Elucidation of the Alum Shale kerogen structure using a multi-disciplinary approach

The significance and validity of integrating data obtained from a variety of analytical techniques to understand, elucidate and model kerogen's complex chemical structure is reported here using degradative (open and closed system pyrolysis, chemical oxidation), non-degradative (¹³C CP/MAS NMR) and optical (incident white light and blue light) methods. Seven Cambrian Alum Shale samples, ranging in maturity from immature to post-mature with respect to petroleum generation, were studied and were chosen for their simple geological history, uniform organic matter type and high organic carbon content. The Alum Shale kerogens, which primarily consist of algal organic matter, liberate low molecular weight gaseous and aromatic compounds on pyrolysis and give mostly branched dicarboxylic acids on chemical oxidation. ¹³C NMR spectroscopy shows that the Alum Shale kerogens are anomalously rich in oxygen-bearing functional groups (such as C = O, ArCO, CHO, CH_xO), most of which apparently remain intact within the kerogen macro-molecule (KMM) through the diagenetic and catagenetic stages. Fragments released by different degradative techniques are quantified and the aromaticity (f_a), O/C and relative proportions of various carbon types estimated by ¹³C NMR. A synthesis of these data has allowed us to better understand the chemistry of the Alum Shale kerogen.     

The Quaternary history of the Wash fluvial network, UK

This paper appraises and compares the Middle-Upper Pleistocene sedimentary sequences preserved in the fluvial systems draining into the Fenland Basin and the Wash estuary. Of the main Fenland rivers the longest records, which extend back to the initial Anglian (glacial) formation of the basin, are found in the Great Ouse and its tributaries, particularly the Cam and the Nar. These sequences preserve sediments representing all four post-Anglian interglacials. The Nene also has an extensive post-Anglian history, with evidence for a Hoxnian estuary that is presumed to have been the precursor of the Wash. North of the Nene, however, the Welland and Witham (proto-Trent) have relatively short sequences, which are thought to commence with a later (post-Anglian-pre-Devensian) glaciation that affected Lincolnshire and fed the previously-recognized Tottenhill outwash delta south of Kings Lynn. Prior to Devensian deglaciation the Witham valley was occupied by the Trent, which was the trunk river of the late Middle Pleistocene Wash system. During periods of low sea level the river would have extended north-eastwards across what is now the floor of the North Sea, possibly via the Inner Silver Pit. Several of the central Fenland sequences show evidence of infrequent terrace formation during the late Quaternary, although this might in part be due to poor vertical separation between terraces, so that differentiating them has been difficult; this has been exacerbated by mixed biostratigraphical signals due to the preservation of sediments representing more than one interglacial beneath a single terrace surface. In several of the systems there is evidence for valley rejuvenation to the lowest terrace or valley-floor level during the MIS 4-3 transition. The observed differences within what, during the predominant periods of lower sea level, would have been a single Wash river system are difficult to explain.     

Using FTIR spectroscopy to characterise the soil mineralogy and geochemistry of cryoconite from Aldegondabreen glacier,Svalbard

Mineralogical and geochemical diversity in cryoconite granules from Aldegondabreen glacier was investigated using FTIR spectroscopy. Results suggest that the technique is an effective tool for investigating mineralogy and identifying spatial differences in geochemistry, based upon characteristic spectral signatures.     

Supercritical gas sorption on moist coals

The effect of moisture on the CO₂ and CH₄ sorption capacity of three bituminous coals from Australia and China was investigated at 55 °C and at pressures up to 20 MPa. A gravimetric apparatus was used to measure the gas adsorption isotherms of coal with moisture contents ranging from 0 to about 8%. A modified Dubinin–Radushkevich (DR) adsorption model was found to fit the experimental data under all conditions. Moisture adsorption isotherms of these coals were measured at 21 °C. The Guggenheim–Anderson–de Boer (GAB) model was capable of accurately representing the moisture isotherms over the full range of relative pressures.Moist coal had a significantly lower maximum sorption capacity for both CO₂ and CH₄ than dry coal. However, the extent to which the capacity was reduced was dependent upon the rank of the coal. Higher rank coals were less affected by the presence of moisture than low rank coals. All coals exhibited a certain moisture content beyond which further moisture did not affect the sorption capacity. This limiting moisture content was dependent on the rank of the coal and the sorbate gas and, for these coals, corresponded approximately to the equilibrium moisture content that would be attained by exposing the coal to about 40–80% relative humidity. The experimental results indicate that the loss of sorption capacity by the coal in the presence of water can be simply explained by volumetric displacement of the CO₂ and CH₄ by the water. Below the limiting moisture content, the CO₂ sorption capacity reduced by about 7.3 kg t^− 1 for each 1% increase in moisture. For CH₄, sorption capacity was reduced by about 1.8 kg t^− 1 for each 1% increase in moisture.The heat of sorption calculated from the DR model decreased slightly on addition of moisture. One explanation is that water is preferentially attracted to high energy adsorption sites (that have high energy by virtue of their electrostatic nature), expelling CO₂ and CH₄ molecules.     

