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.     

Broadband seismic source data acquisition and processing to delineate iron oxide deposits in the Blötberget mine-central Sweden

A prototype electromagnetic vibrator, referred to here as E-Vib, was upgraded and developed for broadband hardrock and mineral exploration seismic surveys. We selected the iron oxide mine in Blötberget, central Sweden, for a test site in 2019 for the newly developed E-Vib because of the availability of earlier seismic datasets (from 2015 to 2016) for verification of its performance for hardrock imaging purposes. The two-dimensional data acquisition consisted of a fixed geometry with 550 receiver locations spaced at every 5 m, employing both cabled and wireless seismic recorders, along an approximately 2.7 km long profile. The E-Vib operated at every second receiver station (i.e. 10 m spacing) with a linear sweep of 2–180 Hz and with a peak force of 7 kN. The processing workflow took advantage of the broadband signal generated by the E-Vib in this challenging hardrock environment with varying ground conditions. The processed seismic section shows a set of reflections associated with the known iron oxide mineralization and a major crosscutting reflection interpreted to be from a fault system likely to be crosscutting the mineralization. The broadband source data acquisition and subsequent processing helped to improve signal quality and resolution in comparison with the earlier workflows and data where a drophammer seismic source was used as the seismic source. These results suggest new possibilities for the E-Vib source for improved targeting in hardrock geological settings.     

An experimental study of the effect of iron on magnesiochloritoid-talc-clinochlore-kyanite stability

The influence of Fe on the reaction clinochlore+kyanite&ding3F;magnesiochloritoid+talc (1) was determined experimentally as a function of pressure (1.6-2.6 GPa) and composition at 600 and 540 °C. Analytical electron microscopy (AEM) was used to determine the compositions of the coexisting phases in these complex multiphase run products. Within the compositional range studied (x_Fe^bulk=0.12-0.34), chlorite solid solutions were always richer in magnesium than the coexisting chloritoid solid solutions. Fractionation of Fe into the chloritoid extends the stability field of the assemblage chloritoid plus talc towards lower pressures. However, the extent of the stability field for increasing x_Fe is less than one would expect for ideal mixing behaviour in chloritoid and chlorite, and indicates a moderate positive deviation from ideality for chloritoid solid solutions. The thermodynamic data for magnesiochloritoid given in two earlier studies are in good agreement with the present experiments, those of a third study yield pressures which are much too high, at least compared with the experiments at 600 °C.     

Paleoenvironmental analysis of a middle Wisconsinan biota site, southwestern Virginia, U.S.A.

The Ratcliff Site in southwestern Virginia lies in a small second-order stream valley filled with approximately 3.5 m of organic-rich deposits that contain bones of mammoth, mastodon, deer (or antelope), logs, and plant macrofossils. Radiocarbon analyses indicate the age of the organic-rich sediment ranges from > 44,000 to 29,100 ¹⁴C yr BP, a time period with no fossil remains reported in this region of the Appalachians. Analyses of field observations, textural data, organic carbon content, and plant macrofossils indicate that the organic-rich sediments contain interbedded standing-water and debris-flow deposits. Up to 6 m of oxidized debris-flow sediments bury the organic-rich sediments. The presence of Rubus parviflorus (Thimble Berry) throughout the deposit indicates the site had a boreal environment from > 44,000 to 29,100 ¹⁴C yr BP. Plant macrofossil evidence indicates the uplands had stands of spruce/jack-pine forests while the valley contained ponds and associated wetlands. Three debris flows occurred at the site between approximately 38,000 and 29,000 ¹⁴C yr BP, suggesting a recurrence interval for major storms of approximately 3000 yr, even though the apparent stability of the boreal environment implies a climate not conducive to catastrophic rainstorms. This conflicting combination of features suggests that during the middle Wisconsinan this area experienced generally cool climates, dominated by polar air masses, but was punctuated by relatively brief warm periods marked by incursions of tropical air masses.     

Cu(II) adsorption at the calcite-water interface in the presence of natural organic matter: Kinetic studies and molecular-scale characterization

We have characterized the adsorption of Suwannee River humic acid (SRHA) and Cu(II) on calcite from preequilibrated solutions at pH 8.25. Sorption isotherms of SRHA on calcite follow Langmuir-type behavior at SRHA concentrations less than 15 mg C L⁻¹, whereas non-Langmuirian uptake becomes evident at concentrations greater than 15 mg C L⁻¹. The adsorption of SRHA on calcite is rapid and mostly irreversible, with corresponding changes in electrostatic properties. At pH 8.25, Cu(II) uptake by calcite in the presence of dissolved SRHA decreases with increasing dissolved SRHA concentration, suggesting that formation of Cu-SRHA aqueous complexes is the primary factor controlling Cu(II) sorption at the calcite surface under the conditions of our experiments. We also observed that surface-bound SRHA has little influence on Cu(II) uptake by calcite, suggesting that Cu(II) coordinates to calcite surface sites rather than to surface-bound SRHA.Cu K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) spectroscopic results show that the local coordination of Cu adsorbed at the calcite surface is very similar in the presence and absence of SRHA. Ca backscatterers at ∼3.90 Å indicate that Cu(II) forms tetragonally distorted inner-sphere adsorption complexes in both binary and ternary systems. Subtle differences in the XANES and EXAFS between binary sorption samples and ternary sorption samples, however, prevent us from ruling out the formation of ternary Cu-SRHA surface complexes. Our findings demonstrate that SRHA plays an important role in controlling the fate and transport of Cu(II) in calcite-bearing systems.     

