Nitrogen components in ureilites

Abundances and isotopic compositions of nitrogen and argon have been investigated in bulk samples as well as in acid-resistant C-rich residues of a suite of ureilites consisting of six monomict (Haverö, Kenna, Lahrauli, ALH81101, ALH82130, LEW85328), three polymict (Nilpena, EET87720, EET83309), and the diamond-free ureilite ALH78019. Nitrogen in bulk ureilites varies from 6.3 ppm (in ALH 78019) to ∼55 ppm (in ALH82130), whereas C-rich acid residues have ∼65 to ∼530 ppm N, showing approximately an order of magnitude enrichment, compared with the bulk ureilites, somewhat less than trapped noble gases. Unlike trapped noble gases that show uniform isotopic composition, nitrogen shows a wide variation in δ¹⁵N values within a given ureilite as well as among different ureilites. The variations observed in δ¹⁵N among the ureilites studied here suggest the presence of at least five nitrogen components. The characteristics of these five N components and their carrier phases have been identified through their release temperature during pyrolysis and combustion, their association with trapped noble gases, and their carbon (monitored as CO + CO₂ generated during combustion). Carrier phases are as follows: 1) Amorphous C, as found in diamond-free ureilite ALH78019, combusting at ≤500°C, with δ¹⁵N = -21‰ and accompanied by trapped noble gases. Amorphous C in all diamond-bearing ureilites has evolved from this primary component through almost complete loss of noble gases, but only partial N loss, leading to variable enrichments in ¹⁵N. 2) Amorphous C as found in EET83309, with similar release characteristics as component 1, δ¹⁵N ≥ 50‰ and associated with trapped noble gases. 3) Graphite, as clearly seen in ALH78019, combusting at ≥700°C, δ¹⁵N ≥ 19‰ and devoid of noble gases. 4) Diamond, combusting at 600-800°C, δ¹⁵N ≤ -100‰ and accompanied by trapped noble gases. 5) Acid-soluble phases (silicates and metal) as inferred from mass balance are expected to contain a large proportion of nitrogen (18 to 75%) with δ¹⁵N in the range -25‰ to 600‰. Each of the ureilites contains at least three N components carried by acid-resistant C phases (amorphous C of type 1 or 2, graphite, and diamond) and one acid-soluble phase in different proportions, resulting in the observed heterogeneity in δ¹⁵N. In addition to these five widespread components, EET83309 needs an additional sixth N component carried by a C phase, combusting at <700°C, with δ¹⁵N ≥ 153‰ and accompanied by noble gases. It could be either noble gas-bearing graphite or more likely cohenite. Some excursions in the δ¹⁵N release patterns of polymict ureilites are suggestive of contributions from foreign clasts that might be present in them.Nitrogen isotopic systematics of EET83309 clearly confirm the absence of diamond in this polymict ureilite, whereas the presence of diamond is clearly indicated for ALH82130. Amorphous C in ALH78019 exhibits close similarities to phase Q of chondrites.The uniform δ¹⁵N value of −113 ± 13 ‰ for diamond from both monomict and polymict ureilites and its independence from bulk ureilite δ¹⁵N, Δ¹⁷O, and %Fo clearly suggest that the occurrence of diamond in ureilites is not a consequence of parent body-related process. The large differences between the δ¹⁵N of diamond and other C phases among ureilites do not favor in situ shock conversion of graphite or amorphous C into diamond. A nebular origin for diamond as well as the other C phases is most favored by these data. Also the preservation of the nitrogen isotopic heterogeneity among the carbon phases and the silicates will be more consistent with ureilite formation models akin to “nebular sedimentation” than to “magmatic” type.     

The carbon isotopic composition of diamonds: relationship to diamond shape,color, occurrence and vapor composition

