13C Nuclear magnetic resonance studies of kerogen from Cretaceous black shales thermally altered by basaltic intrusions and laboratory simulations

Cretaceous black shales from DSDP Leg 41, Site 368 in the Eastern Atlantic Ocean were thermally altered during the Miocene by an intrusive basalt. The sediments overlying and underlying the intrusive body were subjected to high temperatures (up to ~ 500°C) and, as a result, their kerogen was significantly altered. The extent of this alteration has been determined by examination by means of ¹³C nuclear magnetic resonance, using cross polarization/magic-angle spinning (CP/MAS). Results indicate that the kerogen becomes progressively more aromatic in the vicinity of the intrusive body. Laboratory heating experiments, simulating the thermal effects of the basaltic intrusion, produced similar results on unaltered shale from the drill core. The ¹³C CP/MAS results appear to provide a good measure of thermal alteration.     

[1H] and [13C]NMR studies on the importance of aromatic structures in fulvic and humic acids

To obtain information on the contribution of aromatic fragments to the chemical structure of humic substances, we carried out a study on the [¹H]NMR and [¹³C]NMR spectra of humic and fulvic acids and their oxidative degradation products extracted from an Andosol soil.[¹H]NMR spectra of all organic fractions present considerable adsorption between 7.4 and 8.8 ppm, due to the presence of aromatic protons.The percentages of aromatic protons in respect to the total amount of protons are as follows: FA 20%, HA 19%, degraded FA < 12%, degraded HA 14%. The values indicate that the contribution of aromatic structures to the humic substances is significant, also considering that they are highly substituted.The degraded fractions contain smaller amounts of aromatic protons, because degradation causes the opening of the aromatic rings. Thus results obtained from the degradation do not seem to be reliable for defining the importance of aromatic structures in humic substances.Also the [¹³C]NMR spectra show signals in the aromatic region which derive from unsubstituted carbon atoms, while signals originating from tertiary carbon atoms merge with the noise. We believe that, at present, [¹H]NMR spectroscopy is more suited for studying the role played by aromatic compounds in organic soil fractions.     

Mixing rates in Shagawa Lake,Minnesota, sediments as determined from 106Ru profiles

Rates of surficial sediment mixing and sediment burial are measured in Shagawa Lake, Minnesota, using radionuclide tracers. Based on ¹⁰⁶Ru profiles in 16 cores, mixing rates average 13 cm²/yr within the upper 9 cm of sediment. Two other nuclides, ²¹⁰Pb and ¹³⁷Cs, provide further evidence for calculation of mixing rates. In addition, ²¹⁰Pb profiles estimate sediment burial rates (about 0.4 cm/yr). Mixing estimates are shown to be fairly insensitive both to uncertainties in sediment burial rates and to temporal patterns of ¹⁰⁶Ru deposition.     

Pyrolysis-high resolution gas chromatography and pyrolysis gas chromatography-mass spectrometry of kerogens and kerogen precursors

A series of kerogens and kerogen precursors isolated from DSDP samples, oil shales and Recent algal mats have been examined by Curie point pyrolysis-high resolution gas chromatography and gas chromatography-mass spectrometry. This study has shown that the three main types of kerogens (marine, terrestrial and mixtures of both) can be characterized using these techniques. The marine (algal) kerogens yield principally aliphatic products and the terrestrial kerogens yield more aromatic and phenolic products with some n-alkanes and n-alkenes. The yields of n-alkanes and n-alkenes increase and phenols decrease with increasing geologic age, however, pyrolysis-GC cannot be used to characterize the influence of short term diagenesis on the kerogen structure.     