Pravčice Rock Arch (Bohemian Switzerland National Park, Czech Republic) deterioration due to natural and anthropogenic weathering

The dominant factors affecting the development of weathering forms on the Prav?ice Rock Arch (PRA) (Bohemian Switzerland National Park, Czech Republic) are discussed, based on the in situ monitoring of weathering forms, as well as on laboratory studies of materials taken from this site. The in situ monitoring shows the progressive development of distinct weathering forms (delamination of case-hardened rock surfaces, cyclic efflorescence, and granular disintegration of exposed weakly cemented rock mass) in specific portions of the PRA, whose location is controlled by lithology, jointing/local hydrodynamics, and exposure to climatic factors. From the analysis of efflorescence, the dominance of sulphates is evident; particularly of gypsum and alums. However, the synergistic effects of the several salt species (that also include minor nitrates and chlorides) upon the mechanical disintegration of sandstone can be expected.     

Quantifying the seasonal variations in fluvial and eolian sources of terrigenous material to Cariaco Basin,Venezuela

The varved sediments that accumulate in the Cariaco Basin provide a detailed archive of the region’s climatic history, including a record of the quantity of fluvial and wind-transported material. In this study, we examine the sedimentological characteristics (clay mineralogy and grain size) of both surface sediments and sinking lithogenic material collected from sediment trap samples over a three-year period from 1997 to 2000. Data from biweekly sediment trap samples show a tri-modal particle size distribution, with prominent peaks at 2, 22 and 80 μm, indicating sediment contributions from both eolian and fluvial sources. The clay mineralogy of the water column samples collected from 1997 to 1999 also shows distinctive characteristics of eolian and fluvial material. An examination of surface sediment samples from the Cariaco Basin indicates that the Unare River is the main source of riverine sediments to the eastern sub-basin. By combining these sedimentological proxies, we estimate that ～10% of the terrigenous material delivered to the Cariaco Basin is eolian, while ～90% is fluvial. This represents an annual dust accumulation rate of ～0.59 mg/cm²/yr. Since aerosols are closely linked to climate variability, the ability to quantify paleo-dust fluxes using sedimentological characteristics will be a useful tool for future paleoclimate studies looking at sub-Saharan aridity and latitudinal migration of the Intertropical Convergence Zone.     

Compensatory mitigation in marine ecosystems: Which indicators for assessing the “no net loss” goal of ecosystem services and ecological functions?

Recent years have seen increasing interest in the concepts of compensation and ecosystem services. Regulation systems in the United States dealing with environmental protection (Superfund Act, Oil Pollution Act, National Environment Policy Act, Clean Water Act, Endangered Species Act, etc.) require those responsible for damage to ecosystem services to compensate for it “physically” and restore these services for the benefit of the entire population. This article, using simple indicators of compensation identified in the literature, attempts to analyze what types of ecological compensation are adopted, how performance is assessed, how standards on ecological equivalencies are adopted, and what are the costs of this compensation. To perform this analysis, compensatory measures carried out during the last ten years in the case of coastal and marine ecosystems in Florida have been addressed. The results show that: analysis criteria for the equivalencies between ecosystem services lost due to damage and ecosystem services gained due to compensatory measures are questionable; most compensation monitoring is for a relatively brief period of time and the data obtained during this period may be insufficient for assessing the net effect of the compensatory measure; the weaknesses regarding criteria for the equivalencies and the uncertainty about the relevant time-scale can be counter-balanced by increasing the area of compensation, a problematic solution at best.     

Holocene vegetational history of the Kootenai River Valley,Montana

Pollen records in the Kootenai and Fisher River drainages in western Montana reveal a fivezone sequence of Holocene vegetation change. Deposition of Glacier Peak Ash-Layer G (ca. 10,540 ± 660 yr B.P.) in the lowermost sediments (clay intermixed with pebbles) at Tepee Lake gives a minimum date for the initiation of sedimentation. Initial vegetation on the newly deglaciated terrain was dominated by Pinus (probably white bark pine) with small amounts of Gramineae, Picea and Abies, reflecting a relatively cool, moist macroclimate. Two vegetation units appear to contribute to Pollen Zone II (ca. 11,000–7100 yr B.P.): arboreal communities with pines, along with Pseudotsuga or Larix, or both, and treeless vegetation dominated by Artemisia. Pollen Zone II represents an overall warmer macroclimate than occurred upon ice withdrawal. After ca. 7100 yr B.P. (Pollen Zone III) diploxylon pines became a major pollen contributor near both Tepee Lake and McKillop Creek Pond, indicating an expansion of xerophytic forest (P. contorta and P. ponderosa) along with an increase in the prominence of Pseudotsuga menziesii or Larix occidentalis, or both. Artemisia briefly expanded coverage near Tepee Lake concomitant with the Mazama ashfall ca. 6700 yr B.P. A short-term climatic trend with more available water began after ca. 4000 yr B.P. as Abies (probably A. grandis) along with Picea engelmannii became a more regular component of the forest surrounding both sites. Emergence of the modern macroclimate is indicated primarily with the first regular appearance of Tsuga heterophylla in the pollen record by ca. 2700 yr B.P., synchronous with the development of western hemlock forest within the same latitudes in northern Idaho and northeastern Washington.