Three hundred and thirty new ¹³C analyses of diamonds are presented, indicating, in conjunction with earlier published work, a range of about 30%. in the carbon isotopic composition of diamonds. The frequency distribution of diamond δ¹³C analyses shows a very pronounced mode at ?5 to ?6%.vs PDB, a large negative skewness, and a sharp boundary at about ?1%.. Analyses of diamonds from the Premier and Dan Carl mines, South Africa, demonstrate that: (1) differences in ¹³C content that can be related to diamond color and shape are smaller than 1%.; (2) the mean ¹³C content of kimberlite carbonates is 1–2%. lower than that of associated diamonds; (3) significant differences in ¹³C content exist between the mean isotopic compositions of diamonds from these two pipes; (4) the variability in δ¹³C differs from one mine to the other.Computations were carried out evaluating the effect on the ¹³C content of diamonds of: (i) various precipitation processes; (ii) the abundance of the species H₂, H₂O, CH₄, CO, CO₂ and O₂ in the vapor; (iii) the initial isotopic composition variability of the source carbon; (iv) variations of the carbon isotope effects resulting from changes in pressure and temperature and (v) reservoir effects (Rayleigh fractionation). Fifty-eight genetic models were investigated for compatibility with the ¹³C distribution in diamonds and associated carbonate. The modeling does not permit an unambiguous answer to the question whether or not a vapor participated in diamond formation, although the presence of methane during diamond formation is compatible with the carbon isotopic composition data, possible oxygen fugacities in the mantle and with the composition of gases liberated from diamonds. In all probability carbon isotope effects in the diamond formation process were small, and the very large range in δ¹³C observed was inherited from the source 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.     

Carbon isotopic composition of diamonds from the Archangelsk diamond province

The first data are reported on the carbon isotopic composition of diamond crystals from the Grib pipe kimberlite deposit of the Archangelsk diamond province (ADP). The δ¹³C value of the crystals ranges from ?2.79 to ?9.61‰. The isotopic composition of carbon was determined in three zoned crystals (δ¹³C of ?5.8 ?6.96 ‰, ?5.64/ ?5.85 ‰, and ?5.94/ ?5.69 ‰), two “diamond in diamond” samples (diamond inclusion with δ¹³C of ?4.05 and ?6.34 ‰ in host diamond crystals with δ¹³C of ?8.05 and ?7.54 ‰, respectively), and two samples of coated diamonds (cores with δ¹³C of ?6.98 and ?6.78‰ and coats with δ¹³C of ?7.51 and ?8.01 ‰, respectively). δ¹³C values were obtained for individual diamond crystals from bort-type aggregates (δ¹³C of ?4.24/ ?4.05 ‰, ?6.58/ ?7.48 ‰, and ?5.48/ ?6.08 ‰). Correlations were examined between the carbon isotopic composition of diamonds and their crystal morphology; the color; the concentration of nitrogen, hydrogen, and platelet defects; and mineral inclusions content. It was supposed that the observed δ¹³C variations in the crystals are most likely related to the fractionation of carbon isotopes rather than to the heterogeneity of carbon sources involved in diamond formation. The isotopic characteristics of diamonds from the Grib pipe were compared with those of previously investigated diamonds from the Lomonosov deposit. It was found that diamonds from these relatively closely spaced kimberlite fields are different; this also indicates the existence of spatially localized peculiarities of isotope fractionation in processes accompanying diamond formation.     

Graphite content and isotopic fractionation between calcite-graphite pairs in metasediments from the Mgama Hills,Southern Kenya

Amphibolite-grade metasediments from the Mgama Hills region, Kenya, contain conspicuous quantities of graphite, most probably derived from organic progenitor materials. The highest graphite contents (5.1–20.4%) are found in schists whereas calcite marbles intercalated in the sequence contain relatively low amounts (0.1–2.0%). The graphitic constituents are consistently enriched in ¹³C relative to common sedimentary organic material, with the highest isotopic ratios in graphite from the marbles (δ¹³C = ?7.3 ± 5.0%.; n = 10). Carbon isotope fractionations between calcite and graphite mostly vary between 3.3 and 7.1‰, which comes close to both empirically recorded and thermodynamically calculated fractionations in the temperature range of the upper amphibolite faciès (550–650°C). However, larger values occasionally encountered in the marbles suggest that complete isotopic equilibrium is not always attained in amphibolite-facies metamorphism.     

