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.     

Total nitrogen in lunar soils,breccias and rocks

The total nitrogen contents of a number of lunar samples from Apollo 16 and 17 missions are reported. Solar wind is the main source for the observed excess nitrogen in most fines. Total nitrogen in the soils is found to be proportional to the solar wind rare gases Ar³⁶ and Xe¹³². Linear correlations are also noted between the agglutinate contents of the soils and their carbon and nitrogen contents. Seventeen soils (Apollo 15, 16 and 17) have been sieved and nitrogen has been measured in various grain size fractions. An inverse correlation between the mean grain diameter and the nitrogen contents is seen, showing that a large fraction of the solar wind nitrogen is surface correlated. An apparent volume component, due to the presence of agglutinates, is found in most soils.     

Nitrogen and xenon in acid residues of iron meteorites

Total nitrogen, measured by neutron activation analysis, is highly enriched in residues from iron meteorites obtained by dissolution of the metal in dilute H₂SO₄, relative to the bulk value. On the average, the residues, representing 3% mass, contain 22% of total N. Group IA has more dissolved N than IIIA. Lithium and Ir show a distribution pattern parallel to N. Total Xe has been measured in several residues and its isotopic composition is, similar to atmospheric Xe for mass numbers 131 to 136 but not for ¹²⁴Xe and ¹²⁶Xe which are strongly depleted in the non-magnetic residues. It is suggested that iron meteorites have trapped in their micro-inclusions, some pre-solar nebular matter which is isotopically heterogeneous.     

Total nitrogen in meteorites

Total N has been measured in a number of meteorites by neutron activation analysis using the reaction N¹⁴(n, p)C¹⁴. From each meteorite a number of chips have been analysed to investigate the variation of N contents in a sample. Many meteorites are found to contain a heterogeneous distribution of N. Eighteen chondrites, mostly of the classes C3, H4, H5, L4, L5, L6 and LL6, and six achondrites are found to have average N contents of 10–45 ppm. These do not show any clear-cut dependence of N on petrological group. However, the inherent heterogeneity or the fact that from most meteorite classes only single falls were studied might be responsible for this lack of correlation. In Cold Bokkeveld (C2) N is high (420 ppm). Unlike C, N content of ureilites is low (26 ppm). Nitrogen is enriched in the non-magnetic as compared to the magnetic fractions in H-group chondrites. Analyses of sieved Bjurböle phases show no enrichment of N in finer matrix material, nor any depletion in chondrules. In two gas-rich meteorites, Kapoeta and Assam, there is no excess N in the dark phases. Nine iron meteorites and three mesosiderites were analysed. Twenty analyses of Canyon Diablo and seven of Odessa establish a very heterogeneous N distribution in these meteorites.     

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.     

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.     

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.     

Trace elements in primitive meteorites—V. Abundance patterns of thirteen trace elements and interelement relationships in enstatite chondrites

Neutron activation analysis was used to determine As, Au, Bi, Cd, Co, Cu, Ga, In, Sb, Se, Te, Tl and Zn in 11 samples representing 9 chondrites of grades E4–6. These chondrites exhibit systematic intra- and inter-grade differences particularly for highly-variable elements, the differences being E4 ? E3 > E6 ? E5. The abundance pattern for these 13 and an additional 16 elements in E3-6 chondrites differs from those of other primitive meteorites—the carbonaceous and unequilibrated ordinary chondrites. A search for statistically-significant interelement relationships among the 13 elements (for grades E4–6) reveal that 40 elementpairs are linearly and/or exponentially correlated. Similar consideration of data for 37 elements in 12 chondrites (grades E3–6) reveals that 191 element-pairs exhibit such relationships, 170 involving linear and/or exponential correlations, the remainder involving anti-correlations. The patterns depicting these relationships—i.e. the correlation profiles—and elemental abundance patterns, factor analysis and two-element correlation diagrams are consistent with all enstatite chondrites representing a single evolutionary sequence. The primary process responsible for the chemical trends of these chondrites involved thermal fractionation accompanied by geochemical fractionation of sulfide-plus-metal from silicate, probably during condensation and accretion of solid material from the solar nebula. Chalcophile elements may have been fractionated during condensation or, after accretion, during thermal metamorphism in the parent body. No genetic model proposed thus far accounts for the detailed chemical trends, although the constrained equilibrium theory and two-component condensation theories qualitatively seem most satisfactory. The correlation profiles of enstatite, carbonaceous and unequilibrated ordinary chondrites are distinctly different, pointing to major differences in the formation conditions of these different sorts of primitive meteorites.     

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.     

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.     

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.     

On volatile element trends in gas-rich meteorites

Study of 10 volatile elements (and non-volatile Co) in co-existing light and dark portions of 5 gas-rich chondrites indicates patterns of distinct but non-uniform enrichment of volatile elements. Only Cs is enriched in all samples; Hi and Tl enrichments covary. The observed enrichments are inconsistent with prior suggestions of admixture of C1 or C2 chondritic matter, whether pristine or partly devolatilized, but suggest that both light and dark portions of each chondrite represents a compositionally more extended sampling of parental nebular material than hitherto known.     

Sulphur isotope effects in the high temperature oxidation of troilite

Troilite oxidation in air at 1200°C gives sulphur dioxide which is slightly enriched (~0.3%.) in ³⁴S. No systematic variations were seen of the isotopic compositions of product sulphur dioxide or residual troilite with extent of conversion. We speculate that the oxidation reaction takes place at the surface of the molten troilite in such a way as to inhibit mixing between the reacting outer layers and the unreacted liquid substrate so that Rayleigh behaviour with extent of reaction is not observed.     

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.     

Stable carbon isotope ratios in Astrangia danae: evidence for algal modification of carbon pools used in calcification

Stable carbon isotope ratios have been measured in skeletons of the temperature shallow water scleractinian coral, Astrangia danae. δ¹³C values ranging from ?5.42 to ?7.30%. revealed the expected depletion of ¹³C in skeletal carbonate relative to sea water bicarbonate. Differences among the ratios could not be attributed to collection site and were not correlated to skeletal morphology. Values of δ¹³C were directly related to zooxanthellae density for all colonies, so that as zooxanthellae concentration increased, δ¹³C valued increased. Colonies maintained under high temperature conditions were offset from the normal, exhibiting ratios less enriched in ¹³C than similar colonies from natural conditions. These trends supported the models of Weber and Goreau in which the carbon pools used in calcification are modified by algal photosynthesis. Direct evidence of physiological differences between symbiotic and asymbiotic colonies of A. danae has also been provided.     

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.     

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.     

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.     

Thermal metamorphism of primitive meteorites—X. Additional trace elements in Allende (C3V) heated to 1400° C

We report data for Ag, As, Cd, Cs, Co, Cu, Rb, Sb, Te, Tl and Zn in Allende samples subjected to week-long heating at 400–1400°C in a low-pressure H₂ environment. Temperatures of incipient release for these 11 and 5 additional elements tend to be ordered in a manner similar to postulated condensation sequences during cooling of nebular material but there are differences. Losses progress with temperature but neither the extent of loss nor apparent activation energies for mobilization would have been predictable to even a zeroth order approximation. Elemental retentivity trends and interelement correlation patterns for Allende (C3V) and Murchison (C2) differ markedly indicating a substantially different trace element siting, hence loss trends for these two chondrites.     

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.