Carbon,hydrogen and nitrogen isotopes in solvent-extractable organic matter from carbonaceous chondrites

Solvent extractions were done on the carbonaceous chondrites Murray, Murchison, Orgueil and Renazzo, using CCl₄ and CH₃OH. Between 2 and 10% of the total carbon in these meteorites is extractable by ordinary techniques, most of it in CH₃OH. After demineralization with HF, perhaps as much as 30% of the total carbon in Murray may be extractable with CH₃OH. The extracts from Renazzo have isotopic ratios which suggest that they are mainly terrestrial organic matter, with lesser contributions from indigenous organics. The CH₃OH-soluble organic matter from Murchison and both untreated and HF-treated Murray has δ¹³C values of about +5 to + 10%. and δ¹⁵N values of about +90 to +100%., both of which are significantly higher than the bulk meteorite values. The Orgueil CH₃OH-extract also has a δ¹⁵N value well above the value in residual organic matter. Values for δD of +300 to +500%. are found for the CH₃OH-soluble organic matter. The combined data for C, H and N isotopes makes it highly unlikely that the CH₃OH-soluble components are derivable from, or simply related to, the insoluble organic polymer found in the same meteorites. A relationship is suggested between the event that formed hydrous minerals in CI1 and CM2 meteorites and the introduction of water-soluble (methanol-soluble) organic compounds. Organic matter soluble in CCl₄ has essentially no nitrogen, and δ³C and δD values are lower than for CH₃OH-soluble phases. Either there are large isotopic fractionations for carbon and hydrogen between different soluble organic phases, or the less polar components are partially of terrestrial origin.     

Nitrogen isotopic composition of macromolecular organic matter in interplanetary dust particles

Nitrogen concentrations and isotopic compositions were measured by ion microprobe scanning imaging in two interplanetary dust particles L2021 K1 and L2036 E22, in which imaging of D/H and C/H ratios has previously evidenced the presence of D-rich macromolecular organic components. High nitrogen concentrations of 10-20 wt% and δ¹⁵N values up to +400‰ are observed in these D-rich macromolecular components. The previous study of D/H and C/H ratios has revealed three different D-rich macromolecular phases. The one previously ascribed to macromolecular organic matter akin the insoluble organic matter (IOM) from carbonaceous chondrites is enriched in nitrogen by one order of magnitude compared to the carbonaceous chondrite IOM, although its isotopic composition is still similar to what is known from Renazzo (δ¹⁵N = +208‰).The correlation observed in macromolecular organic material between the D- and ¹⁵N-excesses suggests that the latter originate probably from chemical reactions typical of the cold interstellar medium. These interstellar materials preserved to some extent in IDPs are therefore macromolecular organic components with various aliphaticity and aromaticity. They are heavily N-heterosubstituted as shown by their high nitrogen concentrations >10 wt%. They have high D/H ratios >10⁻³ and δ¹⁵N values ≥ +400‰. In L2021 K1 a mixture is observed at the micron scale between interstellar and chondritic-like organic phases. This indicates that some IDPs contain organic materials processed at various heliocentric distances in a turbulent nebula. Comparison with observation in comets suggests that these molecules may be cometary macromolecules. A correlation is observed between the D/H ratios and δ¹⁵N values of macromolecular organic matter from IDPs, meteorites, the Earth and of major nebular reservoirs. This suggests that most macromolecular organic matter in the inner solar system was probably issued from interstellar precursors and further processed in the protosolar nebula.     

Molecular and compound-specific isotopic characterization of monocarboxylic acids in carbonaceous meteorites

Low molecular weight monocarboxylic acids are the most abundant water soluble organic compounds in the Murchison and many other CM type carbonaceous chondrites. In this study, we examined the monocarboxylic acids in Murchison and EET96029.20 carbonaceous meteorites using a new sample preparation and introduction technique for gas chromatograph recently developed for volatile, water-soluble organic compounds: solid phase micro-extraction (SPME). We identified more than 50 monocarboxylic acids from Murchison compared with the 18 compounds reported previously. Formic acid, a known interstellar molecule, has been fully analyzed in these carbonaceous meteorites, with its δD value suggesting an interstellar origin. We determined both carbon and hydrogen isotopic ratios of individual monocarboxylic acids in Murchison, to better define the origins and genetic relationships of these compounds. The compound-specific isotopic data reveal a large enrichment in ¹³C (δ¹³C up to + 32.5‰) and particularly D (δD up to + 2024‰). The branched acids are substantially enriched in both ¹³C and D relative to the straight chain acids, with those branched acids containing a quaternary carbon showing the greatest isotopic enrichment. The isotopic difference may be attributed to variations in the different synthetic regimes or terrestrial input of straight chain acids.     

