A review of advanced catalyst development for Fischer-Tropsch synthesis of hydrocarbons from biomass derived syn-gas

Fischer-Tropsch synthesis (FTS) is a process which converts syn-gas (H2 and CO) to synthetic liquid fuels and valuable chemicals. Thermal gasification of biomass represents a convenient route to produce syn-gas from intractable materials particularly those derived from waste that are not cost effective to process for use in biocatalytic or other milder catalytic processes. The development of novel catalysts with high activity and selectivity is desirable as it leads to improved quality and value of FTS products. This review paper summarises recent developments in FT-catalyst design with regards to optimising catalyst activity and selectivity towards synthetic fuels. © 2014 the Partner Organisations.

Benthic foraminiferal record of the Pleistocene uplift of the sedimentary deposits of the Burica Peninsula (Costa Rica-Panama) as a result of Cocos Ridge subduction beneath the Central American Arc

This study used paleobathymetric interpretations from benthic foraminiferal assemblages to determine the timing of the initial subduction of the Cocos Ridge beneath the Costa Rica-Panama Arc and the associated amount of uplift. Forty-seven samples from four stratigraphic sections of the Burica and the Armuelles formations yielded 217 identified species. Foraminiferal paleoecology and cluster analyses indicated paleobathymetric differences within and between the sections. Maximum and minimum uplift rates were calculated from the biochronology, elevation, paleobathymetry and estimated eustatic changes. Large decreases in paleobathymetry were mainly due to the initial middle Pleistocene subduction of the Cocos Ridge in less than 0.5 Ma. Uplift rates were uneven across the Burica Peninsula, as follows: La Vaca 4.5–0.8 m/ky, Rabo de Puerco 2.8–0.7 m/ky, San Bartolo–Chiquito 2.7–0.8 m/ky, and eastern coast 8.0–1.5 m/ky. These differences probably resulted from Cocos Ridge asymmetry and differential uplift of tectonic blocks.

The effects of manipulation of sedimentary iron and organic matter on sediment biogeochemistry and seagrasses in a subtropical carbonate environment

The microbial metabolism of organic matter (OM) in seagrass beds can create sulfidic conditions detrimental to seagrass growth; iron (Fe) potentially has ameliorating effects through titration of the sulfides and the precipitation of iron-sulfide minerals into the sediment. In this study, the biogeochemical effects of Fe availability and its interplay with sulfur and OM on sulfide toxicity, phosphorous (P) availability, seagrass growth and community structure were tested. The availability of Fe and OM was manipulated in a 2 × 2 factorial experiment arranged in a Latin square, with four replicates per treatment. The treatments included the addition of Fe, the addition of OM, the addition of both Fe and OM as well as no addition. The experiment was conducted in an oligotrophic, iron-deficient seagrass bed. Fe had an 84.5% retention efficiency in the sediments with the concentration of Fe increasing in the seagrass leaves over the course of the experiment. Porewater chemistry was significantly altered with a dramatic decrease in sulfide levels in Fe addition plots while sulfide levels increased in the OM addition treatments. Phosphorus increased in seagrass leaves collected in the Fe addition plots. Decreased sulfide stress was evidenced by heavier δ34S in leaves and rhizomes from plots to which Fe was added. The OM addition negatively affected seagrass growth but increased P availability; the reduced sulfide stress in Fe added plots resulted in elevated productivity. Fe availability may be an important determinant of the impact that OM has on seagrass vitality in carbonate sediments vegetated with seagrasses.

Radiogenic neodymium, strontium and lead isotopes of authigenic and detrital sedimentary phases and stable oxygen and carbon isotopes of benthic foraminifera from gravity cores SO213-59-2 and SO213-60-1 (central South Pacific).