Evaluation of alkaline permanganate oxidation method for the characterization of young kerogen

Alkaline potassium permanganate oxidation of a young kerogen (lacustrine) and 34 model compounds (saturated and unsaturated fatty acids, hydroxy acid, aliphatic dicarboxylic acids, aliphatic alcohols, normal hydrocarbon, β-carotene, phenolic acids, benzenecarboxylic acids, carbohydrates, amino acids and proteins) were conducted, followed by GC and GC-MS analysis of the degradation products. The stability of the degradation products of kerogen in permanganate solution and the relationship between degradation products and kerogen building blocks were determined.The results showed that aliphatic acids C₁₂–C₁₆ monocarboxylic acids and C₆–C₁₀ α,ω-dicarboxylic acids) were rather susceptible to oxidation compared with benzenecarboxylic acids and the former were degraded into lower molecular weight decarboxylic acids. It was concluded that oxidation at milder conditions (60° C, 1 hr) is appropriate for qualitative and quantitative characterization of the aliphatic structure of young kerogen. It was noteworthy that benzoic acid was produced in a significant amount by oxidation of amino acids (phenylalanine) and proteins, C₁₈-isoprenoidal ketone from phytol, and C₈ and C₉ α,ω-dicarboxylic acids from unsaturated fatty acids, respectively; furthermore, 2,2-dimethyl succinic and 2,2-dimethyl glutaric acids were produced from β-carotene.     

GC-MS characterisation of C27 and C28 triterpanes in sediments and petroleum

Earlier studies have shown that an unusual C₂₇ triterpane is abundant in sediments from the Norwegian Continental Shelf and the North Sea. This compound was assigned the tentative structures 24,28,30-trisnormoretane or 25,28,30-trisnormoretane, but we have now shown from detailed retention time measurements and a reinterpretation of the mass spectral data that its correct structure is 17α(H),18α (H),21β(H)-25,28,30-trisnorhopane. Two other triterpanes, 25,28,30-trisnormoretane and 28,30-bisnormoretane, have also been identified as minor constituents of extracts of sediments from the North Sea. Possible origins for these compounds are discussed.     

Surface study of HF- and HFH2SO4-treated feldspar using Auger electron spectroscopy

Auger electron spectroscopy has been used to study K-feldspar that has been reacted with both aqueous 10% HF and a 50% mixture of a 10% HF/0.1 N H₂SO₄ solution. In the feldspar/HF system, the resulting feldspar surface was shown to have been fluorinated; depth profiling, using argon ion sputtering, showed the fluorination to have occurred substantially into the mineral bulk. In the feldspar/ $\text{HF}\text{H}{}_2\text{SO}{}_4$ system, the resulting surface contained both fluorine and sulfur. The fluorination had again penetrated into the bulk, but the sulfur could be removed with mild argon ion sputtering. The $\text{Al}\text{F}$ signal ratio was much lower on the feldspar surface treated with the 10% HF/0.1 N H₂SO₄ solution than the feldspar surface treated with the weaker 10% HF acid solution.     

Chemical studies of L chondrites—III. Mobile trace elements and 40Ar39Ar ages

We report data for trace elements Ag, Au, Bi, Cd, Co, Cs, Ga, In, Rb, Se, Te, Tl and Zn determined by radiochemical neutron activation analysis in L4–6 chondrites with undisturbed ⁴⁰Ar release patterns or with patterns showing some disturbance in the 4.4–4.6 Gyr plateau indicating shock-induced loss. Mean concentrations are lower, many significantly so, in 16 chondrites with disturbed patterns than in 4 with undisturbed ones, consistent with shock-induced mobilization. Similar trends were noted earlier in L4–6 chondrites having mineralogically observable shock indicators: mean concentrations are lower in strongly shocked (i.e. > 22 GPa) than in mildly shocked (<22 GPa) samples. From trace element contents, L4–6 chondrites with undisturbed ⁴⁰Ar release patterns are mildly shocked but chondrites with disturbed patterns are more strongly heated, on average, than those of shock facies d-f (i.e. 22 to > 57 GPa). Pooling these populations, significantly lower mean concentrations of nearly all trace elements in 26 strongly shocked L4–6 chondrites than in 14 mildly shocked ones indicate loss in shock-formed FeS-Fe eutectic and/or by vaporization during cooling of shock-heated collisional debris. Two-element correlations and the pattern of them, i.e. correlation profiles, are also consistent with this picture. Trace elements can act as thermometers for collisional episodes in L4–6 chondrites but not for earlier thermal fractionations, unless compensation can be made for late shock heating.     