Carbon,hydrogen and nitrogen in carbonaceous chondrites: Abundances and isotopic compositions in bulk samples

Whole-rock samples of 25 carbonaceous chondrites were analysed for contents of C, H and N and δ¹³C, δD and δ¹⁵N. Inhomogeneous distribution of these isotopes within individual meteorites is pronounced in several cases. Few systematic intermeteorite trends were observed; N data are suggestive of isotopic inhomogeneity in the early solar system. Several chondrites revealed unusual compositions which would repay further, more detailed study. The data are also useful for classification of carbonaceous chondrites; N abundance and isotopic compositions can differentiate existing taxonomic groups with close to 100% reliability; Al Rais and Renazzo clearly constitute a discrete “grouplet”; and there are hints that both CI and CM groups may each be divisible into two subgroups.     

SPORE-POLLEN COMPLEXES OF UPPER DEVONIAN OF THE RUSSIAN PLATFORM

Carbonaceous units commonly host or are closely related to lode-gold mineralization in the mesothermal Fazenda Maria Preta (FMP) and Fazenda Canto (FC) deposits of the Paleoproterozoic Rio Itapicuru greenstone belt of northeastern Brazil. In these deposits, the carbonaceous matter occurs mainly as: (1) straight to anastomosing seams (Type I) along or transecting the rock fabric, or as stylolitic structures in quartz veins; (2) single grains composed of an agglomerate of highly anisotropic subgrains (Type II); or (3) single grains with a homogeneous internal texture (Type III), which are either enclosed in Type-I carbonaceous seams or disseminated in the rock matrix. Type-I carbonaceous matter commonly hosts or is overgrown by the gold-related sulfide paragenesis, particularly arsenopyrite, whereas both Type I and Type II enclose crystals of arsenopyrite or occur as inclusions and in sharp contact with the sulfide phases.

The three morphological types of carbonaceous matter exhibit similar Raman spectral characteristics, with distinct D and O peaks at wave numbers between 1351 cm^?1 and 1357 cm^?1, and 1585 cm^?1 and 1598 cm^?1, respectively. In contrast to the FMP deposit, the carbonaceous matter of the FC deposit shows D peaks of higher intensities than the O peaks. The O peaks are accompanied by an additional disorder-induced band on the high wave number side (≈ 1622 cm^?1), and the O/D peak intensity ratios are higher and the half-height O-peak widths smaller. These spectral parameters indicate that the carbonaceous matter in both deposits corresponds to some form of microcrystalline disordered graphitic material and defines a graphitization trend from the FMP to the FC deposit.

The carbonaceous matter of the FMP deposit is isotopically lighter (δ¹³C = ?23.3‰ to ?30.8‰; x = ?27.4 ± 1.8‰ relative to PDB) than the carbonaceous material of the FC (δ¹³C = ?18.5‰ to ?21.0‰, x = ?19.7 ± 0.9‰). These δ¹³C values, together with the geologic evidence, point toward a primarily biogenic organic origin for the carbonaceous matter. The marked differences in the Raman spectral parameters and the δ₁₃C values are interpreted as resulting from different degrees of thermal maturation of carbonaceous matter attained during the regional greenschist metamorphism and granite intrusions of the Rio Itapicuru greenstone belt.

The δ¹³C compositions of CO₂ resulting from the oxidation or hydrolysis of the carbonaceous matter, calculated by applying the equilibrium CO₂-graphite fractionation, fall within the range ?9.7‰ to ?18.8‰ at 360 to 420°C (FMP deposit) and ?6.0° to ?10.0° at 390 to 455°C (FC deposit). These calculated δ¹³C values are lower than those obtained from primary fluid-inclusion CO₂ in gold-bearing veins (?6.0° to ?10.2° for the FMP deposit; ?2.8° to ?4.9° for the FC deposit) and imply that the thermal maturation process of the carbonaceous matter contributed little to changes in the chemistry and isotopic composition of the ore fluid. The presence of the carbonaceous matter may have been an important factor in gold deposition during fluid-carbon interaction, acting: (1) as a chemical trap, by reducing the f(O₂) of the ore fluids or enhancing fluid immiscibility by adding small quantities of CH₄ and N₂ to the fluid phase; and/or (2) as a physical barrier, by adsorbing gold on its surface as activated carbon.     