Experimental paleotemperature equation for planktonic foraminifera

Small live individuals of Globigerinoides sacculifer which were cultured in the laboratory reached maturity and produced garnets. Fifty to ninety percent of their skeleton weight was deposited under controlled water temperature (14° to 30°C) and water isotopic composition, and a correction was made to account for the isotopic composition of the original skeleton using control groups.Comparison of. the actual growth temperatures with the calculated temperature based on paleotemperature equations for inorganic CaCO₃ indicate that the foraminifera precipitate their CaCO₃ in isotopic equilibrium. Comparison with equations developed for biogenic calcite give a similarly good fit. Linear regression with Craig's (1965) equation yields: $\text{t = ?0.07 + 1.01}\text{t}\text{?}\text{(r= 0.95)}$ where t is the actual growth temperature and $\text{t}\text{?}$ Is the calculated paleotemperature. The intercept and the slope of this linear equation show that the familiar paleotemperature equation developed originally for mollusca carbonate, is equally applicable for the planktonic foraminifer G. sacculifer.Second order regression of the culture temperature and the delta difference (δ¹⁸Oc ? δ¹⁸Ow) yield a correlation coefficient of r = 0.95: $\text{t}\text{?}\text{= 17.0 ? 4.52(δ}{}^{18}\text{Oc ? δ}{}^{18}\text{Ow) + 0.03(δ}{}^{18}\text{Oc ? δ}{}^{18}\text{Ow)}{}^2$$\text{t}\text{?}\text{, δ}{}^{18}\text{Oc}$ and δ¹⁸Ow are the estimated temperature, the isotopic composition of the shell carbonate and the sea water respectively.A possible cause for nonequilibnum isotopic compositions reported earlier for living planktonic foraminifera is the improper combustion of the organic matter.     

Light element geochemistry of the Apollo 16 site

Pronounced variations in abundances and isotopic compositions of some light elements in soils from the Apollo 16 site are interpreted in terms of differing degrees of solar wind exposure for an originally, and approximately, homogeneous regolith. Carbon abundances in soils are compatible with a model in which equilibrium is established, after 10⁴-10⁵ yr, between solar wind input and loss by H stripping. However, this model does not explain the observed C isotopic distribution, suggesting that other sources of C or other processes, or both, are also important. Carbon abundances in rocks from Apollo 16 are higher (average 40 ppm) than at other landing sites although their isotopic compositions, ?35 < δ¹³C < ?16%. PDB, are normal. Abundances of N and, to a less extent, He and H in soils correlate with C as does a fraction of metallic Fe attributed to in situ reduction of indigenous Fe²⁺ by solar wind H.Fillet soil 67461 apparently contains solar wind C and N in a relatively unfractionated form, yielding an upper limit to solar wind (δ¹³C of ?16%., PDB and a value of 3.4 for $\text{C}\text{N}$ in the solar wind.Sulfur at the Apollo 16 site represents a paradox in that, although abundances in soils are apparently controlled by local rock S contents, they also correlate, for all but one sample, with δ³⁴S, which itself is apparently controlled by surface exposure age. A complex lunar S cycle is suggested.     

Etude pedogenetique et isotopique des neoformations de calcite dans un sol sur craie: Caracteristiques et origines

Cryoturbated facies are found at the boundary between soil horizons and Cretaceous chalk. Several types of secondary calcite appear in soil horizons: orange coloured and rounded (partially dissolved) nodules, deeply coloured angular aggregates, transparent isolated rhombs and polycrystalline nodules, needles. The carbon and oxygen isotope compositions of these calcites are correlated: δ¹³C = 4.9δ¹⁸O_PDB + 15.9End members of this correlation are the orange rounded nodules (δ¹³C ? + 8%., $\text{δ}{}^{18}\text{O ? ?1.5‰}$) and the transparent angular polycrystalline nodules (δ¹³C ? ?13; δ¹⁸O ? ?6).Partially dissolved nodules have formed under periglacial climatic conditions. Crystallisation would have occurred under the following (equilibrium) environmental conditions: δ¹⁸O_SMOW (soil solution) ?7, δ¹³C (gaseousCO₂) ? ?5.2, t ? ?2°C. Soil solution was enriched in ¹⁸O by evaporation and atmospheric CO₂ was enriched in ¹³C as compared to present day. Transparent polycrystalline nodules are compatible with present day environmental conditions: δ¹⁸O (soil solution) ranging from ?9 to ?4 and δ¹³C (soil CO₂) ranging from ?24.5 to ?23. These nodules crystallize between May and October at soil temperatures ranging from 10 to 25°C, from evaporated soil solutions. Angular coloured aggregates may form under present day winter conditions for temperatures between 0 and 10°C. However they may also result from present accretion of fragments of periglacial nodules.All recent secondary calcite results from CO₂ degassing and evaporation of soil solutions. Degassing is controlled by the gradient of CO₂ partial pressure within the soil profile. During winter this gradient is low and the resulting calcite precipitation is not significant. During summer a large difference in pCO₂ appears between the root zone and deep soil horizons. The degassing accounts for an increase of about 2‰ in δ¹³C of the total dissolved inorganic carbon and of the related solid carbonate. Evaporation is the main driving force for secondary calcite precipitation.     

