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.     

Relict olivine grains, chondrule recycling, and implications for the chemical, thermal, and mechanical processing of nebular materials

Chondrules and isolated forsterites in five low-subtype ordinary chondrites [NWA 3127 (LL3.1), Sahara 97210 (LL3.2), Wells (LL3.3), Chainpur (LL3.4), and Sahara 98175 (LL3.5)] were studied using petrographic, EMPA, and SIMS techniques to better constrain the origin of chondrules and the olivine grains within them. Our results imply that igneous crystallization, vapor fractionation, redox effects, and open-system behavior were important processes. All olivine grains, including normal, relict, and isolated forsterite grains, show evidence for igneous fractionation under disequilibrium conditions, with olivine crystallizing during rapid cooling (closer to 2000 °C/h than to 100 °C/h). Vapor fractionation is manifested by anti-correlated abundances between refractory elements (Al, Sc, Y, Ti, Ca, V) and volatile elements (Cr, Mn, P, Rb, Fe) in olivine. Redox effects are evidenced in various ways, and imply that Fe, Co, Ni, and P were partitioned more into metal, and V was partitioned more into olivine, under reducing conditions in the most FeO-poor melts. There is no obvious evidence for systematic variations in olivine composition according to meteorite subtype, but shock melting in Sahara 97210 resulted in the injection of glass-derived melt into olivine, resulting in artificially high abundances of Ba, Sr, Na, Ti, and some other incompatible elements in olivine. Terrestrial weathering in a hot desert environment may have mobilized Ba and Sr in some glasses.Our data suggest that chondrules in ordinary chondrites experienced repeated thermal, chemical, and mechanical processing during a “recycling” process over an extended time period, which involved multiple episodes of melting under fluctuating redox and heating conditions, and multiple episodes of chondrule break-up in some cases. Forsterite grains, including normal grains in forsterite-bearing type I chondrules, the cores of isolated forsterites, and relict forsterite in type II chondrules, all crystallized from similar, refractory melts under reducing conditions; relict Mg-olivine and isolated forsterite grains were thus derived from type I chondrules. Olivine in type II chondrules, including normal grains and ferroan overgrowths on relict Mg-olivine, crystallized from more volatile-rich, oxidized, and relatively unfractionated melts. Relict dusty olivine grains in type I chondrules were derived from type II chondrules during incomplete melting episodes involving reduction and some vaporization, with clear (non-dusty) grains in dusty olivine-bearing chondrules crystallizing from the reduced and partly vaporized melts. Melt compositions parental to normal olivine grains in type I and II chondrules are systematically enriched in refractory elements compared to bulk chondrule compositions, implying that chondrules often experienced open-system exchange with more volatile-rich surroundings after some olivine had crystallized, possibly while the chondrules were still partly molten. Type II chondrules could have been derived from type I chondrules by the addition of relatively volatile-rich material, followed by re-melting and little evaporation under oxidizing conditions. In contrast, type I chondrules could have been derived from type II chondrules by re-melting involving more-or-less evaporation under reducing conditions. Chemical, oxygen isotope, and petrographic data are best accommodated by a model in which there were several (>2-3, sometimes ?4-5) melting episodes for most chondrules in ordinary chondrites.     

Cloning of a chub metallothionein cDNA and development of competitive RT-PCR of chub metallothionein mRNA as a potential biomarker of heavy metal exposure

Metallothionein has been assayed in a range of aquatic animal tissues as an indicator of metal exposure. We sequenced chub (Leuciscus cephalus) metallothionein cDNA which showed over 90% homology to common carp, goldfish and stone loach and 77% homology to rainbow trout sequences for metallothionein. We then used the extended primer method to develop an accurate quantitative competitive RT-PCR assay for metallothionein mRNA. RT-PCR was used to measure metallothionein mRNA in feral chub from a range of field sites, with different levels of heavy metal pollution, in the West Midlands, UK. Measurements were complemented by analysis of liver and gill metallothionein protein by capillary electrophoresis. There was no significant difference in the metallothionein protein levels between fish of different rivers and there was no evidence of elevation of mRNA at the sites of highest metal exposure. The level of metal exposure (e.g. zinc, nickel and cadmium each ranging between 15 and 28 microg/l ) at the pH (7.5-8.5) of these rivers appears insufficient to elevate hepatic or gill metallothionein in chub. A lack of elevation of hepatic metallothionein mRNA in chub exposed to zinc, copper and manganese for 24 h and 10 days in the laboratory also suggests a non-responsiveness of this species.     