Hydrogen and carbon isotopes of petroleum and related organic matter

$\text{D}\text{H}$ and ${}^{13}\text{C}{}^{12}\text{C}$ ratios were measured for 114 petroleum samples and for several samples of related organic matter. δD of crude oil ranges from ?85 to ?181‰, except for one distillate (?250‰) from the Kenai gas field; δ¹³C of crude oil ranges from ?23.3 to ?32.5‰, Variation in δD and δ¹³C values of compound-grouped fractions of a crude oil is small, 3 and 1.1%., respectively, and the difference in δD and δ¹³C between oil and coeval wax is slight. Gas fractions are 53–70 and 22.6–23.2‰ depleted in D and ¹³C, respectively, relative to the coexisting oil fractions.The δD and δ¹³C values of the crude oils appear to be largely determined by the isotopic compositions of their organic precursors. The contribution of terrestrial organic debris to the organic precursors of most marine crude oils may be significant.     

Molecular and compound-specific hydrogen isotope analyses of insoluble organic matter from different carbonaceous chondrite groups

We have conducted the first systematic analyses of molecular distribution and δD values of individual compounds in pyrolysates of insoluble organic matter (IOM) from different carbonaceous chondrite groups, using flash pyrolysis coupled to gas chromatography-mass spectrometry and compound-specific D/H analysis. IOM samples from six meteorites of different classifications, Elephant Moraine (EET) 92042 (CR2), Orgueil (CI1), Allan Hills (ALH) 83100 (CM1/2), Murchison (CM2), ALH 85013 (CM2), and Tagish Lake (C2) were isolated and studied. Except for the pyrolysate of Tagish Lake IOM, pyrolysates of all five meteorite IOM samples were dominated by an extensive series of aromatic (C₁ to C₇ alkyl-substituted benzenes, C₀ to C₂ alkyl-substituted naphthalenes), with aliphatic (straight chain and branched C₁₀ to C₁₅ alkanes) hydrocarbons and several S- and O- containing compounds (C₁ to C₂ alkylthiophenes, benzothiophene, benzaldehyde) being also present. The strong similarity in the pyrolysates of different carbonaceous chondrites suggests certain common characteristics in the formation mechanisms of IOM from different meteorites. The Tagish Lake IOM sample is unique in that its pyrolysate lacks most of the alkyl-substituted aromatic hydrocarbons detected in other meteorite IOM samples, suggesting distinctively different formation processes. Both bulk δD values of meteorite IOMs and weighted-average δD values of individual compounds in pyrolysates show a decreasing trend: CR2 > CI1 > CM2 > C2 (Tagish Lake), with the EET 92042 (CR2) IOM having the highest δD values (∼2000‰ higher than other samples). We attribute the high D contents in the IOM to primitive interstellar organic sources.     

Multi-stage fluid incursion in the Palaeozoic basement-hosted Saint-Salvy ore deposit (NW Montagne Noire,southern France)

The Saint-Salvy vein-hosted Zn (+Ge) deposit occurs in an E–W fault system which flanks the southern margin of the late Variscan Sidobre granite, and cross-cuts Cambrian black shales of the Palaeozoic basement. Comprehensive mineralogical and geochemical studies of vein samples have revealed four mineralizing events (M1–M4) related to late and post-Variscan tectonic events. A further late-stage event may be related to weathering.M1 (=skarn deposits) and M2 (=patchily mineralized quartz veinlets) are associated with granite emplacement. Quartz contains low salinity, H₂OCO₂(NaCl)-dominated fluids(⩽6wt% NaCl equiv.) of relatively high temperature (300–580°C), trapped under moderate to high pressure. Estimated M1 fluid δD and calculated fluidδ¹⁸O plot within the metamorphic water field. There appears to be no involvement of magmatic fluids.By contrast, M3 (= barren quartz) and M4 (= zinciferous economic mineralization) stages have H₂OCO₂NaClCaCl₂ fluid inclusions with high salinities (23–25 wt% NaCl equiv.) and low temperatures(∼ 80–140°C), which were trapped under low-pressure conditions. The high salinity and NaCl + CaCl₂ content of both M3 and M4 indicates that their parent fluids leached evaporitic salts. M3 fluids are meteoric water dominated, falling close to the meteoric water line (δD andδ¹⁸O averaging −64 and −8‰, respectively). M4 fluids have highly distinctive δD averaging −101‰, and calculated fluidδ¹⁸O varying from−1.2to+7.1‰. The unusually low δD composition of M4 suggests the involvement of “organic” fluids, in which H is derived directly or indirectly from organic matter. The relatively highδ¹⁸O of M4 fluids indicates that considerable isotopic exchange with sedimentary material took place, displacing theδ¹⁸O from the meteoric water line. The data imply interaction of meteoric waters with evaporite and hydrocarbon-bearing sedimentary sequences, most probably the adjacent Aquitain Basin.The main economic mineralization (M4 stage) took place during a tensional event, probably coincident with the Lias-Dogger transition.Calculatedδ³⁴S_H2S of M4 sulphide(+5.4to+8.2‰) is almost identical toδ³⁴S of local Cambrian sulphides(+4.7to+9.4‰) suggesting a genetic link. Abundant siderite associated with M4 sphalerite hasδ¹³C ranging from−2.6to−4.4‰ indicating that carbon was sourced from sedimentary carbonate mobilized by, or equilibrated with the hydrothermal fluid.Late-stage sulphides exhibit extraordinary and highly distinctiveδ³⁴S. Sphalerite has extremely low δ³⁴S(−42.5to−50.5‰), whereas pyrite has an extraordinary large range from−33.2‰to+74.3‰. Closed system sulphate reduction is held to be responsible for the extremely highδ³⁴S: whereas more open system reduction produces the very low values. The coincidence of isotopically lowδ¹³C(−7.6to−11.9‰) for co-genetic calcite suggests the involvement of organic matter in the reduction process.     