Kinetic-simulating experiment combined with GC-IRMS analysis: application to identification and assessment of coal-derived methane from Zhongba Gas Field (Sichuan Basin, China)

The main purpose of this study is to model the δ¹³C values of methane derived from coal by combining kinetic-simulating experiment with the gas chromatography-isotope ratio mass spectrum (GC-IRMS) analysis. The stable carbon isotopic variation of methane in pyrolysates with heating temperature indicates that the assumptions for both a constant kinetic isotope effect (α) and a uniform initial isotopic composition (δ¹³C_o) are impractical for explaining the carbon isotopic fractionation during coalification. For purposes of simplification, two approaches are used in this paper to deal with the heterogeneity of terrestrial organic matter. One is that, assuming a uniform initial isotopic composition (i.e., δ¹³C_{i, o}=δ¹³C_o) for all methane-generating precursors in coal, the isotopic variation of methane is fitted by adjusting ΔE_{a, i} (E_{a¹³C, i}−E_{a¹²C, i}) for each hypothetical reaction. The other is that, assuming a constant kinetic isotope effect during the whole gas formation, that is all ΔE_{a, i} values are identical, the modeling of methane isotopic composition is achieved by changing the ¹³CH₄ generation potential of each reaction (f_{i, ¹³C}), namely, by adjusting the initial δ¹³C value (δ¹³C_{i, o}) for each methane-generating precursor. Results of the kinetic calculation shows that the two simulating methods can yield a similar result at a geological heating rate of 2 °C/My, which further demonstrates that those natural gases with methane δ¹³C value being approximately −36‰ are possibly sourced from the upper Triassic coal measure strata in the Northwestern Sichuan Basin.     

Carbon isotopic thermometry calibrated by dolomite-calcite solvus temperatures

The temperature dependence of carbon isotopic fractionations between calcite and graphite, and between dolomite and graphite are calibrated by the calcite-dolomite solvus geothermometry using marbles collected from the contact metamorphic aureole in the Kasuga area, central Japan. The carbon isotopic fractionations (Δ¹³C_Cc-Gr and Δ¹³C_DoGr) systematically decrease with increasing metamorphic temperature. The concordant relationships between the fractionations and solvus temperatures are approximately linear with T^?2 over the temperature range. 400° to 680°C: Δ¹³C_CcGr (%.) = 5.6 × 10⁶ × T^?2 (K) ? 2.4 Δ¹³C_DoGr (%.) = 5.9 × 10⁶ × T^?2 (K) ? 1.9 These systematic relationships between fractionation and temperature suggest that carbon isotopic equilibria between carbonates and graphite were attained in many cases. The equation for the calcite-graphite system has a slope steeper than Bottinga's (1969) results. It is, however, in good agreement with that of Valley and O'Neil (1981) in the temperature range from 600° to 800°C.Because of the relatively high sensitivity to temperature, these isotopic geothermometers are useful for determining the temperatures in moderate- to high-grade metamorphosed carbonate rocks.     

Distribution,abundance and carbon isotopic composition of gaseous hydrocarbons in Big Soda Lake,Nevada: An alkaline,meromictic lake

