Stable carbon-isotopic compositions of lipids isolated from the ammonia-oxidizing chemoautotroph Nitrosomonas europaea

For the ammonia-oxidizing bacterium Nitrosomonas europaea, grown autotrophically using semicontinuous culturing, average biomass was depleted in ¹³C relative to CO₂ dissolved in the medium by ca. 20‰ and the total-lipid extract was depleted in ¹³C relative to biomass by 3.7‰. The n-alkyl lipids (weighted average of fatty acids) and isoprenoid lipids (weighted average of hopanoids) were both depleted in ¹³C relative to biomass by about 9‰. The large depletion in the isoprenoid lipids seems to indicate that isotopic fractionations associated with the biosynthesis of methylerythritol phosphate (MEP) affected at least two carbon positions in each isoprene unit. Among the fatty acids, trans-9-hexadecenoic acid was most depleted (13.0‰ relative to biomass), followed by cis-9- hexadecenoic acid (9.6‰) and hexadecanoic acid (6.9‰). Isotopic relationships between the three acids suggest that significant isotope effects were associated with the desaturation and cis to trans isomerization of fatty acids. Given these observations, hopanoids produced by ammonia-oxidizing bacteria growing in natural waters are likely to be depleted in ¹³C by 26–30‰ relative to dissolved CO₂. Since CO₂ at aquatic oxyclines is often depleted in ¹³C, the range of δ values expected for hopanoids is ca. −34‰ to −55‰. The δ values of geohopanoids observed in numerous studies and attributed to unspecified chemoautotrophs fall within this range.     

The carbon isotopic response of algae, (cyano)bacteria, archaea and higher plants to the late Cenomanian perturbation of the global carbon cycle: Insights from biomarkers in black shales from the Cape Verde Basin (DSDP Site 367)

The stable carbon isotopic compositions of free and sulfur (S)-bound biomarkers derived from algae, (cyano)bacteria, archaea and higher plants and total organic carbon (TOC) during the first phase of the late Cenomanian/Turonian oceanic anoxic event (OAE) were measured in black shales deposited in the southern proto-Atlantic Ocean in the Cape Verde basin (DSDP Site 367) to determine the response of these organisms to this major perturbation of the global carbon cycle resulting from widespread burial of marine organic matter. The average positive isotope excursions of TOC and biomarkers varied from 5.1‰ to 8.3‰. The δ¹³C values were cross correlated to infer potential common sources of biomarkers. This revealed common sources for C₃₁ and C₃₂ hopanes but no 1:1 relationship for pristane and phytane. The correlation of δ¹³C_TOC with the δ¹³C value of sulfur (S)-bound phytane is the strongest. This is because S-bound phytane is derived from phytol that originates from all marine primary producers (algae and cyanobacteria) and thus represents a weighted average of their carbon isotopic compositions. The δ¹³C values of S-bound phytane and C₃₅ hopane were also used to estimate pCO₂ levels. Before the OAE burial event, pCO₂ levels are estimated to be ca. 1300 ppmv using both biomarkers and the independent maximum Rubisco fractionation factors. At times of maximum organic carbon burial rates during the OAE, reconstructed pCO₂ levels are estimated to be ca. 700 ppmv. However, compared to other C/T OAE sections the positive isotope excursion of S-bound phytane is also affected by an increased production during the OAE. When we compensate for this, we arrive at pCO₂ levels around 1000 ppmv, a reduction of ca. 25%. This indicates that burial of organic matter can have a large effect on atmospheric CO₂ levels.     

Thermal stability of ladderane lipids as determined by hydrous pyrolysis

Anaerobic ammonium oxidation (anammox) has been recognized as a major process resulting in loss of fixed inorganic nitrogen in the marine environment. Ladderane lipids, membrane lipids unique to anammox bacteria, have been used as markers for the detection of anammox in marine settings. However, the fate of ladderane lipids after sediment burial and maturation is unknown. In this study, anammox bacterial cell material was artificially matured by hydrous pyrolysis at constant temperatures ranging from 120 to 365 °C for 72 h to study the stability of ladderane lipids during progressive dia- and catagenesis. HPLC-MS/MS analysis revealed that structural alterations of ladderane lipids already occurred at 120 °C. At temperatures >140 °C, ladderane lipids were absent and only more thermally stable products could be detected, i.e., ladderane derivatives in which some of the cyclobutane rings were opened. These diagenetic products of ladderane lipids were still detectable up to temperatures of 260 °C using GC-MS. Thus, ladderane lipids are unlikely to occur in ancient sediments and sedimentary rocks, but specific diagenetic products of ladderane lipids will likely be present in sediments and sedimentary rocks of relatively low maturity (i.e., C₃₁ hopane 22S/(22S + 22R) ratio <0.2 or ββ/(αβ + βα + ββ) ratio of >0.5).     

