 25 cm intervals. The studied peat deposit section is represented by oligotrophic (0–100 cm), mesotrophic (100–175 cm), and eutrophic (175–275 cm) peat, and this is underlain by basal sediments (from 275 cm). About 30 minerals were detected using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Raman spectroscopy. The observed minerals are divided into detrital, clay, and authigenic phases. The detrital minerals found included quartz, feldspar, ilmenite, rutile, magnetite, zircon, and monazite. When passing from basal to oligotrophic bog sediments, the clay minerals changed from illite-smectite to kaolinite. Authigenic minerals are represented by carbonates (calcite and dolomite), iron (hydro-)oxides, galena, sphalerite, pyrite, chalcopyrite, Zn-Pb-S mineral, barite, baritocelestine, celestine, tetrahedrite, cassiterite, REE phosphate, etc. The regular distribution of mineral inclusions in peat is associated with the (bio)geochemical evolution of the environment. The formation of authigenic Zn, Pb and Sb sulfides is mainly confined to anaerobic conditions that exist in the eutrophic peat and basal sediments. The maximum amount of pyrite is associated with the interval of 225–250 cm, which is the zone of transition from basal sediments to eutrophic peat. The formation of carbonate minerals and the decreasing concentration of clay in the association with local sulfide formation (galena, sphalerite, chalcopyrite, stibnite) begins above this interval. The peak of specific carbonation appears in the 125–150 cm interval of the mesotrophic peat, which is characterized by pH 4.9–4.5 of pore water. Kaolinite is the dominant clay mineral in the oligotrophic peat. Gypsum, galena, chalcopyrite, sphalerite, and relicts of carbonate are noted in association with kaolinite. Changes in oxygen concentrations are reflected in newly formed mineral associations in corresponding intervals of the peat. This can be explained by the activity of microbiological processes such as the anaerobic oxidation of methane (AOM) and bacterial sulfate reduction (BSR), expressed in specific carbonatization (100–225 cm) and sulfidization (175–250 cm), respectively.

Authigenesis of ferrimagnetic iron sulfide minerals (greigite and monoclinic pyrrhotite) occurred across the Paleocene‐Eocene Thermal Maximum (PETM) within the Bakchar oolitic ironstone in southeastern Western Siberia. Co‐occurrence of these minerals is associated with diagenetic environments that support anaerobic oxidation of methane, which has been validated by methane fluid inclusion analysis in the studied sediments. In modern settings, such ferrimagnetic iron sulfide formation is linked to upward methane diffusion in the presence of minor dissolved sulfide ions. The PETM was the most extreme Cenozoic global warming event and massive methane mobilization has been proposed as a major contributor to the globally observed warming and carbon isotope excursion associated with the PETM. The studied sediments provide rare direct evidence for methane mobilization during the PETM. Magnetic iron sulfide formation associated with methanogenesis in the studied sediments can be explained by enhanced local carbon burial across the PETM. While there is no strong evidence to link local methane venting with more widespread methane mobilization and global warming, the magnetic, petrographic, and geochemical approach used here is applicable to identifying authigenic minerals that provide telltale signatures of methane mobility that can be used to assess methane formation and mobilization through the PETM and other hyperthermal climatic events.