The South Pacific is a sensitive location for the variability of the global oceanic thermohaline circulation given that deep waters from the Atlantic Ocean, the Southern Ocean, and the Pacific Basin are exchanged. Here we reconstruct the deep water circulation of the central South Pacific for the last two glacial cycles (from 240,000 years ago to the Holocene) based on radiogenic neodymium (Nd) and lead (Pb) isotope records complemented by benthic stable carbon data obtained from two sediment cores located on the flanks of the East Pacific Rise. The records show small but consistent glacial/interglacial changes in all three isotopic systems with interglacial average values of -5.8 and 18.757 for epsilon Nd and 206Pb/204Pb, respectively, whereas glacial averages are -5.3 and 18.744. Comparison of this variability of Circumpolar Deep Water (CDW) to previously published records along the pathway of the global thermohaline circulation is consistent with reduced admixture of North Atlantic Deep Water to CDW during cold stages. The absolute values and amplitudes of the benthic delta13C variations are essentially indistinguishable from other records of the Southern Hemisphere and confirm that the low central South Pacific sedimentation rates did not result in a significant reduction of the amplitude of any of the measured proxies. In addition, the combined detrital Nd and strontium (87Sr/86Sr) isotope signatures imply that Australian and New Zealand dust has remained the principal contributor of lithogenic material to the central South Pacific.

TOC, TN, and sedimentary d15N and d13C ratios of sediment core SO201-2-85

We present high-resolution records of sedimentary nitrogen (d15Nbulk) and carbon isotope ratios (d13Cbulk) from piston core SO201-2-85KL located in the western Bering Sea. The records reflect changes in surface nitrate utilization and terrestrial organic matter contribution in submillennial resolution that span the last 180 kyr. The d15Nbulk record is characterized by a minimum during the penultimate interglacial indicating low nitrate utilization (~62-80%) despite the relatively high export production inferred from opal concentrations along with a significant reduction in the terrestrial organic matter fraction (mterr). This suggests that the consumption of the nitrate pool at our site was incomplete and even more reduced than today (~84%). d15Nbulk increases from Marine Isotope Stage (MIS) 5.4 and culminates during the Last Glacial Maximum, which indicates that nitrate utilization in the Bering Sea was raised during cold intervals (MIS 5.4, 5.2, 4) and almost complete during MIS 3 and 2 (~93-100%). This is in agreement with previous hypotheses suggesting that stronger glacial stratification reduced the nutrient supply from the subeuphotic zone, thereby increasing the iron-to-nutrient ratio and therefore the nitrate utilization in the mixed surface layer. Large variations in d15Nbulk were also recorded from 180 to 130 ka BP (MIS 6), indicating a potential link to insolation and sea-level forcing and its related feedbacks. Millennial-scale oscillations were observed in d15Nbulk and d13Cbulk that might be related to Greenland interstadials.

Chemical composition of bottom sediments and sedimentary rocks from the Pilippine Sea

Data on chemical composition of bottom sediments from some polygons in the Philippine Sea are reported. Areal and vertical variability of major and trace element contents in bottom sediments is analyzed for clarifying sedimentation features and diagenetic migration of the elements in the upper part of the sedimentary sequence.

Sedimentary record of the western Amundsen Sea Embayment after the last glacial maximum

Reliable dating of glaciomarine sediments deposited on the Antarctic shelf since the Last Glacial Maximum (LGM) is very challenging because of the general absence of calcareous (micro-) fossils and the recycling of fossil organic matter. As a consequence, radiocarbon (14C) ages of the acid-insoluble organic fraction (AIO) of the sediments bear uncertainties that are very difficult to quantify. In this paper we present the results of three different chronostratigraphic methods to date a sedimentary unit consisting of diatomaceous ooze and diatomaceous mud that was deposited following the last deglaciation at five core sites on the inner shelf in the western Amundsen Sea (West Antarctica). In three cores conventional 14C dating of the AIO in bulk sediment samples yielded age reversals down-core, but at all sites the AIO 14C ages obtained from diatomaceous ooze within the diatom-rich unit yielded similar uncorrected 14C ages ranging from 13,517±56 to 11,543±47 years before present (yr BP). Correction of these ages by subtracting the core-top ages, which are assumed to reflect present-day deposition (as indicated by 21044 Pb dating of the sediment surface at one core site), yielded ages between ca. 10,500 and 8,400 calibrated years before present (cal yr BP). Correction of the AIO ages of the diatomaceous ooze by only subtracting the marine reservoir effect (MRE) of 1,300 years indicated deposition of the diatom-rich sediments between 14,100 and 11,900 cal yr BP. Most of these ages are consistent with age constraints between 13.0 and 8.0 ka BP for the diatom-rich unit, which we obtained by correlating the relative palaeomagnetic intensity (RPI) records of three of the sediment cores with global and regional reference curves for palaeomagnetic intensity. As a third dating technique we applied conventional 53 radiocarbon dating of the AIO included in acid-cleaned diatom hard parts that were extracted from the diatomaceous ooze. This method yielded uncorrected 14C ages of only 5,111±38 and 5,106±38 yr BP, respectively. We reject these young ages, because they are likely to be overprinted by the adsorption of modern atmospheric carbon dioxide onto the surfaces of the extracted diatom hard parts prior to sample graphitisation and combustion for 14C dating. The deposition of the diatom-rich unit in the western Amundsen Sea suggests deglaciation of the inner shelf before ca. 13 ka BP. The deposition of diatomaceous oozes on other parts of the Antarctic shelf around the same time, however, seems to be coincidental rather than directly related.

