Diverse Nanoassemblies of Graphene Quantum Dots and Their Mineralogical Counterparts

Complex structures from nanoparticles are found in rocks, soils, and sea sediments but the mechanisms of their formation are poorly understood, which causes controversial conclusions about their genesis. Here we show that graphene quantum dots (GQDs) can assemble into complex structures driven by coordination interactions with metal ions commonly present in environment and serve a special role in Earth’s history, such as Fe3+ and Al3+. GQDs self- assemble into mesoscale chains, sheets, supraparticles, nanoshells, and nanostars. Specific assembly patterns are determined by the effective symmetry of the GQDs when forming the coordination assemblies with the metal ions. As such, maximization of the electronic delocalization of Ï - orbitals of GQDs with Fe3+ leads to GQD- Fe- GQD units with D2 symmetry, dipolar bonding potential, and linear assemblies. Taking advantage of high electron microscopy contrast of carbonaceous nanostructures in respect to ceramic background, the mineralogical counterparts of GQD assemblies are found in mineraloid shungite. These findings provide insight into nanoparticle dynamics during the rock formation that can lead to mineralized structures of unexpectedly high complexity.Complex structures from nanoparticles are found in rocks, soils, and sea sediments but the mechanisms of their formation are poorly understood. It is shown that graphene quantum dots (GQDs) can assemble into complex structures driven by coordination interactions with metal ions commonly present in the environment and play a special role in Earth’s history, such as Fe3+ and Al3+.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/155475/1/anie201908216_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/155475/2/anie201908216.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/155475/3/anie201908216-sup-0001-misc_information.pd

Diverse Nanoassemblies of Graphene Quantum Dots and Their Mineralogical Counterparts

Complex structures from nanoparticles are found in rocks, soils, and sea sediments but the mechanisms of their formation are poorly understood, which causes controversial conclusions about their genesis. Here we show that graphene quantum dots (GQDs) can assemble into complex structures driven by coordination interactions with metal ions commonly present in environment and serve a special role in Earth’s history, such as Fe3+ and Al3+. GQDs self- assemble into mesoscale chains, sheets, supraparticles, nanoshells, and nanostars. Specific assembly patterns are determined by the effective symmetry of the GQDs when forming the coordination assemblies with the metal ions. As such, maximization of the electronic delocalization of Ï - orbitals of GQDs with Fe3+ leads to GQD- Fe- GQD units with D2 symmetry, dipolar bonding potential, and linear assemblies. Taking advantage of high electron microscopy contrast of carbonaceous nanostructures in respect to ceramic background, the mineralogical counterparts of GQD assemblies are found in mineraloid shungite. These findings provide insight into nanoparticle dynamics during the rock formation that can lead to mineralized structures of unexpectedly high complexity.Komplexe Strukturen aus Nanopartikeln sind in Gesteinen, Böden und Meeressedimenten zu finden, aber die Mechanismen ihrer Entstehung sind kaum verstanden. Es wird gezeigt, dass sich Graphenquantenpunkte (GQDs) zu komplexen Strukturen zusammenfügen können, angetrieben durch Koordinationswechselwirkungen mit Metallionen wie Fe3+ and Al3+, die in der Umwelt häufig vorkommen und eine besondere Rolle in der Erdgeschichte spielen.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/155470/1/ange201908216.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/155470/2/ange201908216_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/155470/3/ange201908216-sup-0001-misc_information.pd

Frontispiece: Diverse Nanoassemblies of Graphene Quantum Dots and Their Mineralogical Counterparts

Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/155530/1/anie202082262.pd

Frontispiz: Diverse Nanoassemblies of Graphene Quantum Dots and Their Mineralogical Counterparts

Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/155477/1/ange202082262.pd

Pollen record with radiocarbon datings from Faddeyevskiy Island, Laptev Sea

Pollen, plant macrofossil, loss-on-ignition and radiocarbon analyses of a 1.4-m section in thermokarst topography from Faddeyevskiy Island (75°20'N, 143°50'E, 30 m elevation) provides new information on Late Pleistocene interstadial environmental history of this high Arctic region. Conventional radiocarbon dates (25,700 ± 1000, 32,780 ± 500, 35,200 ± 650 yr BP) and two AMS dates (29,950 ± 660 and 42,990 ± 1280 yr BP) indicate that the deposits accumulated during the Kargian (Boutellier) interval. Numerous mammoth (Mammuthus primigenius) remains that have been collected in vicinity of the site in this study were radio-carbon dated to 36,700-18,500 yr BP. Rare bison (Bison priscus) bones were dated to 32,200 ± 600 and 33,100 ± 320 yr BP. Poaceae, Cyperaceae, and Artemisia pollen dominate the spectra with some Ranunculaceae, Caryophyllaceae, Rosaceae, and Asteraceae. The pollen spectra reflect steppe-like (tundra-steppe) vegetation, which was dominant on the exposed shelf of the Arctic Ocean. Numerous Carex macrofossils suggest that the summer climate was at least 2°C warmer than today. The productivity of the local vegetation during the Kargian interstadial was high enough to feed the population of grazing mammals

