Molecular and isotopic partitioning of low-molecular-weight hydrocarbons during migration and gas hydrate precipitation in deposits of a high-flux seepage site

Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone.Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (> 99.85 mol.% of ∑[C₁–C₄, CO₂]). Molecular ratios of LMWHC (C₁/[C₂ + C₃] > 1000) and stable isotopic compositions of methane (δ¹³C = ? 53.5‰ V-PDB; D/H around ? 175‰ SMOW) indicated predominant microbial methane formation. C₁/C₂₊ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by > 0.03 mol.% (∑[C₁–C₄, CO₂]) relative to the other gas types and the virtual lack of ¹⁴C–CH₄ indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely.As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% ∑(C₁–C₄, CO₂)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of ¹⁴C–CH₄ (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.     

Migrating magmatism in the northern US Cordillera: in situ U–Pb geochronology of the Idaho batholith

New in situ laser ablation-inductively coupled plasma-mass spectrometry and sensitive high-resolution ion microprobe U–Pb geochronology of zircons from the Idaho batholith and spatially overlapping Challis intrusions reveals a series of discrete magmatic belts of different ages and compositions. Following the accretion of the Blue Mountains province to North America along the Salmon River suture zone, two compositionally diverse belts of metaluminous plutons formed both adjacent to the suture and well inboard of it. These were constructed from ~100 to 85 Ma and were followed by a voluminous pulse of peraluminous magmatism, forming the bulk of the Atlanta lobe and largest fraction of the batholith between ~80 and 67 Ma. Around 70 Ma, a later and more spatially restricted suite of metaluminous plutons formed around the Bitterroot lobe of the batholith. This was followed by another pulse of voluminous peraluminous magmatism in the Bitterroot lobe, lasting from ~66 to 54 Ma. The changes from low volume metaluminous to high volume peraluminous magmatism may reflect a combination of changes in the angle and segmentation of the subducting Farallon plate and over thickening of the continental lithosphere. All of these features were then cut by plutons and dikes associated with the Challis volcanic field, lasting from ~51 to 43 Ma. Inherited components are pervasive in zircons from most phases of the batholith. While Precambrian components are very common, zircons also often contain cores or mantles that are 5–20 million years older than their rims. This suggests that the early phases of the batholith were repeatedly cannibalized by subsequent magmas. This also implies that the older suites may have been originally more aerially extensive than their currently exposed forms.     

Stable sulfur isotopes in the water column of the Cariaco Basin

Previous geochemical and microbiological studies in the Cariaco Basin indicate intense elemental cycling and a dynamic microbial loop near the oxic-anoxic interface. We obtained detailed distributions of sulfur isotopes of total dissolved sulfide and sulfate as part of the on-going CARIACO time series project to explore the critical pathways at the level of individual sulfur species. Isotopic patterns of sulfate (δ³⁴S_SO4) and sulfide (δ³⁴S_H2S) were similar to trends observed in the Black Sea water column: δ³⁴S_H2S and δ³⁴S_SO4 were constant in the deep anoxic water (varying within 0.6‰ for sulfide and 0.3‰ for sulfate), with sulfide roughly 54‰ depleted in ³⁴S relative to sulfate. Near the oxic-anoxic interface, however, the δ³⁴S_H2S value was ∼3‰ heavier than that in the deep water, which may reflect sulfide oxidation and/or a change in fractionation during in situ sulfide production through sulfate reduction (SR). δ³⁴S_H2S and Δ³³S_H2S data near the oxic-anoxic interface did not provide unequivocal evidence to support the important role of sulfur-intermediate disproportionation suggested by previous studies. Repeated observation of minimum δ³⁴S_SO4 values near the interface suggests ‘readdition’ of ³⁴S-depleted sulfate during sulfide oxidation. A slight increase in δ³⁴S_SO4 values with depth extended over the water column may indicate a reservoir effect associated with removal of ³⁴S-depleted sulfur during sulfide production through SR. Our δ³⁴S_H2S and Δ³³S_H2S data also do not show a clear role for sulfur-intermediate disproportionation in the deep anoxic water column. We interpret the large difference in δ³⁴S between sulfate and sulfide as reflecting fractionations during SR in the Cariaco deep waters that are larger than those generally observed in culturing studies.     