Optical water type discrimination and tuning remote sensing band-ratio algorithms: Application to retrieval of chlorophyll and Kd(490) in the Irish and Celtic Seas

This paper assesses the feasibility of applying remote sensing algorithms based on blue/green reflectance ratios to Case 2 waters. Two algorithms from the SeaDAS (NASA) image processing package, OC4v4 for surface chlorophyll concentration, Chl, and K(490) for the attenuation coefficient for downward irradiance at 490 nm, K_d(490), were investigated using an extensive set of observations from the Irish and Celtic Seas. In situ data from a profiling radiometer were used as inputs for the algorithms to avoid uncertainties in atmospheric correction procedures, and direct measurements of Chl and K_d490 and were used for validation purposes. The standard versions of the algorithms performed poorly: OC4v4 generally overestimated Chl (with a very low coefficient of determination), and K(490) progressively underestimated K_d490 for values greater than 0.3 m⁻¹. A two-step procedure for level 2 product generation was therefore devised in which the numerical coefficients of OC4v4 and K(490) were tuned for the two optical water types known to occur most frequently in this region (McKee, D., Cunningham, A., 2006. Identification and characterisation of two optical water types in the Irish Sea from in situ inherent optical properties and seawater constituents. Estuarine, Coastal and Shelf Science 68, 305–316) by statistical regression on a data set of 102 stations from the Irish and Celtic Seas. The water types were distinguished by the magnitude of their normalised water leaving radiance signals at 665 nm, nL_w(665), and appropriate versions of the tuned algorithms applied to each water type. When this procedure was tested on an independent data set of 19 stations from the Bristol Channel, Chl values were recovered with an RMS error of 0.36 mg m⁻³ and K_d(490) values with an RMS error of 0.095 m⁻¹. The identification of water types from water-leaving radiance signals, and the application of band-ratio algorithms tuned for specific water types, may therefore provide a simple means of improving the quality of remote sensing products in optically complex shelf seas.     

Molecular and bulk isotopic analyses of organic matter in marls of the Mulhouse Basin (Tertiary, Alsace, France)

Contents of 13C in kerogens and carbonates in 21 samples from a core of the MAX borehole, Mulhouse Evaporite Basin, range from -27.3 to -23.5 and -3.7 to -1.8% vs PDB, respectively. Organic nitrogen in the same samples is enriched in 15N relative to atmospheric N2 by 12.2-15.7%. Hydrogen indices and delta values for kerogens vary systematically with facies, averaging 493 mg HC/g Corg and -25.7% in the most saline facies (dominated by inputs from aquatic sources) and 267 mg HC/g Corg and -23.7% in the least saline facies (50/50 aquatic/terrigenous). Values of delta were measured for individual aliphatic hydrocarbons from three samples representing three different organic facies. For all samples, terrigenous inputs were unusually rich in 13C, the estimated delta value for bulk terrigenous debris, apparently derived partly from CAM plants, being -22.5%. In the most saline facies, isotopic evidence indicates the mixing of 13C-depleted products of photosynthetic bacteria with 13C-enriched products of halotolerant eukaryotic algae. At lower salinities, a change in the producer community is marked by a decrease in the 13C content of algal lipids. The content of 13C in algal lipids increases in the least saline facies, due either to succession of different organisms or to decreased concentrations of dissolved CO2.     

Molecular indicators for palaeoenvironmental change in a Messinian evaporitic sequence (Vena del Gesso, Italy). II: High-resolution variations in abundances and 13C contents of free and sulphur-bound carbon skeletons in a single marl bed

The extractable organic matter of 10 immature samples from a marl bed of one evaporitic cycle of the Vena del Gesso sediments (Gessoso-solfifera Fm., Messinian, Italy) was analyzed quantitatively for free hydrocarbons and organic sulphur compounds. Nickel boride was used as a desulphurizing agent to recover sulphur-bound lipids from the polar and asphaltene fractions. Carbon isotopic compositions (delta vs PDB) of free hydrocarbons and of S-bound hydrocarbons were also measured. Relationships between these carbon skeletons, precursor biolipids, and the organisms producing them could then be examined. Concentrations of S-bound lipids and free hydrocarbons and their delta values were plotted vs depth in the marl bed and the profiles were interpreted in terms of variations in source organisms, 13 C contents of the carbon source, and environmentally induced changes in isotopic fractionation. The overall range of delta values measured was 24.7%, from -11.6% for a component derived from green sulphur bacteria (Chlorobiaceae) to -36.3% for a lipid derived from purple sulphur bacteria (Chromatiaceae). Deconvolution of mixtures of components deriving from multiple sources (green and purple sulphur bacteria, coccolithophorids, microalgae and higher plants) was sometimes possible because both quantitative and isotopic data were available and because either the free or S-bound pool sometimes appeared to contain material from a single source. Several free n-alkanes and S-bound lipids appeared to be specific products of upper-water-column primary producers (i.e. algae and cyanobacteria). Others derived from anaerobic photoautotrophs and from heterotrophic protozoa (ciliates), which apparently fed partly on Chlorobiaceae. Four groups of n-alkanes produced by algae or cyanobacteria were also recognized based on systematic variations of abundance and isotopic composition with depth. For hydrocarbons probably derived from microalgae, isotopic variations are well correlated with those of total organic carbon. A resistant aliphatic biomacromolecule produced by microalgae is, therefore, probably an important component of the kerogen. These variations reflect changes in the depositional environment and early diagenetic transformations. Changes in the concentrations of S-bound lipids induced by variations in conditions favourable for sulphurization were discriminated from those related to variations in primary producer assemblages. The water column of the lagoonal basin was stratified and photic zone anoxia occurred during the early and middle stages of marl deposition. During the last stage of the marl deposition the stratification collapsed due to a significant shallowing of the water column. Contributions from anaerobic photoautotrophs were apparently associated with variations in depth of the chemocline.     