Comparison of oil shales and kerogen concentrates by C nuclear magnetic resonance

Six oil shales and their kerogen concentrates have been studied using ¹³C CP/MAS NMR techniques to study the distribution of organic carbon species. It is found that if the aromatic and aliphatic regions are divided at about 80 or 100 ppm, the apparent aromaticities of a raw shale and its kerogen concentrate are in good agreement. The presence of oxygen-substituted carbons in the raw shales and their depletion in the kerogen concentrates are observed and discussed.     

A geochemical reconstruction of oil generation in the Barrow Sub-basin of Western Australia

A suite of crude oils and petroleum source rock extracts from the Barrow Sub-basin of Western Australia have been analysed for biological marker compounds by capillary GC-MS, and for volatile hydrocarbons by whole oil capillary GC. These analyses were used to calculate values for twenty-three biomarker parameters in order to assess aspects of source type, maturity, migration and biodegradation of the hydrocarbons.The crude oils had a source in the Upper Jurassic Dingo Claystone formation. These hydrocarbons accumulated in the reservoir sands and in some cases were biodegraded. Several accumulation and biodegradation episodes have been recognised while the basin continued to subside, which resulted in a suite of oils showing marked differences in composition.     

SrCa and MgCa ratios in polygenetic carbonate allochems from a Michigan marl lake

Rapid accumulation of CaCO₃ is occurring in Littlefield Lake, a marl lake located in central Michigan. The sediment, which is 95% CaCO₃, primarily consists of eight different genetic groups of carbonate allochems. These include calcite muds, sands, algal oncoids and Chara encrustations, as well as the dominant aragonitic gastropods Valvota tricarinota. Gyraulus deflectus and Amnicola integra. and the dominant aragonitic pelecypod Sphaerium partumeium. Samples of each of these groups were analyzed for Ca, Sr and Mg. Molar $\text{Mg}\text{Ca}$ ratios are primarily controlled by allochem mineralogy, with calcitic forms having $\text{Mg}\text{Ca}$ ratios 5–10 times larger than aragonitic (shelled) forms. The $\text{Sr}\text{Ca}$ ratios are primarily controlled by biochemical fractionation, and are significantly lower than $\text{Sr}\text{Ca}$ ratios of inorganically precipitated aragonite from other settings. Partition coefficients were determined for both Sr and Mg for each carbonate allochem group and, based on comparisons with results reported by other workers, the partition coefficients determined here are generally considered ‘typical’ or representative values for biogeneous freshwater carbonates. An analysis of variance of the data indicates that most genera and species of carbonate-secreting organisms in marl lakes have highly characteristic $\text{Sr}\text{Ca}$ and $\text{Mg}\text{Ca}$ ratios. These ratios can potentially serve as geochemical tracers in future investigations of lacustrine carbonate diagenesis. Both Sr and Mg are influenced by grain size and/or surface area, probably due to the presence of these elements in non-lattice-held (exchangeable) positions.     

Stable hydrogen isotopes in iron oxides—II. DH variations among natural goethites

Goethite samples analyzed for this study have a δD range from ?202 to ?98 per mil with a corresponding δD range of associated waters from about ?110 to +7 per mil. Goethites with the most positive δD values are from marine environments. Goethite-water equilibrium $\text{D}\text{H}$ fractionation factors measured in this laboratory at 100°C and 145°C and estimated for sedimentary temperatures from data on natural samples have values of about 0.900 at all three temperatures. These data suggest that goethite δD values may be a direct, temperature-independent measure of the δD values of the waters with which the goethite last equilibrated. Most of the goethite δD values in this study reflect the δD values of the modern waters in the locales of origin.Substitution of Mn and/or Al for Fe in the goethite structure may affect the mineral-water fractionation factor. Manganese appears to decrease the value of α. The effect of Al substitution on α has not yet been measured, but preliminary arguments suggest that increasing Al content could increase α values.     