A new particulate Mn-Fe-P-shuttle at the redoxcline of anoxic basins

Pelagic redoxclines of anoxic basins and deeps form the suboxic transition between oxygenated surface and anoxic or even sulfidic bottom waters. Intense element cycling, favoured by elevated microbial activity, causes steep gradients of physico-chemical parameters, nutrients and redox-sensitive trace metals. This study presents a conceptual model for authigenic particle formation at pelagic redoxclines, which is based on the tight coupling of Mn, Fe, and P cycles. Besides the well-known occurrence of Mn-oxides, textural (SEM-EDX) and geochemical (ICP-OES, ICP-MS) analyses of particles from the redoxclines of the Black Sea and the Baltic Sea (Gotland Basin, Landsort Deep) evidence the existence of earlier postulated Fe-oxyhydroxo-phosphates and emphasize mixed phases consisting of Mn-oxides and Fe-oxyhydroxo-phosphates as a new solid species. Most of the analyzed particles are star-shaped, of about 5 μm in size, and occur as single particles or aggregates without any morphological differences between Mn-oxides, Fe-oxyhydroxo-phosphates, and mixed phases. Throughout the redoxcline, these minerals show a general succession with maximum abundance of Mn-oxides above the redoxcline followed by mixed phases and almost pure Fe-phosphates within and below the redoxcline, respectively. Molar Fe/P ratios of single particles argue against the formation of known pure Fe-phosphates like vivianite or strengite at the lower end of the redox transition zone, but are consistent with recent experimental findings for colloidal P-bearing hydrous ferric oxides. Moreover, morphological similarities suggest the formation of irregular Fe-oxyhydroxo coatings due to oxidation of upward diffusing Fe²⁺ by oxygen and stepwise replacement of Mn(IV) by Fe(III) on sinking MnO_x particles followed by immediate adsorption or even co-precipitation of phosphate. Batch-type experiments using biogenic MnO_x particles demonstrate the efficient potential of Fe²⁺ oxidation by sinking MnO_x particles. When entering sulfidic waters MnO_x particles are progressively reduced leading to an increasing relative abundance of Fe- and P-rich particles. In deeper parts of the water column these particles are also reductively dissolved, thereby releasing Fe²⁺ and phosphate to the water column. This Mn-Fe-P-shuttle likely affects phosphate transport throughout the water column and thus impacts primary production at least over longer time scales. Furthermore, the particulate Mn-Fe-P-shuttle must have played an important role for the cycling of P and certain trace metals in ancient ocean basins, e.g., during certain periods of Cretaceous black shale formation and should be considered in future mass balances and modeling approaches dealing with oxic/anoxic interfaces of aquatic ecosystems.     

巨型翼龙类能够飞行吗？

Many pterodactyloids had wingspans that vastly exceed those of any other flying animals, living or extinct. Ornithocheiroids and neoazhdarchidans were particularly large pterosaurs that regularly attained wingspans over 4 m. Certain members of these groups – Pteranodontia and Azhdarchidae – attained the largest wingspans of any pterosaurs, making them the largest flying animals known.     

Submarine channel levee shape and sediment waves from physical experiments

Submarine channel levees aggrade through repeated overspill events from the channel axis. The shape of the levees may therefore reflect some characteristic(s) of the overspilling flow. It has been noted that basin floor levees typically have a relatively low-relief and taper exponentially to their termination; in contrast slope channel levees may be much steeper close to the channel. A simple physical experiment was performed where a surge-like sediment-laden current flowed through a curved channel. Significant overspill occurred and generated a deposit flanking the channel on either side. The experiment was repeated 25 times to build up low-relief channel-levees. It was found that in proximal areas, levees were steep and characterised by power-law decays, a transitional zone of logarithmically thinning levee was found a little further down-channel, followed by exponential decays in medial to distal areas. The style of levee decay is a function of spatial variation in overbank sedimentation rates. Where flows rapidly lose momentum and deposit across the grain-size spectrum, i.e., in proximal areas, levees tend to be steep; farther down the channel, the steep levee slope gives way to a more gradually tapering deposit. In more distal parts of the channel, deposition is directly related to sediment settling velocity (rather than the suspended load exceeding flow transport capacity as is the case in proximal areas), the deposit reflects this with relatively simple exponential thickness decays. Additionally, small-scale sediment waves developed under lee wave conditions on the inner-bend overbank. The waves initially migrated slightly towards the channel, but as the style of overspill evolved due to intra-channel deposition, flows moved out of the lee wave window and sedimentation became out of phase with the wavelength of the features and the topography was healed.     