Distribution and isotopic composition (δ¹³C) of low molecular weight hydrocarbon gases were studied in Big Soda Lake (depth = 64 m), an alkaline, meromictic lake with permanently anoxic bottom waters. Methane increased with depth in the anoxic mixolimnion (depth = 20–35 m), reached uniform concentrations (55 μM/l) in the monimolimnion (35–64 m) and again increased with depth in monimolimnion bottom sediments (>400 μM/kg below 1 m sub-bottom depth). The μ¹³C[CH₄] values in bottom sediment below 1 m sub-bottom depth (<?70 per mil) increased with vertical distance up the core (δ¹³C[CH₄] = ?55 per mil at sediment surface). Monimolimnion δ¹³C[CH₄] values (?55 to ?61 per mil) were greater than most δ¹³C[CH₄] values found in the anoxic mixolimnion (92% of samples had δ¹³C[CH₄] values between ?20 and ?48 per mil). No significant concentrations of ethylene or propylene were found in the lake. However ethane, propane, isobutane and n-butane concentrations all increased with water column depth, with respective maximum concentrations of 260, 80, 23 and 22 nM/l encountered between 50–60 m depth. Concentrations of ethane, propane and butanes decreased with depth in the bottom sediments. Ratios of $\text{CH}{}_4\text{[C}{}_2\text{H}{}_6\text{+ C}{}_3\text{H}{}_8\text{]}$ were high (250–620) in the anoxic mixolimnion, decreased to ~161 in the monimolimnion and increased with depth in the sediment to values as high as 1736. We concluded that methane has a biogenic origin in both the sediments and the anoxic water column and that C₂-C₄ alkanes have biogenic origins in the monimolimnion water and shallow sediments. The changes observed in δ¹³C[CH₄] and $\text{CH}{}_4\text{(C}{}_2\text{H}{}_6\text{+ C}{}_3\text{H}{}_8\text{)}$ with depth in the water column and sediments are probably caused by bacteria] processes. These might include anaerobic methane oxidation and different rates of methanogenesis and C₂ to C₄ alkane production by microorganisms.     

The isotopic composition of carbonatite and kimberlite carbonates and their bearing on the isotopic composition of deep-seated carbon

New carbon and oxygen isotopic compositions of carbonates from 14 carbonatite and 11 kimberlite occurrences are reported. A review of the available data on the carbon isotopic composition ranges of carbonatite and kimberlite carbonates shows that they are similar and overlap that of diamonds. The mean carbon isotopic composition of carbonates from 22 selected carbonatite complexes (?5.1%., s = ±l.4%.vsPDB) is indistinguishable from that of 13 kimberlite pipes (?4.7%. s = ±1.2%.) as well as that of 60 individual diamond analyses (?5.8%., s = 1.8%.). The oxygen isotopic compositions of kimberlite carbonates, however, are enriched in O¹⁸ by several permil with respect to those of carbonates from the subvolcanic type of carbonatite.The data suggest that not all carbonatite, kimberlite and diamond occurrences have the same average carbon isotopic composition and that significant differences exist between them. Carbon isotopic composition measurements available for the East African Rift system suggest geographic and/or tectonic groupings e.g. carbonate lavas, tuffs and intusive carbonatites associated with the Eastern Rift yield a range of δC¹³ values from ?5.8 to ?7.4%., similar to that of the carbonate rocks associated with the Western Rift volcanism (?5.8 to ?7.9%.). In contrast the interrift area encompassing Lakes Victoria, Malawi (Nyasa) and Chilwa, apparently are characterized by carbonatitic carbonates of higher C¹³ content (?2.4 to ?4.4%.).If carbonatite and kimberlite carbonates as well as diamonds represent deep seated carbon, the mean isotopic composition of this carbon is estimated as ?5.2%. and the range is ?2 to ?8%. The selection of any particular value within this range to be used as a criterion of deep-seated origin is at the moment not warranted. Indeed, the choice of any specific composition for such carbon may be meaningless, as the source of kimberlite, carbonatite and diamond carbon may not be isotopically uniform.     

The isotopic composition of carbonaceous matter in a metamorphic profile from the Swiss Alps

44 Δ¹³C-values for carbonaceous matter in a metamorphic profile from the Swiss Alps have been determined. The analyzed samples range from unmetamorphosed sediments to staurolite schists. The carbon isotopic composition is more-or-less constant with δ-values around ?25%. in the unmetamorphosed sediments, but shifts towards higher ¹³C-content with increasing grade of metamorphism. δ¹³C values of around ?11%. were measured in the rocks of the highest metamorphic grade.     

Stable carbon isotopes of graphite from Bogala Mine,Sri Lanka

The ratios of the carbon isotopes ¹³C and ¹²C of twenty-four graphite samples from Bogala Mine, Sri Lanka have been determined. The graphites are isotopically very similar (mean value $\text{?7.76? °}{}^{13}\text{C}{}_{\mathrm{PDB}}$; range $\text{<2?}$). Three models for the biogenic or abiogenic origin of the graphite deposit are discussed.     