Cripple Creek and other alkaline-related gold deposits in the southern Rocky Mountains, USA: influence of regional tectonics

Alkaline-related epithermal vein, breccia, disseminated, skarn, and porphyry gold deposits form a belt in the southern Rocky Mountains along the eastern edge of the North American Cordillera. Alkaline igneous rocks and associated hydrothermal deposits formed at two times. The first was during the Laramide orogeny (about 70-40 Ma), with deposits restricted spatially to the Colorado mineral belt (CMB). Other alkaline igneous rocks and associated gold deposits formed later, during the transition from a compressional to an extensional regime (about 35-27 Ma). These younger rocks and associated deposits are more widespread, following the Rocky Mountain front southward, from Cripple Creek in Colorado through New Mexico. All of these deposits are on the eastern margin of the Cordillera, with voluminous calc-alkaline rocks to the west. The largest deposits in the belt include Cripple Creek and those in the CMB. The most important factor in the formation of all of the gold deposits was the near-surface emplacement of relatively oxidized volatile-rich alkaline magmas. Strontium and lead isotope compositions suggest that the source of the magmas was subduction-modified subcontinental lithosphere. However, Cripple Creek alkaline rocks and older Laramide alkaline rocks in the CMB that were emplaced through hydrously altered LREE-enriched rocks of the Colorado (Yavapai) province have ²⁰⁸Pb/²⁰⁴Pb ratios that suggest these magmas assimilated and mixed with significant amounts of lower crust. The anomalously hot, thick, and light crust beneath Colorado may have been a catalyst for large-scale transfer of volatiles and crustal melting. Increased dissolved H₂O (and CO₂, F, Cl) of these magmas may have resulted in more productive gold deposits due to more efficient magmatic-hydrothermal systems. High volatile contents may also have promoted Te and V enrichment, explaining the presence of fluorite, roscoelite (vanadium-rich mica) and tellurides in the CMB deposits and Cripple Creek as opposed to deposits to the south. Deep-seated structures of regional extent that formed during the Proterozoic allowed the magmas to rise to shallow crustal levels. Proterozoic sites of intrusions at 1.65, 1.4, and 1.1 Ga were also important precursors to alkaline-related gold deposits. Many of the larger gold deposits are located at sites of Proterozoic intrusions, and are localized at the intersection of northeast-trending ductile shear zones formed during Mesoproterozoic deformation, and an important north-trending fault formed during 1.1 Ga rifting.     

Using streamflow characteristics to explore permafrost thawing in northern Swedish catchments

The recent and rapid warming of the Arctic leads to thawing of permafrost, which influences and changes subsurface water-flow systems in such landscapes. This study explores the utility of catchments as “sentinels of change” by considering long-term discharge data from 17 stations on unregulated rivers in northern Sweden and analyzing trends in annual minimum discharge and recession flow characteristics. For the catchments considered, the annual minimum discharge has increased significantly (based on the Mann Kendall test at a 95 % confidence level) in nine of the catchments and decreased significantly in one catchment. Considering changes in recession-flow characteristics, seven catchments showed significant trends consistent with permafrost thawing while two catchments showed significant trends in the opposite direction. These results are mechanistically consistent with generic physically based modeling studies and the geological setting, as the catchments considered span the spatial limit of permafrost extent. This study illuminates the potential for using hydrologic observations to monitor changes in catchment-scale permafrost. Further, this opens the door for research to isolate the mechanisms behind the different trends observed and to gauge their ability to reflect actual permafrost conditions at the catchment scale.     