A compound-specific n-alkane δC and δD approach for assessing source and delivery processes of terrestrial organic matter within a forested watershed in northern Japan

We measured molecular distributions and compound-specific hydrogen (δD) and stable carbon isotopic ratios (δ¹³C) of mid- and long-chain n-alkanes in forest soils, wetland peats and lake sediments within the Dorokawa watershed, Hokkaido, Japan, to better understand sources and processes associate with delivery of terrestrial organic matter into the lake sediments. δ¹³C values of odd carbon numbered C₂₃-C₃₃n-alkanes ranged from −37.2‰ to −31.5‰, while δD values of these alkanes showed a large degree of variability that ranged from −244‰ to −180‰. Molecular distributions in combination with stable carbon isotopic compositions indicate a large contribution of C3 trees as the main source of n-alkanes in forested soils whereas n-alkanes in wetland soil are exclusively derived from marsh grass and/or moss. We found that the n-alkane δD values are much higher in forest soils than wetland peat. The higher δD values in forest samples could be explained by the enrichment of deuterium in leaf and soil waters due to increased evapotranspiration in the forest or differences in physiology of source plants between wetland and forest. A δ¹³C vs. δD diagram of n-alkanes among forest, wetland and lake samples showed that C₂₅-C₃₁n-alkanes deposited in lake sediments are mainly derived from tree leaves due to the preferential transport of the forest soil organic matter over the wetland or an increased contribution of atmospheric input of tree leaf wax in the offshore sites. This study demonstrates that compound-specific δD analysis provides a useful approach for better understanding source and transport of terrestrial biomarkers in a C3 plant-dominated catchment.     

Interstellar organic matter in meteorites

Hydrogen which is highly enriched in deuterium is present in organic matter in a variety of meteorites including non-carbonaceous chondrites. The concentrations of this hydrogen are quite large. For example Renazzo contains 140 μmoles/g of the 10,000‰ δD hydrogen. The $\text{D}\text{H}$ ratios of hydrogen in the organic matter vary from 8 × 10^?5 to 170 × 10^?5 (δD ranges from ? 500‰ to 10,000‰) as compared to 16 × 10^?5 for terrestrial hydrogen and 2 × 10^?5 for cosmic hydrogen. The majority of the unequilibrated primitive meteorites contain hydrogen whose $\text{D}\text{H}$ ratios are greater than 30 × 10^?5. If the $\text{D}\text{H}$ ratios in these compounds were due to enrichment relative to cosmic hydrogen by isotope exchange reactions, it would require that these reactions take place below 150 K. In addition the organic compounds having $\text{D}\text{H}$ ratios above 50 × 10^?5 would require temperatures of formation of < 120 K. These types of deuterium enrichments must take place by ion-molecule reactions in interstellar clouds where both ionization and low temperatures exist. Astronomically observed $\text{D}\text{H}$ ratios in organic compounds in interstellar clouds are typically 180 × 10^?5 and range between about 40 × 10^?5 and 5000 × 10^?5. The $\text{D}\text{H}$ values we have determined are the lower limits for the organic compounds derived from interstellar molecules because all processes subsequent to their formation, including terrestrial contamination, decrease their $\text{D}\text{H}$ ratios.In contrast, the $\text{D}\text{H}$ ratios of hydrogen associated with hydrated silicates are relatively uniform for the meteorites we have analyzed with an average value of 14 × 10^?5; very similar to the terrestrial value. These phyllosilicates values suggest equilibration of H₂O with H₂ in the solar nebula at temperatures of about 200 K and higher.The ${}^{13}\text{C}{}^{12}\text{C}$ ratios of organic matter, irrespective its $\text{D}\text{H}$ ratio, lie well within those observed for the earth. If organic matter originated in the interstellar medium, our data would indicate that the ${}^{13}\text{C}{}^{12}\text{C}$ ratio of interstellar carbon five billion years ago was similar to the present terrestrial value.Our findings suggest that other interstellar material, representing various inputs from various stars, in addition to the organic matter is preserved and is present in the meteorites which contain the high $\text{D}\text{H}$ ratios. We feel that some elements existing in trace quantities which possess isotopic anomalies in the meteorites may very well be such materials.     