Mineralogy and composition of Kuroko deposits from northeastern Honshu and their possible modern analogues from the Izu-Ogasawara (Bonin) Arc south of Japan: Implications for mode of formation

The Kuroko deposits of NE Honshu are a key type deposit for the study of volcanogenic massive sulfide deposits. However, these deposits have not been studied in detail since the early 1980's and knowledge of their mode of formation is now dated. In this study, we present the analysis of 12 samples of the Kuroko deposits, 12 samples of submarine hydrothermal minerals from the Sunrise deposit and 6 samples from Suiyo Seamount, both of which are located on the Izu-Ogasawara (Bonin) Arc, for 27 elements. For the Kuroko deposit, Cd>Sb>Ag>Pb>Hg>As>Zn>Cu are highly enriched, Au>Te>Bi>Ba>Mo are moderately enriched, In>Tl are somewhat enriched and Fe is not significantly enriched relative to the average continental crust. Within each of these deposits, a similar pattern of element associations is apparent: Zn–Pb with As, Sb, Cd, Ag, Hg, Tl and Au; Fe–Cu–Ba with As, Sb, Ag, Tl, Mo, Te and Au; Si–Ba with Ag and Au; CaSO₄. The enrichment of the chalcophilic elements in these deposits is consistent with hydrothermal leaching of these elements from the host rocks which are dominantly rhyolite–dacite in the case of the Kuroko deposits, rhyolite in the case of the Sunrise deposit and dacite–rhyolite in the case of the Suiyo Seamount deposit. However, this pattern of element enrichment is also similar to that observed in fumarolic gas condensates from andesitic volcanoes. This suggests that there may be a significant magmatic contribution to the composition of the hydrothermal fluids responsible for the formation of the Kuroko deposits, although it is not yet possible to quantify the relative contributions of these two sources of elements.The compositional data show that Sunrise and Suiyo Seamount deposits are much closer compositionally to the Kuroko deposits from NE Honshu than are the submarine hydrothermal deposits from the JADE site in the Okinawa Trough which contain, on average, significantly higher concentrations of Pb, Zn, Sb, As and Ag than each of these deposits. In spite of the greater similarity in tectonic setting of the Hokuroku Basin in which the Kuroko deposits formed to the Okinawa Trough (intracontinental rifted back-arc basin) compared to Myojin Knoll and Suiyo Seamount (active arc volcanoes), it appears that submarine hydrothermal deposits from Myojin Knoll and Suiyo Seamount are closer analogues of the Kuroko deposit than are those from the Okinawa Trough. The present data are consistent with the magmatic hydrothermal model for the formation of Kuroko-type deposits as formulated by Urabe and Marumo [Urabe, T., Marumo, K., 1991. A new model for Kuroko-type deposits of Japan. Episodes 14, 246–251].     

Mapping Proterozoic unconformity-related uranium deposits in the Rockhole area, Northern Territory, Australia using landsat ETM+

The Rockhole area, Northern Territory, Australia, hosts a number of Proterozoic unconformity-related uranium deposits. The geology of the area features within Paleoproterozoic rocks of the Pine Creek Orogen, near the unconformity with overlying platform cover sandstone of the Paleo- to Mesoproterozoic McArthur Basin. Landsat Enhanced Thematic Mapper plus (ETM+) data was used in the Rockhole area to assist in mapping geological structures and lithology, and to identify anomalous concentrations of ferrous minerals, the product of alteration, which can be indicators of buried uranium mineralization. Several image-processing procedures were applied to the ETM+ data to identify, isolate and enhance mineralogical information as simple and complex false color composites. ETM+ 754 shown as red green and blue respectively was the best simple image. Overall, complex images based on Principal Component Analysis proved to be the most useful products. Sandstone, shale and siltstone, the target lithologies, Koolpin Formation, the target stratigraphic unit, and bleaching pattern due to the removal of iron(II) compounds, the target alteration pattern, were confidently mapped to provide information required by the mineral emplacement model, which ultimately identified areas of likely uranium mineralization. Thus the contrasting behavior of the two principle oxidation states of uranium and iron can be utilized to map/delineate bleached alteration zones associated with economic concentrations of uranium using multispectral sensors like Landsat or better hyperspectral sensors.     