Sedimentary record of the western Amundsen Sea Embayment

The Amundsen Sea Embayment (ASE) drains approximately 35% of the West Antarctic Ice Sheet (WAIS) and is one of the most rapidly changing parts of the cryosphere. In order to predict future ice-sheet behaviour, modellers require long-term records of ice-sheet melting to constrain and build confidence in their simulations. Here, we present detailed marine geological and radiocarbon data along three palaeo-ice stream tributary troughs in the western ASE to establish vital information on the timing of deglaciation of the WAIS since the Last Glacial Maximum (LGM). We have undertaken multi-proxy analyses of the cores (core description, shear strength, x-radiographs, magnetic susceptibility, wet bulk density, total organic carbon/nitrogen, carbonate content and clay mineral analyses) in order to: (1) characterise the sedimentological facies and depositional environments; and (2) identify the horizon(s) in each core that would yield the most reliable age for deglaciation. In accordance with previous studies we identify three key facies, which offer the most reliable stratigraphies for dating deglaciation by recording the transition from a grounded ice sheet to open marine environments. These facies are: i) subglacial, ii) proximal grounding-line, and iii) seasonal open-marine. In addition, we incorporate ages from other facies (e.g., glaciomarine diamictons deposited at some distance from the grounding line, such as glaciogenic debris flows and iceberg rafted diamictons and turbates) into our deglacial model. In total, we have dated 78 samples (mainly the acid insoluble organic (AIO) fraction, but also calcareous foraminifers), which include 63 downcore and 15 surface samples. Through careful sample selection prior to dating, we have established a robust deglacial chronology for this sector of the WAIS. Our data show that deglaciation of the western ASE was probably underway as early as 22,351 calibrated years before present (cal 44 yr BP), reaching the mid-shelf by 13,837 cal yr BP and the inner shelf to within c.10-12 km of the present ice shelf front between 12,618 and 10,072 cal yr BP. The deglacial steps in the western ASE broadly coincide with the rapid rises in sea-level associated with global meltwater pulses 1a and 1b, although given the potential dating uncertainty, additional, more precise ages are required before these findings can be fully substantiated. Finally, we show that the rate of ice-sheet retreat increased across the deep (up to1,600 m) basins of the inner shelf, highlighting the importance of reverse slope and pinning points in accelerated phases of deglaciation.

The response of lake margin sedimentary systems to climatically driven lake level fluctuations : Middle Devonian, Orcadian Basin, Scotland

Peer reviewed

First recorded occurrence of detrital baddeleyite (ZrO2) in sedimentary rock (Smith Bank Formation, Triassic, Central North Sea)

Peer reviewed

Regional Magma Plumbing and emplacement mechanisms of the Faroe-Shetland Sill Complex : Implications for magma transport and petroleum systems within sedimentary basins

Peer reviewed

Fluvial geomorphic elements in modern sedimentary basins and their potential preservation in the rock record : A review

We appreciate very helpful reviews by Dr. Martin Stokes and three anonymous reviewers and editor Dr. Richard Marston. We also appreciate the encouragement for writing this paper from Dr. Timothy Horscroft. We acknowledge support of the sponsors of the Fluvial Systems Research Group consortium, BP, BG, Chevron, ConocoPhillips and Total.

The response of lake margin sedimentary systems to climatically driven lake level fluctuations : Middle Devonian, Orcadian Basin, Scotland

Peer reviewed

First recorded occurrence of detrital baddeleyite (ZrO2) in sedimentary rock (Smith Bank Formation, Triassic, Central North Sea)

Peer reviewed

Regional Magma Plumbing and emplacement mechanisms of the Faroe-Shetland Sill Complex : Implications for magma transport and petroleum systems within sedimentary basins

Peer reviewed