The First Hop: Use of Beaufort Sea Deltas by Hatch-Year Semipalmated Sandpipers

River deltas along Alaska’s Beaufort Sea coast are used by hatch-year semipalmated sandpipers (Calidris pusilla) after leaving their terrestrial natal sites, but the drivers of their use of these stopover sites on the first “hop” of fall migration are unknown. We quantified sandpiper temporal distribution and abundance as related to food resources at three river deltas during the beginning of their fall migration (post-breeding period) to compare the habitat quality among these deltas. We conducted population counts, sampled invertebrates, and captured birds to collect blood samples from individuals for triglyceride and stable isotope analyses to determine fattening rates and diet. Patterns of sandpiper and invertebrate abundance were complex and varied among deltas and within seasons. River deltas were used by sandpipers from late July to late August, and peak sandpiper counts ranged from 1000 to 4000 individuals, of which 98% were hatch-year semipalmated sandpipers. Isotopic signatures from blood plasma samples indicated that birds switched from a diet of upland tundra to delta invertebrate taxa as the migration season progressed, suggesting a dependence on delta invertebrates. Despite differences in diet among deltas, we found no differences in fattening rates of juvenile sandpipers as indicated by triglyceride levels. The number of sandpipers was positively associated with abundance of Amphipoda and Oligochaeta at the Jago and Okpilak-Hulahula deltas; an isotopic mixing model indicated that sandpipers consumed Amphipoda and Oligochaeta at Jago, mostly Chironomidae at Okpilak-Hulahula and Spionidae at Canning. Regardless of the difference in sandpiper diets at the Beaufort Sea deltas, their similar fattening rates throughout the season indicate that all of these stopover sites provide a critical food resource for hatch-year sandpipers beginning their first migration.     

Large-strain deformation and strain partitioning in polyphase rocks: Dislocation creep of olivine–magnesiowüstite aggregates

Aggregates composed of olivine and magnesiowüstite have been deformed to large strains at high pressure and temperature to investigate stress and strain partitioning, phase segregation and possible localization of deformation in a polyphase material. Samples with 20 vol.% of natural olivine and 80 vol.% of (Mg_0.7Fe_0.3)O were synthesized and deformed in a gas-medium torsion apparatus at temperatures of 1127 °C and 1250 °C, a confining pressure of 300 MPa and constant angular displacement rates equivalent to constant shear strain rates of 1–3.3 × 10^− 4 s^− 1. The samples deformed homogeneously to total shear strains of up to γ  15. During constant strain rate measurements the flow stress remained approximately stable at 1250 °C while it progressively decreased after the initial yield stress at the lower temperature. Mechanical data, microstructures and textures indicate that both phases were deforming in the dislocation creep regime. The weaker component, magnesiowüstite, controlled the rheological behavior of the bulk material and accommodated most of the strain. Deformation and dynamic recrystallization lead to grain refinement and to textures that were not previously observed in pure magnesiowüstite and may have developed due to the presence of the second phase. At 1127 °C, olivine grains behaved as semi-rigid inclusions rotating in a viscous matrix. At 1250 °C, some olivine grains remained largely undeformed while deformation and recrystallization of other grains oriented for a-slip on (010) resulted in a weak foliation and a texture typical for pure dry olivine aggregates. Both a-slip and c-slip on (010) were activated in olivine even though the nominal stresses were up to 2 orders of magnitude lower than those needed to activate these slip systems in pure olivine at the same conditions.     

Contrasting isotopic signatures between anthropogenic and geogenic Zn and evidence for post-depositional fractionation processes in smelter-impacted soils from Northern France

Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ⁶⁶Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2σ) to +0.34 ± 0.17‰ (2σ) at the lowest horizons and from +0.38 ± 0.45‰ (2σ) to +0.76 ± 0.14‰ (2σ) near the surface. The δ⁶⁶Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ⁶⁶Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe₂O₄)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ⁶⁶Zn values of +0.81 ± 0.20‰ (2σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ⁶⁶Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ⁶⁶Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.     

Major and trace element geochemistry of Lake Bogoria and Lake Nakuru,Kenya, during extreme draught

The physico-chemical properties of water samples from the two athalassic endorheic lakes Bogoria and Nakuru in Kenya were analysed. Surface water samples were taken between July 2008 and October 2009 in weekly intervals from each lake. The following parameters were determined: pH, salinity, electric conductivity, dissolved organic carbon (DOC), the major cations (FAAS and ICP-OES) and the major anions (IC), as well as certain trace elements (ICP-OES). Samples of superficial sediments were taken in October 2009 and examined using Instrumental Neutron Activation Analysis (INAA) for their major and trace element content including rare earth elements (REE). Both lakes are highly alkaline with a dominance of Na > K > Si > Ca in cations and HCO₃ > CO₃ > Cl > F > SO₄ in anions. Both lakes also exhibited high concentrations of Mo, As and fluoride. Due to an extreme draught from March to October 2009, the water level of Lake Nakuru dropped significantly. This created drastic evapoconcentration, with the total salinity rising from about 20‰ up to 63‰. Most parameters (DOC, Na, K, Ca, F, Mo and As) increased with falling water levels. A clear change in the quality of DOC was observed, followed by an almost complete depletion of dissolved Fe from the water phase. In Lake Bogoria the evapoconcentration effects were less pronounced (total salinity changed from about 40‰ to 48‰). The distributions of REE in the superficial sediments of Lake Nakuru and Lake Bogoria are presented here for the first time. The results show a high abundance of the REE and a very distinct Eu depletion of Eu/Eu* = 0.33–0.45.