Determination of hydrocarbon distributions in oils and sediment extracts by gas chromatography—high resolution mass spectrometry

The distributions of steroid and triterpenoid hydrocarbons in crude oils and sedimentary rock extracts can be routinely determined by the direct injection of the sample into a gas chromatograph coupled to a mass spectrometer (GC-MS). The mass spectrometer is operated at a resolution of about 2500 (10% valley), and only the ion intensities at selected accurate mass values, diagnostic of the structural types of interest, are monitored throughout the analysis. The distributions, so obtained, find application in the assessment of the source and thermal maturity of crude oil accumulations in the subsurface. This technique eliminates chromatographic separation steps and combines two analyses in one. Thus, more geological samples and reference mixtures may be analyzed in a given time.     

Phosphate beneficiation by calcination. Prediction of P2O5 in the product,mining and plant control

A method is described to predict P₂O₅ content in the product (of phosphate beneficiation by calcination) as a function of the composition of an untreated and also of a washed raw material. The method consisted of: (a) developing an on-line multielement analysis by XRF; (b) finding the elemental and mineralogical relationships in the product, by factor analysis; (c) determination of the independent variables; (d) finding the relationships between the concentrations of the impurity variables in the raw material and in the product; (e) developing a linear model to predict P₂O₅ content. The predictions are used for mining and for plant control.     

Effects of age on the chemical structure of paleosol humic acids and fulvic acids

Humic acids and fulvic acids were extracted from six paleosols in Southern Italy. Humic acids (HAs) constituted between 96.5 and 99.2% of the total extracts; the remaining materials consisted of fulvic acids (FAs). Radiocarbon ages of the HAs ranged from about 6,000 to close to 29,000 years B.P., δ¹³C values averaged $\text{?25.6 ± 0.3‰}$ The HAs were characterized by chemical (elemental and functional group analyses) and spectroscopic (IR, ESR, ¹³CNMR, E₄/E₆ ratios) methods. FAs were characterized by chemical methods, E₄/E₆ ratios and IR spectra.The chemical and spectroscopic analyses showed practically no differences in the chemical structure and composition of the six HAs and FAs, so that age appeared to have little effect on these parameters. The paleosols were found to be closed systems with low polysaccharide and protein contents, thus providing unfavorable substrates for microbial activity. The preservation of the humic materials in the paleosols may have been due to low biological activity and/or to retention by amorphous minerals. The HAs did not appear to be affected by temperatures higher than 170–200°C over the 23,000 year period which we observed.     

Cumberland Falls chondritic inclusions—II. Trace element contents of forsterite chondrites and meteorites of similar redox state

Mineralogic study of black inclusions in the Cumberland Falls enstatite achondrite revealed that they constitute a highly unequilibrated chondritic suite distinct from other chondrite groups. This highly shocked suite, the forsterite (F) chondrites, exhibits mineralogic trends apparently produced during primary nebular condensation and accretion over a broad redox range. We analyzed these samples and possibly related meteorites for Ag, As, Au, Bi, Cd, Co, Cs, Ga, In, Rb, Sb, Se, Te, Tl, U and Zn, trace elements known to yield important genetic information. The results demonstrate the compositional coherence and distinctiveness of the F chondrite suite relative to other chondrites. The Antarctic aubrite, ALH A78113, may include more F chondrite material. Trace element contents do not vary with mineral compositions hence do not reflect redox variations during formation of F chondrite parental matter. Trace element mobilization—during secondary heating episodes in the F chondrite parent or during its disruptive collision with the enstatite meteorite parent body—is not detectable. Chemical trends in F chondrites apparently reflect primary nebular processes. Cosmochemical fractionation of lithophiles from siderophiles and chalcophiles occurred at moderately high temperatures, certainly higher than those existing during formation of primitive carbonaceous, enstatite and ordinary chondrites of petrologic type ≤3.     

