Stable carbon isotope evidence for two sources of organic matter in coastal sediments: seagrasses and plankton

Organic carbon from sediments collected in Texas seagrass meadows was enriched in ¹³C by an average of 6.6% relative to organic carbon from offshore sediments. Within the South Texas hay system examined. δ¹³C values became increasingly more typical of offshore sediments with increasing distance from seagrass meadows. This permits the use of carbon isotope data as a measure of the relative contributions of seagrasses and plankton to sedimentary organic matter.     

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.     

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.     

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.     

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.     

Thermal metamorphism of primitive meteorites—XL The enstatite meteorites: origin and evolution of a parent body

We report neutron activation data for Ag, As, Bi, Cd, Co, Cs, Cu, Ga, In, Rb, Se, Te, Tl and Zn in samples of Abee heated at temperatures of 1000–1400°C in a low-pressure environment (initially ~ 10^?5 atm H₂) and in 9 enstatite achondrites (aubrites) and the silicate portion of the unique stony-iron, Mt Egerton. Trace element losses in heated Abee progress with temperature, the lowest retention being 2.4 × 10^?6 of initial contents. These data indicate trace element loss above 1000°C via diffusion-controlled processes having apparent activation energies of 8–55 kcal/mol ; only Co exhibits a significantly higher energy. These trace element data and those for aubrites, Mt Egerton and E4–6 chondrites, and mineralogic and isotopic evidence link all enstatite meteorites to a common parent body. Volatile, mobile elements vary inversely with cobalt content in aubrites and Mt Egerton but directly in E4–6 chondrites; this is inconsistent with all genetic models positing fractionation of such elements during nebular condensation and accretion. However, the data are consistent with the idea that aubrites and Mt. Egerton reflect fractional crystallization of a magma produced from enstatite chondrite-like parent material (probably E6) and late introduction of chalcophiles and mobile elements transported by FeS-Fe eutectic from an E4–6 region experiencing open-system metamorphism. As suggested earlier, the only primary process that affected enstatite meteorites involved fractionation of non-volatile lithophiles from sulfides and metal during condensation and accretion of chondritic parent material from the nebula. If, as seems likely, volatile/mobile elements reflect secondary processes, they can only be used to establish alteration conditions within the enstatite parent body and not to estimate temperatures during primary nebular condensation and accretion.     

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.     

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.     

Matrix isolation technique for the study of some factors affecting the partitioning of trace elements

Some of the factors that affect the preferred positions of cations in ionic-solid solutions were investigated utilizing vibrational spectroscopy. Solid solutions of the sulfate and chromate ions codoped with La³⁺ and Ca²⁺ in a KBr host lattice were examined as a function of the polyvalent-cation concentration. The cation—anion pairing process was found to be random for Ca²⁺ whereas the formation of La³⁺SO₄^2? ion-pairs with a C_2v bonding geometry is highly preferential to any type of La³⁺CrO₄^2? ion-pair formation. The relative populations of ion-pair site configurations are discussed in terms of an energy—entropy competition which can be applied to the partition of trace elements during magmatic processes.     

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.     

Thermal metamorphism of primitive meteorites—III. Ten trace elements in Krymka L3 chondrite heated at 400–1000°C

Ten trace elements were determined by neutron activation analysis in Krymka (L3) chondrite samples heated for 1 week, at 100°C increments, from 400 to 1000°C in a low-pressure environment (initially 10^?5 atm H₂). As in other samples studied. Co seems unaffected by heating; ~50% of Cs and Ga are lost only at 1000°C and losses of other elements increase with temperature to extremes of ～ 25% for Se and 95–99% for Ag, Bi, In, Te, T1 and Zn. Where comparison is possible, ‘open-system’ losses are generally in the order Krymka (L3) > Abee (E4) > Allende (C3). Treating elemental mobilization as representing a kinetic process involving diffusion from spherical grains of uniform size Ag, Bi, In, Te, Tl and Zn are lost from a single host phase or by a single process. This differs from trends shown by many of these elements in Abee and Allende and terrestrial basalt BCR-1. Loss of Tl apparently involves a process with a low activation energy, perhaps desorption. Loss of other elements apparently reflects diffusion-controlled process(es).Trace element contents, patterns of statistically significant interelement relationships, factor analysis and two-element correlation diagrams for unheated and heated Krymka and ‘as-received’ L3-6 chondrites are very different. Thus, significant open-system metamorphism during the genesis of L-group chondrites are not supported by these data. This contrasts sharply with the picture for enstatite chondrites, indicating substantial differences in the origin of various chondritic groups.     

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.     

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.     

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.     

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.     

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.     

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.     

The influence of minerals on the pyrolysis of kerogens

The effect of mineral matter on the laboratory pyrolysis of sediments, kerogens and coals, and of coal macerals mixed with either alumina, bentonite, kaolinite, or calcium carbonate has been investigated. Some minerals are more active than others in effecting changes in the composition of the pyrolysate. The relative content of low molecular weight pyrolysis products is higher for kerogens pyrolyzed in a mineral matrix than for isolated kerogens. Our limited data suggests that this is due to both condensation and gasification of higher molecular weight constituents in the ‘primary’ pyrolysate. Differences in the content of aromatic versus aliphatic compounds have been noted when pyrograms from coal macerals are compared with pyrograms from coal maceral-mineral mixtures. We conclude that mineralogy is important in controlling the composition of kerogen pyrolysis products.