Oxygen,hydrogen and carbon isotope studies of the franciscan formation,Coast Ranges,California

Analyses of 230 Franciscan rock and mineral samples, including the San Luis Obispo ophiolite, show that metamorphism produces no change in the δ¹⁸O of the graywackes (+11 to +14), but that igneous rocks become enriched in ¹⁸O by 2–6% and the cherts depleted by 5–10%. The shales are of two types, a high-¹⁸O type (+16 to +20) associated with chert and a low-¹⁸O type isotopically and mineralogically similar to the graywackes. The vein quartz (δ = + 15 to + 20) is invariably richer in ¹⁸O than the host rock quartz and in most of the rocks the δ¹⁸O of the clastic quartz is similar to the δ¹⁸O of the whole rock. Mineral assemblages are typically not in isotopic equilibrium. Although the δ¹⁸O values are very uniform (+13 to +16). the δ¹³C of vein aragonite and calcite is widely variable (0 to ? 14), implying that a major source of the carbon is oxidized organic material. The δD values of 83 igneous and sedimentary rocks are -45 to -80, exceptions are the Fe-rich minerals howieite and deerite, which have δD = ?100. All of these samples could have equilibrated with H₂O having δD ≈ +10 to ?20 and δ¹⁸O ≈ ?3 to +8. assuming temperatures of 100–300°C. However, the serpentines (δD ≈ ?85 to ?110) and the vein minerals (δD = ?23 to ?55) are exceptions. The vein minerals are 10–20%, richer in deuterium than the adjacent wall rocks; they formed from a relatively D-rich metamorphic water, typically at lower temperatures than did their host rocks. The isotopic compositions of the other Franciscan rocks were affected by three distinct events: (1) hydrothermal alteration of the ophiolite complexes and volcanic rocks as a result of submarine igneous activity at a spreading center or in an island-arc environment; (2) low-temperature, high-pressure regional metamorphism and diagenesis; and (3) a late-stage, very low temperature (<100°C) alteration of the ultramafic bodies by meteoric ground waters, producing lizardite-chrysotile serpentine. In the first two cases, the pore fluid involved in the alteration of the Franciscan rocks was sea water. However, this water became somewhat depleted in D and enriched in ¹⁸O during blueschist metamorphism, evolving to values of δD ≈ ? 20 and δ¹⁸O ≈ + 6 to + 8 at the highest grades. Except for one graywacke sample, the meteoric waters that affected the serpentinites did not significantly change the $\text{D}\text{H}$ ratios of the OH-bearing minerals in any other Franciscan rock.The δ¹⁸O values of orogenic andesites are too low for such magmas to have formed by direct partial melting of Franciscan-type materials in a subduction zone. Andesites either form in some other fashion, or the melts must undergo thorough isotopic exchange with the upper mantle. The great Cordilleran granodiorite-tonalite batholiths, however, are much richer in ¹⁸O and may well have formed by large-scale melting or assimilation of Franciscan-type rocks. The range of δD values of Franciscantype rocks is identical to the ?50 to ?80 range shown by most igneous rocks. This suggests that ‘primary magmatic H₂O’ throughout the world may be derived mainly by partial melting of Franciscantype materials, or by dehydration of such rocks in the deeper parts of a Benioff zone.     

Oxygen and hydrogen isotopic studies of ore deposition and metamorphism at the Raul mine,Peru