Trace elements in primitive meteorites—VI. Abundance patterns of thirteen trace elements and interelement relationships in unequilibrated ordinary chondrites

Neutron activation analysis was used to determine As, Au, Bi, Cd, Co, Cu, Ga, In, Sb, Se, Te, Tl and Zn in 13 different unequilibrated ordinary chondrites (UOC), i.e. those having chemicallyinhomogeneous silicates. This study together with prior data completes our coverage of this group of 23 primitive chondrites. Four elements are quite variable in UOC (Cd—20 x, In—30 x, Bi—300 x and Tl—1300 x), the others varying by 2–8 x. Three highly-depleted elements—Bi, In and Tl—are richer by 5–35 x in unequilibrated chondrites than in their equilibrated congeners. All 3 elements vary directly in characteristic fashion with disequilibrium parameters for olivine and pyroxene in UOC and generally with petrologic type 3 > 4 > 5 > 6. The data do not provide unambiguous evidence for nebular fractionation of siderophile elements. Examination of statistically-significant interelement relationships among various ordinary chondrite populations involving 34 elements reveals patterns distinct from those of other chondritic groups. These patterns reflect nebular metal-silicate fractionation which preceded or accompanied thermal fractionation. The results point to significant differences in the formation of primitive carbonaceous, enstatite and ordinary chondrites.     

Demethylated hopanes in crude oils and their applications in petroleum geochemistry

Analyses of some Australian crude oils show that many contain varying concentrations of A/ B-ring demethylated hopanes. These range from C₂₆ to C₃₄ and have been identified from their retention times and mass spectral data as 17α(H)-25-norhopanes. Comparison of hopane and demethylated hopane concentrations and distributions in source-related, biodegraded oils suggests that demethylated hopanes are biotransformation products of the hopanes. Further, it appears that the process occurs at a late stage of biodegradation, after partial degradation of steranes has occurred. Demethylated hopanes are proposed as biomarkers for this stage of severe biodegradation. The presence of these compounds in apparently undegraded crude oils is thought to be due to the presence of biodegraded crude oil residues which have been dissolved by the undegraded crude oil during accumulation in the reservoir sands. The timing of hopane demethylation, relative to the degradation of other compounds, has been assessed and the progressive changes in crude oil composition with increasing extent of biodegradation have been identified. The use of demethylated hopanes as maturity parameters for severely biodegraded crude oils, and the applicability of established biomarker maturity parameters to such oils, are also discussed.     

Microbial lipids of an intertidal sediment—I. Fatty acids and hydrocarbons

A detailed study has been made of the solvent extractable monocarboxylic, dicarboxylic and hydroxylated fatty acids and n-alkanes in a surface intertidal sediment, and the distributions compared to microorganisms cultured from the sediment. Diatoms are shown to contribute most of the monocarboxylic acids, particularly the significant amounts of polyunsaturated acids present, and a small proportion of the n-alkanes. Bacteria contribute between 11 and 14% of the monocarboxylic acids and markers for this, including trans-monounsaturated acids, are proposed. Detritus from the sea-grass Zostera muelleri is a major source of the α-hydroxy-, ω-hydroxy and α,ω-dicarboxylic acids in the sediment and a minor contributor of n-alkanes and long-chain fatty acids.     

Thermal metamorphism of primitive meteorites—VIII. Noble gases,carbon and sulfur in Allende (C3) meteorite heated at 400–1000°C

Noble gases, C and S are lost from Allende samples heated for 1 week at temperatures of 400–1000°C in a low pressure environment. In the extreme, losses of ³He and ⁴He are ~ 100 × while for C. S and Ne, Ar and Kr isotopes and ¹³²Xe. these are ≤10 ×. Except for He, these losses are less severe than those of Bi or Tl from samples heated in the same runs. Significant He. Ne and Ar isotopic fractionation during heating indicates preferential outgassing of specific reservoirs. Apparent activation energies for all species generally indicate loss controlled by a diffusive process. Next to He, ⁴⁰Ar is the most labile of those species considered here but still less so than Bi or Tl. L-group (but not H- or LL-group) chondrites may have lost mobile elements like Tl while being outgassed after late impact-associated heating. A less likely alternative possibility involving a collateral relation between condensation conditions and depth in a parent object may also explain the L-group trend.