Diploptene: an indicator of terrigenous organic carbon in Washington coastal sediments

The pentacyclic triterpene 17 beta(H),21 beta(H)-hop-22(29)-ene (diploptene) occurs in sediments throughout the Columbia River drainage basin and off the southern coast of Washington state in concentrations comparable to long-chain plantwax n-alkanes. The same relationship is evident for diploptene and long-chain n-alkanes in soils from the Willamette Valley. Microorganisms indigenous to soils and soil erosion are indicated as the biological source and physical process, respectively, for diploptene in coastal sediments. Similarity between the stable carbon isotopic composition (delta 13CPDB) of diploptene isolated from soil in the Willamette Valley (-31.2 +/- 0.3%) and from sediments deposited throughout the Washington coastal environment (-31.2 +/- 0.5%) supports this argument. Values of delta for diploptene in river sediments are variable and 8-17% lighter, indicating that an additional biological source such as methane-oxidizing bacteria makes a significant contribution to the diploptene record in river sediments. Selective biodegradation resulting from a difference in the physicochemical association within eroded particles can explain the absence of the more-13C-depleted form of diploptene in Washington coastal sediments, but this mechanism remains unproven.     

Fractionation of carbon isotopes by phytoplankton and estimates of ancient CO2 levels

Reports of the 13C content of marine particulate organic carbon are compiled and on the basis of GEOSECS data and temperatures, concentrations, and isotopic compositions of dissolved CO2 in the waters in which the related phytoplankton grew are estimated. In this way, the fractionation of carbon isotopes during photosynthetic fixation of CO2 is found to be significantly correlated with concentrations of dissolved CO2. Because ancient carbon isotopic fractionations have been determined from analyses of sedimentary porphyrins [Popp et al., 1989], the relationship between isotopic fractionation and concentrations of dissolved CO2 developed here can be employed to estimate concentrations of CO2 dissolved in ancient oceans and, in turn, partial pressures of CO2 in ancient atmospheres. The calculations take into account the temperature dependence of chemical and isotopic equilibria in the dissolved-inorganic-carbon system and of air-sea equilibria. Paleoenvironmental temperatures for each sample are estimated from reconstructions of paleogeography, latitudinal temperature gradients, and secular changes in low-latitude sea surface temperature. It is estimated that atmospheric partial pressures of CO2 were over 1000 micro atm 160 - 100 Ma ago, then declined to values near 300 micro atm during the next 100 Ma. Analysis of a high-resolution record of carbon isotopic fractionation at the Cenomanian-Turonian boundary suggests that the partial pressure of CO2 in the atmosphere was drawn down from values near 840 micro atm to values near 700 micro atm during the anoxic event.     

An estimate of the temperature and abundance of CH4 and other molecules in the atmosphere of Uranus

We present a preliminary analysis of CH₄ absorptions near 6800 Å in new high resolution spectra of Uranus. A curve of growth analysis of the data yields a rotational temperature near 100 K and a CH₄/H₂ ratio that is 1 to 3 times that expected for a solar type composition. The long pathlengths of CH₄, apparently demanded by absorptions near 4700 Å, are qualitatively shown to be the result of line formation in a deep, predominantly Rayleigh scattering atmosphere in which continuum absorption is a strong function of wavelength. The analysis of the CH₄ also yields a minimum value for the effective pressure of line formation (～ 2 atm). This value is shown to be twice that expected on Uranus if the atmosphere were predominantly H₂. It is speculated that large amounts of some otherwise optically inert gas is present in the Uranus atmosphere. N₂ is suggested as a possible candidate since there are cosmogonic reasons why Uranus should contain large amounts of N relative to C, He, and H, and also because the pressure-induced pure rotation spectrum of N₂ could possibly account for the low brightness temperatures that have recently been observed at 33 and 350 μm. If N₂ is present the planet probably possesses a surface at the 10–100 atmosphere level.