The volcano-sedimentary sequence at the Raul mine, central Peru, consists of andesitic volcanics, graywackes, and siltstones, and has been metamorphosed to the upper greenschist-lower amphibolite facies at temperatures of 400–500°C. Isotopic data (O and H) have been collected from: (a) quartz and magnetite from stratiform ores, (b) amphiboles from amphibolite units that host stratiform ores, (c) calcite from late veins, (d) detrital quartz from graywackes, and (e) whole rocks.Interunit differences in quartz and magnetite δ¹⁸O values suggest that these minerals have resisted isotopic exchange during metamorphism, and that quartz-magnetite isotopic temperatures (380–414°C) represent primary formational temperatures. Calculated δ¹⁸O values of water in equilibrium with quartz and magnetite range from 9.1 to 12.6%..Amphibole δ¹⁸O and δD values show no interunit differences and suggest that the amphiboles have exchanged isotopes with a large metamorphic fluid reservoir. Calculated δ¹⁸O_H2O and δD_H2O values range from 8 to 12%. and ?3 to +42%., respectively.δ¹⁸O_H2O values calculated from δ¹⁸O calcite and fluid inclusion filling temperatures range from 7.5 to 10%.. Water extracted from fluid inclusions in calcite has a δD value of ?20%..δ¹⁸O values of metamorphosed graywackes and volcanic sediments are not atypical, but andesitic lavas are ¹⁸O-rich (8–10%.) compared to normal andesites.Waters involved in ore deposition, metamorphism, and late vein formation at Raul are all thought to have a common source, principally seawater. The δ¹⁸O_H2O and δD_H2O values could be produced by evaporation of seawater, shale ultrafiltration, and isotopic exchange with host rocks during deep circulation through the volcano-sedimentary pile.A model is proposed whereby coastal ocean water is restricted from the open sea by volcanic island arcs, and subsequently undergoes evaporation. Circulation of this water is initiated by heat associated with seafloor volcanism. ¹⁸O-enrichment in andesites may be produced by isotopic exchange with high ¹⁸O waters at elevated temperatures and sufficiently high water/rock ratios.     

Simultaneous In Situ Analysis of Carbon and Nitrogen Isotope Ratios in Organic Matter by Secondary Ion Mass Spectrometry

An in situ measurement method for simultaneous determination of carbon and nitrogen isotope ratios in organic matter was developed by secondary ion mass spectrometry with a spatial resolution of ~ 12 μm. Secondary ion intensities of ¹²C^?₂, ¹²C¹³C^?, ¹²C¹⁴N^? and ¹²C¹⁵N^? were simultaneously measured by three Faraday cups and one electron multiplier. Ions of ¹²C₂H^? were measured to monitor hydride interferences and to correct for mass bias. The analytical precisions of δ¹³C and δ¹⁵N values of a reference material (UWLA‐1 anthracite) were 0.16‰ and 0.56‰, respectively (2s). A negative correlation was observed between the mass bias of carbon and ¹²C₂H^?/¹²C^?₂ ratios of examined reference materials. In contrast, there was no correlation between mass bias and hydrogen concentration for nitrogen. The δ¹³C_VPDB and δ¹⁵N_Air values of twenty‐two individual globules of organic matter, found in carbonate rock of the 1878 Ma Gunflint Formation, were determined by the new procedure, ranging from ?33.8‰ to ?33.3‰ and +4.2‰ to 5.8‰, respectively. Means of δ¹³C_VPDB and δ¹⁵N_Air values, ?33.5 ± 0.25‰ and +5.2 ± 0.81‰, are consistent with reported values from bulk sample analysis within analytical precision.     

Tracing the flow of organic matter from primary producers to filter feeders in Ria Formosa lagoon, Southern Portugal

The flow of organic matter along the main navigation channel of Ria Formosa, Portugal, was assessed using determinations of suspended particulate matter (SPM), particulate organic matter (POM), and chlorophyll a (chla) concentrations in conjunction with stable isotope values of primary producers, particulate matter, and two filter feeders. SPM in the lagoon is dominated by inorganic particles comprising 80% of total weight with organic matter averaging about 20%. The algal component of the POM averaged about 5% with the remainder comprised of detritus. The δ¹³C values of primary producers ranged from ?9.1‰ in the intertidal seagrassZostera noltii to ?30.7‰ in the red seaweedBostrychia scorpioides revealing underlying differences in the mechanisms of carbon uptake. The δ¹³C value ofB. scorpioides, which develops entangled on the salt marsh speciesSpartina maritima, suggests that its main source of inorganic carbon is atmospheric CO₂. The δ¹³C values of the high marsh macrophyteSarcocornia perennis significantly increased with distance from the ocean while δ¹³C values ofZ. noltii decreased, probably because higher decomposition of organic matter at inner stations lowers the δ¹³CO₂ value in the water. The δ¹⁵N values of Ulvales, seagrasses, and marsh plants significantly increased from outer stations to inner stations. This increase may be due either to recycling of nitrogen (N) within the marsh (with loss of light N₂ or NH₄) or to inputs of isotopically heavy N from sewage. The δ¹⁵N values of particulate matter showed an opposite trend, which indicates higher microbial degradation of organic matter at the inner lagoon. The data demonstrate that the seston in the lagoon is a mixture of detritus from lagoon primary producers with a minor contribution of microalgae. The filter feeders are most likely assimilating a mixture of phytoplankton and microphytobenthos. Digestion of lagoon seston is selective. The δ¹⁵N values of both muscle and digestive gland of filter feeders showed the opposite gradient of particulate matter indicating that the depleted δ¹⁵N of SPM at inner stations was not assimilated or even ingested. Stable isotopes values did not differ between the filter-feeders—the musselMytilus galloprovincialis collected on buoys and the clamTapes decussatus collected in the sediment—suggesting a considerable mixture of benthic-pelagic organic matter throughout the water column. Assessment of the changes in isotopic decomposition of detritus as it decays is required to refine our understanding of organic matter transfers in detrital food webs.     