Ultrahigh pressure macro diamonds from Copeton (New South Wales, Australia), based on Raman spectroscopy of inclusions

Mining of Cenozoic alluvial deposits at Copeton and Bingara (Eastern Australia) has produced two million macrodiamonds (0.25 ct median size). Raman spectroscopy is used to identify included minerals within uncut Copeton diamonds, with sealed chamber remnant pressures of 31.7 to 35.6 kbar for coesite, 13.6 and 22.7 kbar for clinopyroxene, and 7.6 kbar for grossular garnet. Assuming elastic behaviour, these values generate inclusion entrapment PT loci which intersect, restricting diamond formation conditions: from 250 °C, 43 kbar to 800 °C, 52 kbar. Larger than error (± 100 °C and ± 4 kbar), this range shows a systematic variation in inclusion composition with diamond zoning and N properties. Published research shows 1) Copeton and Bingara diamonds are unique, and 2) modern alluvium in the Bingara district carries mantle-formed garnet, captured by post-tectonic alkali basalt from an extensive diamondiferous ultrahigh pressure (UHP) terrane that stalled at depth because it is dominated by mafic eclogite. The combined Raman and geological results indicate two sets of subduction UHP diamond formation conditions/protolith are required, firstly cooler oceanic slab and secondly including higher temperature continental crust. The Copeton and Bingara stones are UHP macrodiamonds, and Carboniferous ⁴⁰Ar/³⁹Ar age dates on clinopyroxene inclusions should be interpreted as ages of crystallisation, representing the termination of subduction. The characteristic features of ruptured inclusions and etched percussion marks on Copeton and Bingara diamond indicate volcanic delivery to the earth's surface. Alluvial deposits elsewhere in Eastern Australia may carry similar diamond along with diamond of different origin.     

Organic carbon deposition and phosphorus accumulation during Oceanic Anoxic Event 2 in Tarfaya, Morocco

With a multi-proxy approach, an attempt was made to constrain productivity and bottom-water redox conditions and their effects on the phosphorus accumulation rate at the Mohammed Plage section on the Tarfaya coast, Morocco, during the Cenomanian-Turonian Anoxic Event (OAE 2). A distinct δ¹³C_org isotope excursion of +2.5‰ occurs close to the top of the section. The unusually abrupt shift of the isotope excursion and disappearance of several planktonic foraminiferal species (e.g. Rotalipora cushmani and Rotalipora greenhornensis) in this level suggests a hiatus of between 40–60 kyrs at the excursion onset. Nevertheless, it was possible to determine both the long-term environmental history as well as the processes that took place immediately prior to and during OAE 2. TOC% values increase gradually from the base of the section to the top (from 2.5% to 10%). This is interpreted as the consequence of a long-term eustatic sea-level rise and subsidence causing the encroachment of less oxic waters into the Tarfaya Basin. Similarly a reduction in the mineralogically constructed ‘detrital index’ can be explained by the decrease in the continental flux of terrigenous material due to a relative sea-level rise. A speciation of phosphorus in the upper part of the section, which spans the start and mid-stages of OAE 2, shows overall higher abundances of P_reactive mass accumulation rates before the isotope excursion onset and lower values during the plateau. Due to the probable short hiatus, the onset of the decrease in phosphorus content relative to the isotope excursion is uncertain, although the excursion plateau already contains lower concentrations. The C_org/P_total and V/Al ratios suggest that this reduction was mostly likely caused by a decrease in the available bottom oxygen content (probably as a result of higher productivity) and a corresponding fall in the phosphorus retention ability of the sediment. Productivity appears to have remained high during the isotope plateau possibly due to a combination of ocean-surface fertilisation via increased aridity (increased K/Al and Ti/Al ratios) and/or higher dissolved inorganic phosphorus content in the water column as a result of the decrease in sediment P retention. The evidence for decreased P-burial has been observed in many other palaeoenvironments during OAE 2. Tarfaya's unique upwelling paleosituation provides strong evidence that the nutrient recycling was a global phenomenon and therefore a critical factor in starting and sustaining OAE 2.     