Noble gases in ureilites: cosmogenic, radiogenic, and trapped components

Abundances and isotopic compositions of Ne (in bulk samples only), Ar, Kr, and Xe have been investigated in 6 monomict, 3 polymict, and the diamond-free ureilite ALH78019 and their acid-resistant, C-rich residues. Isotopic ratios of Kr and Xe are very uniform and agree with data for ureilites from the literature. The measured ratio ³⁸Ar/³⁶Ar showed large variations due to an experimental artifact. This is shown to be connected to the pressure dependence of the instrumental mass discrimination, which for ureilites with their low abundance of ⁴⁰Ar is different from that of the usual air standard. This observation necessitates a reassessment for the recently reported ³⁶Ar excesses due to possible decay of extinct ³⁶Cl in the Efremovka meteorite.Trapped ²²Ne in the range of (1.4-2.5) × 10⁻⁸ cc STP/g is present in bulk ureilites. A Ne three-isotope plot for polymict ureilites indicates the presence of solar Ne. ²¹Ne-based cosmic ray exposure ages for the 10 ureilites studied range from 0.1 Ma (for ALH78019) to 46.8 Ma (for EET83309)All ureilites may have started with nearly the same initial elemental ratio (¹³²Xe/³⁶Ar)₀, established in the nebula during gas trapping into their carbon carrier phases (diamond, amorphous C) by ion implantation. Whereas diamonds are highly retentive, amorphous C has suffered gas loss due to parent body metamorphism. The correlation of the elemental ratios ¹³²Xe/³⁶Ar and ⁸⁴Kr/³⁶Ar along the mass fractionation line could be understood as a two-component mixture of the unaffected diamond gases and the fractionated (to varying degrees) gases from amorphous C. In this view, the initial ratio (¹³²Xe/³⁶Ar)₀ is a measure of the plasma temperature in the nebula at the formation location of the carbon phases. Its lack of correlation with Δ¹⁷O (a signature of the silicate formation location) indicates that carbon phases and silicates formed independently in the nebula, and not from a carbon-rich magmaThe elemental ratios ¹³²Xe/³⁶Ar and ⁸⁴Kr/³⁶Ar in carbon-rich acid residues show a decreasing trend with depth (inferred from carbon consumption during combustion), which can be interpreted as a consequence of the ion implantation mechanism of gas trapping that leads to greater depth of implantation for lighter mass ionThe similarity between trapped gases in phase Q in primitive chondrites and the C phases in ureilites—for both elemental and isotopic compositions—strongly suggests that phase Q might also have received its noble gases by ion implantation from the nebula. The slight differences in the elemental ratios can be explained by a plasma temperature at the location of phase Q gas loading that was about 2000 K lower than for ureilite C phases. This inference is also consistent with the finding that the trapped ratio ¹²⁹Xe/¹³²Xe (1.042 ± 0.002) in phase Q is slightly higher, compared to that of ureilite C phases (1.035 ± 0.002), as a consequence of in situ decay of ¹²⁹I, and becomes observable due to higher value of I/Xe in phase Q as a result of ion implantation at about 2000 K lower plasma temperature.     

Carbon isotope composition of organic seston and sediments in a Georgia salt marsh estuary

The distribution of δ¹³C values for organic seston and sediment was determined in three sounds in the Spartina marsh estuaries along the Georgia coast, which had high, moderate, and low inputs of freshwater. Organic matter in all three sounds had similar carbon isotope compositions, for the most part within the range of marine values (δ¹³C of ?18%. to ?24%.). It appears that river flow does not introduce significant quantities of particulate C₃ plant material (δ¹³C of ?25%. to ?28%.) to Georgia estuaries. Evaluation of δ¹³C values of estuarine seston and three size fractions of sediment indicated that while Spartina carbon (δ¹³C of ?13%.) can be an important component of organic matter in intertidal sediments (mean δ¹³C of ?14.3%. to ?20.0%.), it is less so in subtidal sediments (mean δ¹³C of ?18.8%. to ?21.2%.), and it is hardly present at all in the seston (mean δ¹³C of ?24.5%.). δ¹³C values of dissolved inorganic carbon (DIC) in several water samples ranged between ?2.5%. and ?5.6%., suggesting that the isotope composition of estuarine DIC is influenced by respiratory CO₂ derived from metabolism of ¹³C-depleted plant carbon. Phytoplankton production utilizing this comparatively light DIC could be a source of relatively negative δ¹³C carbon in the estuary. Additional origins of estuarine organic matter greatly depleted in ¹³C compared to Spartina carbon remain to be identified.     