Carbon,oxygen and sulphur isotope variations in concretions from the Upper Lias of N.E. England

Carbon, oxygen and sulphur isotope data for transects across two pyrite-bearmg carbonate concretions, and their host sediments, from the Upper Lias of N.E. England show symmetrical zonation. δ¹³C_PDB values of the calcite cement (?12.9 to ?15.4%.) indicate that most of it originated from organic matter by bacterial reduction of sulphate, augmented with marine and, to a lesser extent, fermentation derived carbonate. Organic carbon (δ¹³C_PDB = ?26.1 to ?37.0%.). reflects the admixture of allochtho-nous terrestrial organic matter with marine material and the selective preservation of isotopically light organic material through microbiological degradation.Two phases of pyrite are present in each concretion. The earlier framboidal pyrite formed throughout the sediment prior to concretionary growth and has δ³⁴S_CD values of ?22 to ?26%. indicating formation by open system sulphate reduction. The later euhedral phase is more abundant and reaches values of ? 2.5 to ? 5.5%. at concretion margins. This phase of sulphate reduction provided the carbonate source for concretionary growth and occurred in a partially closed system. The δ¹³C and δ³⁴S data are consistent with mineralogical and chemical evidence which suggest that both concretions formed close to the sediment surface. The δ₁₈O values of the calcite in one concretion (δ¹⁸O_PDB = 2.3 to ?4.8%.) indicate precipitation in pore waters whose temperature and isotopic composition was close to that of overlying seawater. The other concretion is isotopically much lighter (δ¹⁸O_PDB?8.9 to ?9.9%.) and large δ¹⁸O differences between concretions in closely-spaced horizons imply that local factors control the isotopic composition of pore waters.     

Deuterium enrichments in chondritic macromolecular material—Implications for the origin and evolution of organics, water and asteroids

Here we report the elemental and isotopic compositions of the insoluble organic material (IOM) isolated from several previously unanalyzed meteorites, as well as the reanalyses of H isotopic compositions of some previously measured samples (Alexander et al., 2007). The IOM in ordinary chondrites (OCs) has very large D enrichments that increase with increasing metamorphism and decreasing H/C, the most extreme δD value measured being almost 12,000‰. We propose that such large isotopic fractionations could be produced in the OC parent bodies through the loss of isotopically very light H₂ generated when Fe was oxidized by water at low temperatures (<200 °C). We suggest that similar isotopic fractionations were not generated in the IOM of CV and CO chondrites with similar metamorphic grades and IOM H/C ratios because proportionately less water was consumed during metamorphism, and the remaining water buffered the H isotopic composition of the IOM even a H was being lost from it.Hydrogen would also have been generated during the alteration of CI, CM and CR carbonaceous chondrites. The IOM in these meteorites exhibit a considerable range in isotopic compositions, but all are enriched in D, as well as ¹⁵N, relative to terrestrial values. We explore whether these enrichments could also have been produced by the loss of H₂, but conclude that the most isotopically anomalous IOM compositions in meteorites from these groups are probably closest to their primordial values. The less isotopically anomalous IOM has probably been modified by parent body processes. The response of IOM to these processes was complex and varied, presumably reflecting differences in conditions within and between parent bodies.The D enrichments associated with H₂ generation, along with exchange between D-rich IOM and water in the parent bodies, means that it is unlikely that any chondrites retain the primordial H isotopic composition of the water ice that they accreted. The H isotopic compositions of the most water-rich chondrites, the CMs and CIs, are probably the least modified and their compositions (δD ? −25‰) suggest that their water did not form at large radial distances from the Sun where ice is predicted to be very D-rich. Yet models to explain the O isotopic composition of inner Solar System bodies require that large amounts of ice were transported from the outer to the inner Solar System.     

The deuterium enrichment of individual amino acids in carbonaceous meteorites: A case for the presolar distribution of biomolecule precursors

The δD values of over 40 amino acids and two pyridine carboxylic acids of the Murchison and Murray meteorites have been obtained by compound-specific isotopic analyses. For compounds with no known terrestrial distribution, these values range from approximately +330‰ (for cyclic leucine) to +3600‰ (for 2-amino-2,3-dimethylbutyric acid). The latter value is the highest ever recorded for a soluble organic compound in meteorites and nears deuterium to hydrogen ratios observed remotely in interstellar molecules. Deuterium content varies significantly between molecular species and is markedly higher for amino acids having a branched alkyl chain. The δD value of Murray l-isovaline, with an enantiomeric excess of ∼ 6% in the meteorite, was within experimental error of that determined for the combined dl-isovaline enantiomers. Overall, the hydrogen isotope composition of meteoritic amino acids is relatively simple and their δD values appear to vary more with the structure of their carbon chains than with the number and relative distribution of their functionalities or ¹³C content. The magnitude and extent of deuterium enrichment shared by many and varied amino acids in meteorites indicate that cosmic regimes such as those found in the interstellar medium were capable of producing, if not all the amino acids directly, at least a suite of their direct precursors that was abundant, varied, and considerably saturated.     