A postglacial relative sea-level database for the Russian Arctic coast

We present the first quality-controlled relative sea-level (RSL) database for the Russian Arctic coast from the Barents Sea in the west to Laptev Sea in the east (29–152oE and 63 to 81oN). The database consists of 385 sea-level index points and 249 limiting dates and spans 24 ka to present. Sea-level indicators are derived from multiple proxies, including isolation basins, raised beaches, glacial erratics, marine terraces, laidas (salt marshes), and deltaic salt marshes. Here, we calculate the indicative meanings for all indicators and evaluated possible elevation errors. We have estimated the ages and uncertainties of index points and limiting dates using the most recent calibration datasets. In the western Russian Arctic (Barents and White Seas), RSL was driven by glacial isostatic adjustment (GIA) due to deglaciation of the Eurasian ice sheet complex. For example, within the Baltic crystalline shield, RSL fell rapidly from 80 to 100 m at 11–12 ka to 15–25 m at ∼4–5 ka. In the Arctic Islands of Franz-Joseph Land and Novaya Zemlya, RSL gradually fell from 25 to 35 m at 9 ka to 5–10 m at 3 ka. The Timan coast and the Kara Sea shelf are characterized by constant RSL rise due to proglacial forebulge collapse; Yamal and the Gydan Peninsula and Novaya Zemlya are all marked by a high LGM position of RSL, followed by a lowstand and consequent rise to a late Holocene highstand of several meters. Data from the Laptev Sea coasts and shelf and the New Siberian Islands demonstrate post-LGM RSL rise with a Holocene highstand of up to 5–10 m, with scatter caused by differential tectonic movements along a diffuse lithospheric plate boundary. The collected database allowed to estimate and discuss the reasons of both spatial and temporal variability of RSL histories in different parts of the Russian Arctic

Winter air temperature in the early and middle Holocene on the eastern coast of Daurkin Peninsula, Chukotka, reconstructed from stable isotopes of ice wedges

The object of research is the Holocene massive ice veins on the Eastern coast of the Daurkin Peninsula, the easternmost part of the Chukotka. Peat bogs with ice veins occur on the surface of marine terraces (near Uelen and Lorino settlements) and on flood plain of the Koolen' Lake; the thickness of peat varies from 0.7 to 2.5 m. Radiocarbon dating of the peat enclosing the investigated ice veins near Uelen and Lorino indicated that the beginning of peat accumulation began at the end of Late Pleistocene - early Holocene, about 11 cal ka BP. On the flood plain of the Koolen' Lake peat bogs began to accumulate in the middle Holocene, i.e. around 6 cal ka BP. At the initial stage of peat bogs formation the rate of peat accumulation was high and could reach 1 cm/10 years. Ice veins occur at a depth of 0.5-1 m, and their lower parts are located in the underlying peat sandy loams and loams. In the upper levels of the peat bogs, narrow present-day ice veins are found, which are sometimes embedded in the upper parts of Holocene veins. A clear sign of syngenetic growth of veins is the upward bending of the layers of the host peat at the lateral contacts with the veins. The main source of water for the formation of ice veins is snow, as evidenced by the ratio of stable isotopes of oxygen and hydrogen and the values of deuterium excesses in the ice. A slight admixture of saline water (probably from a seasonally thawed layer) was noted in the veins near the Lorino settlement. Reconstructions of winter air paleotemperatures, performed on the basis of data of isotope-oxygen composition of ice from the veins, did show that at the period between 11 and 6 cal Ka BP, the mean winter air temperature on the Daurkin Peninsula was by 2-5 °C lower than today, but the air temperature of the coldest month (January or February) was still lower (by 4-8 °C) than today. The noticeable trend of increase of stable isotope values in the ice veins from early Holocene to the present time is indicative of a steady positive trend of mean winter air temperatures in the Holocene