Carbon isotope thermometry in marbles of the Adirondack Mountains, New York

Abstract Carbon isotope thermometry has been applied to coexisting calcite and graphite in marbles from throughout the Adirondack Mountains, New York. Eighty-nine calcite-graphite pairs from the amphibolite grade NW Adirondacks change systematically in temperature north-westwards from 680 to 640 to 670° C over a 30-km distance, reflecting transitions from amphibolite facies towards granulite facies to the north-west and to the south-east. Temperature contours based on calcite-graphite thermometry in the NW Adirondacks parallel mineral isograds, with the orthopyroxene isograd falling above 675° C, and indicate that regional metamorphic temperatures were up to 75° C higher than temperatures inferred from isotherms based on cation and solvus thermometry (Bohlen et al. 1985). Fifty-five calcite-graphite pairs from granulite grade marbles of the Central Adirondacks give regional metamorphic temperatures of 670–780° C, in general agreement with cation and solvus thermometry. Data for amphibolite and granulite grade marbles show a 12%oo range in δ¹³C_cal and δ¹³C_gr. A strong correlation between carbon isotopic composition and the abundance of graphite (C_gr/C_rock) indicates that the large spread in isotopic compositions results largely from exchange between calcite and graphite during closed system metamorphism. The trends seen in δ¹³C _vs. C_gr/C_rock and δ¹³C_cal vs. δ¹³C_gr could not have been preserved if significant amounts of CO₂-rich fluid had pervasively infiltrated the Adirondacks at any time. The close fit between natural data and calculated trends of δ¹³C vs. C_gr/C_rock indicates a biogenic origin for Adirondack graphites, even though low δ¹³C values are not preserved in marble. Delamination of 17 graphite flakes perpendicular to the c-axis reveals isotopic zonation, with higher δ¹³C cores. These isotopic gradients are consistent with new graphite growth or recrystallization during a period of decreasing temperature, and could not have been produced by exchange with calcite on cooling due to the sluggish rate of diffusion in graphite. Samples located >2km from anorthosite show a decrease of 0.5-0.8%oo in the outer 100 μ of the grains, while samples at distances over 8 km show smaller core-to-rim decreases of c.0.2%oo. Correlation between the degree of zonation and distance to anorthosite suggests that the isotopic profiles reflect partial overprinting of higher temperature contact metamorphism by later granulite facies metamorphism. Core graphite compositions indicate contact metamorphic temperatures were 860–890° C within 1 km of the Marcy anorthosite massif. If samples with a significant contact metamorphic effect (Δ(_cal-gr) <3.2%oo) are not included, then the remaining 38 granulite facies samples define the relation Δ¹³C(_cal-gr) = 3.56 ± 10⁶T^-2 (K).     

Associated chemical and carbon isotopic composition variations in diamonds from Finsch and Premier kimberlite,South Africa

The carbon isotopic composition of 66 inclusion-containing diamonds from the Premier kimberlite, South Africa, 93 inclusion-containing diamonds and four diamonds of two diamond-bearing peridotite xenoliths from the Finsch kimberlite, South Africa was measured. The data suggest a relationship between the carbon isotopic composition of the diamonds and the chemical composition of the associated silicates. For both kimberlites similar trends are noted for diamonds containing peridotite-suite inclusions (P-type) and for diamonds containing eclogite-suite inclusions (E-type): Higher δ¹³C P-type diamonds tend to have inclusions lower in SiO₂ (ol), Al₂O₃ (opx, gt), Cr₂O₃, MgO, $\text{Mg}\text{(Mg + Fe)}$ (ol, opx, gt) and higher in FeO (ol, opx, gt) and CaO (gt). Higher δ¹³C E-type diamonds tend to have inclusions lower in SiO₂, Al₂O₃ (gt, cpx), MgO, $\text{Mg}\text{(Mg + Fe)}$ (gt), Na₂O, K₂O, TiO₂ (cpx) and higher in CaO, $\text{Ca}\text{(Ca + Mg)}$ (gt, cpx).Consideration of a number of different models that have been proposed for the genesis of kimberlites, their xenoliths and diamonds shows that they are all consistent with the conclusion that in the mantle, regions exist that are characterized by different mean carbon isotopic compositions.