Carbonates in CM2 chondrites: constraints on alteration conditions from oxygen isotopic compositions and petrographic observations

High-precision measurements of the oxygen isotopic compositions of carbonates (calcite and dolomite) from five CM2 chondrites are presented and put into context of the previously determined mineralogic alteration index (MAI), which places these meteorites into an alteration sequence. The carbonate oxygen isotopic compositions range from +20.0 to +35.7‰ for δ¹⁸O, +8.0 to +17.7‰ for δ¹⁷O, and −0.7 to −2.7‰ for Δ¹⁷O. Carbonate Δ¹⁷O values are inversely correlated with MAI and track the evolution of fluid composition from higher to lower Δ¹⁷O values with increasing alteration on the CM parent body. Similar Δ¹⁷O values for calcite and dolomite fractions from the same splits of the same meteorites indicate that calcite and dolomite in each split precipitated from a single fluid reservoir. However, reversed calcite dolomite fractionations (δ¹⁸O_dol − δ¹⁸O_cc) indicate that the fluid was subject to processes, such as freeze-thaw or evaporation, that fractionated isotopes in a mass-dependent way. Consideration of the carbonate isotopic data in the context of previously proposed models for aqueous alteration of carbonaceous chondrites has provided important insights into both the evolving alteration conditions and the utility of the models themselves. The data as a whole indicate that the isotopic evolution of the fluid was similar to that predicted by the closed-system, two-reservoir models, but that a slightly larger matrix-water fractionation factor may apply. In the context of this model, more altered samples largely reflect greater reaction progress and thus probably indicate more extended times of fluid exposure. Petrographic observations of carbonates reveal a trend of variable carbonate morphology correlated with alteration that is also consistent with changes in the duration of fluid-rock interaction. The data can also be reconciled with fluid-flow models in a restricted region of the parent body, which is consistent with assertions that the different types of carbonaceous chondrites derive from different regions of their parent bodies. In this case, the model results for a 9-km-radius body, and our data place the location of the CM chondrite formation in a 100-m-thick zone 1 km from the surface. The size of this zone could be increased if the model parameters were adjusted.     

Isotope Geochemistry of Groundwater from Fractured Dolomite Aquifers in Central Slovenia

The hydrogeochemistry and isotope geochemistry of groundwater from 85 wells in fractured dolomite aquifers of Central Slovenia were investigated. This groundwater represents waters strongly influenced by chemical weathering of dolomite with an average of δ¹³C_CARB value of +2.2 ‰. The major groundwater geochemical composition is HCO₃ ^? > Ca²⁺ > Mg²⁺. Several differences in hydrogeochemical properties among the classes of dolomites were observed when they were divided based on their age and sedimentological properties, with a clear distinction of pure dolomites exhibiting high Mg²⁺/Ca²⁺ ratios and low Na⁺, K⁺ and Si values. Trace element and nutrient concentrations (SO₄ ^2?, NO₃ ^?) were low, implying that karstic and fractured dolomite aquifers are of good quality to be used as tap water. Groundwater was generally slightly oversaturated with respect to calcite and dolomite, and dissolved CO₂ was up to 46 times supersaturated relative to the atmosphere. The isotopic composition of oxygen (δ¹⁸O_H2O), hydrogen (δD_H2O) and tritium ranged from ?10.3 to ?8.4 ‰, from ?68.5 to ?52.7 ‰ and from 3.5 TU to 10.5 TU, respectively. δ¹⁸O and δD values fell between the GMWL (Global Meteoric Water Line) and the MMWL (Mediterranean Meteoric Water Line) and indicate recharge from precipitation with little evaporation. The tritium activity in groundwater suggests that groundwater is generally younger than 50 years. δ¹³C_DIC values ranged from ?14.6 to ?9.3 ‰ and indicated groundwater with a contribution of degraded organic matter/dissolved inorganic carbon in the aquifer. The mass balances for groundwater interacting with carbonate rocks suggested that carbonate dissolution contributes from 43.7 to 65.4 % and degradation of organic matter from 34.6 to 56.3 %.