Biological influences on modern sulfates: Textures and composition of gypsum deposits from Guerrero Negro,Baja California Sur,Mexico

Gypsum (CaSO₄·2H₂O) deposits from a range of sedimentary environments at Guerrero Negro, Baja California Sur, Mexico were investigated for microscale texture and composition in order to differentiate features formed under substantial microbial influence from those for which microbial effects were relatively minor or absent. Gypsum deposits were classified according to their sedimentary environment, textures, crystal habit, brine composition and other geochemical factors. The environments studied included subaqueous sediments in anchialine pools and in solar salterns, as well as subsurface sediments of mudflats and saltpans. Gypsum that developed in the apparent absence of biofilms included crystals precipitated in the water column and subsedimentary discs that precipitated from phreatic brines. Subsedimentary gypsum developed in sabkha environments exhibited a sinuous microtexture and poikilitically enclosed detrital particles. Water column precipitates had euhedral prismatic habits and extensive penetrative twinning. Gypsum deposits influenced by biofilms included bottom nucleated crusts and gypsolites developing in anchialine pools and saltern ponds. Gypsum precipitating within benthic biofilms, and in biofilms within subaerial sediment surfaces provided compelling evidence of biological influences on crystal textures and habits. This evidence included irregular, high relief surface textures, accessory minerals (S°, Ca-carbonate, Sr/Ca-sulfate and Mg-hydroxide) and distinctive crystal habits such as equant forms and crystals having distorted prism faces.     

Late Quaternary megafloods from Glacial Lake Atna, Southcentral Alaska, U.S.A.

Geomorphic, stratigraphic, geotechnical, and biogeographic evidence indicate that failure of a Pleistocene ice dam between 15.5 and 26 ka generated a megaflood from Glacial Lake Atna down the Matanuska Valley. While it has long been recognized that Lake Atna occupied ≥ 9000 km² of south-central Alaska's Copper River Basin, little attention has focused on the lake's discharge locations and behaviors. Digital elevation model and geomorphic analyses suggest that progressive lowering of the lake level by decanting over spillways exposed during glacial retreat led to sequential discharges down the Matanuska, Susitna, Tok, and Copper river valleys. Lake Atna's size, ∼ 50 ka duration, and sequential connection to four major drainages likely made it a regionally important late Pleistocene freshwater refugium. We estimate a catastrophic Matanuska megaflood would have released 500–1400 km³ at a maximum rate of ≥ 3 × 10⁶ m³ s^{− 1}. Volumes for the other outlets ranged from 200 to 2600 km³ and estimated maximum discharges ranged from 0.8 to 11.3 × 10⁶ m³ s^{− 1}, making Lake Atna a serial generator of some of the largest known freshwater megafloods.     

Paleoclimatic implications of the spatial patterns of modern and LGM European land-snail shell δO

The oxygen isotopic composition of land-snail shells may provide insight into the source region and trajectory of precipitation. Last glacial maximum (LGM) gastropod shells were sampled from loess from Belgium to Serbia and modern land-snail shells both record δ¹⁸O values between 0‰ and − 5‰. There are significant differences in mean fossil shell δ¹⁸O between sites but not among genera at a single location. Therefore, we group δ¹⁸O values from different genera together to map the spatial distribution of δ¹⁸O in shell carbonate. Shell δ¹⁸O values reflect the spatial variation in the isotopic composition of precipitation and incorporate the snails' preferential sampling of precipitation during the warm season. Modern shell δ¹⁸O decreases in Europe along a N-S gradient from the North Sea inland toward the Alps. Modern observed data of isotopes in precipitation (GNIP) demonstrate a similar trend for low-altitude sites. LGM shell δ¹⁸O data show a different gradient with δ¹⁸O declining toward the ENE, implying a mid-Atlantic source due to increased sea ice and a possible southern displacement of the westerly jet stream. Balkan LGM samples show the influence of a Mediterranean source, with δ¹⁸O values decreasing northward.     

Toward critical spatial thinking in the social sciences and humanities

The integration of geographically referenced information into the conceptual frameworks and applied uses of the social sciences and humanities has been an ongoing process over the past few centuries. It has gained momentum in recent decades with advances in technologies for computation and visualization and with the arrival of new data sources. This article begins with an overview of this transition, and argues that the spatial integration of information resources and the cross-disciplinary sharing of analysis and representation methodologies are important forces for the integration of scientific and artistic expression, and that they draw on core concepts in spatial (and spatio-temporal) thinking. We do not suggest that this is akin to prior concepts of unified knowledge systems, but we do maintain that the boundaries to knowledge transfer are disintegrating and that our abilities in problem solving for purposes of artistic expression and scientific development are enhanced through spatial perspectives. Moreover, approaches to education at all levels must recognize the need to impart proficiency in the critical and efficient application of these fundamental spatial concepts, if students and researchers are to make use of expanding access to a broadening range of spatialized information and data processing technologies.