Magnetotelluric investigations for imaging electrical structure of Garhwal Himalayan corridor,Uttarakhand, India

Magnetotelluric investigations have been carried out in the Garhwal Himalayan corridor to delineate the electrical structure of the crust along a profile extending from Indo-Gangetic Plain to Higher Himalayan region in Uttarakhand, India. The profile passing through major Himalayan thrusts: Himalayan Frontal Thrust (HFF), Main Boundary Thrust (MBT) and Main Central Thrust (MCT), is nearly perpendicular to the regional geological strike. Data processing and impedance analysis indicate that out of 44 stations MT data recorded, only 27 stations data show in general, the validity of 2D assumption. The average geoelectric strike, N70°W, was estimated for the profile using tensor decomposition. 2D smooth geoelectrical model has been presented, which provides the electrical image of the shallow and deeper crustal structure. The major features of the model are (i) a low resistivity (<50Ωm), shallow feature interpreted as sediments of Siwalik and Indo-Gangetic Plain, (ii) highly resistive (> 1000Ωm) zone below the sediments at a depth of 6 km, interpreted as the top surface of the Indian plate, (iii) a low resistivity (< 10Ωm) below the depth of 6 km near MCT zone coincides with the intense micro-seismic activity in the region. The zone is interpreted as the partial melting or fluid phase at mid crustal depth. Sensitivity test indicates that the major features of the geoelectrical model are relevant and desired by the MT data.     

Characteristics of spectral aerosol optical depths over India during ICARB

Spectral aerosol optical depth (AOD) measurements, carried out regularly from a network of observatories spread over the Indian mainland and adjoining islands in the Bay of Bengal and Arabian Sea, are used to examine the spatio-temporal and spectral variations during the period of ICARB (March to May 2006). The AODs and the derived Ångström parameters showed considerable variations across India during the above period. While at the southern peninsular stations the AODs decreased towards May after a peak in April, in the north Indian regions they increased continuously from March to May. The Ångström coefficients suggested enhanced coarse mode loading in the north Indian regions, compared to southern India. Nevertheless, as months progressed from March to May, the dominance of coarse mode aerosols increased in the columnar aerosol size spectrum over the entire Indian mainland, maintaining the regional distinctiveness. Compared to the above, the island stations showed considerably low AODs, so too the northeastern station Dibrugarh, indicating the prevalence of cleaner environment. Long-range transport of aerosols from tshe adjoining regions leads to remarkable changes in the magnitude of the AODs and their wavelength dependencies during March to May. HYSPLIT back-trajectory analysis shows that enhanced long-range transport of aerosols, particularly from the west Asia and northwest coastal India, contributed significantly to the enhancement of AOD and in the flattening of the spectra over entire regions; if it is the peninsular regions and the island Minicoy are more impacted in April, the north Indian regions including the Indo Gangetic Plain get affected the most during May, with the AODs soaring as high as 1.0 at 500 nm. Over the islands, the Ångström exponent (α) remained significantly lower (～1) over the Arabian Sea compared to Bay of Bengal (BoB) (～1.4) as revealed by the data respectively from Minicoy and Port Blair. Occurrences of higher values of α, showing dominance of accumulation mode aerosols, over BoB are associated well with the advection, above the boundary layer, of fine particles from the east Asian region during March and April. The change in the airmass to marine in May results in a rapid decrease in α over the BoB.     

Evaluation of coal bed methane potential of coal seams of Sawang Colliery,Jharkhand, India

The coal seams of Sawang Colliery, East Bokaro Coalfields are bituminous to sub-bituminous in nature and categorized as high gaseous seams (degree II to degree III level). These seams have the potential for coal bed methane (CBM) and their maturity increases with increasing depth, as a result of enhanced pressure-temperature conditions in the underground. The vitrinite maceral group composition of the investigated coal seams ranges from 62.50–83.15%, whereas the inertinite content varies from 14.93–36.81%. The liptinite content varies from 0.66% to 3.09%. The maximum micro-pores are confined within the vitrinite group of macerals. The coal seams exhibit vitrinite reflectance values (Ro% calculated) from 0.94% (sample CG-97) to 1.21% (sample CG-119). Proximate analyses of the investigated coal samples reveal that the moisture content (M%) ranges from 1.28% to 2.98%, whereas, volatile matter (VM%) content is placed in the range of 27.01% to 33.86%. The ash content (A%) ranges from 10.92% to 30.01%. Fixed carbon (FC%) content varies from 41.53% to 55.93%. Fuel ratio variation shows a restricted range from 1.53 to 1.97. All the coal samples were found to be strongly caking and forming coke buttons. The present study is based on the adsorption isotherm experiments carried out under controlled P-T conditions for determination of actual gas adsorption capacity of the coal seams. This analysis shows that the maximum methane gas adsorbed in the coal sample CG-81 is 17 m³/t (Std. daf), at maximum pressure of 5.92 MPa and experimental temperature of 30°C. The calculated Langmuir regression parameters P_L and V_L range from 2.49 to 3.75 MPa and 22.94 to 26.88 m³/t (Std. daf), respectively.