Will Meredith

Fossil steroids record the appearance of Demospongiae during the Cryogenian period

The Neoproterozoic era (1,000–542 Myr ago) was an era of climatic extremes and biological evolutionary developments culminating in the emergence of animals (Metazoa) and new ecosystems. Here we show that abundant sedimentary 24-isopropylcholestanes, the hydrocarbon remains of C30 sterols produced by marine demosponges, record the presence of Metazoa in the geological record before the end of the Marinoan glaciation (∼635 Myr ago). These sterane biomarkers are abundant in all formations of the Huqf Supergroup, South Oman Salt Basin, and, based on a new high-precision geochronology, constitute a continuous 100-Myr-long chemical fossil record of demosponges through the terminal Neoproterozoic and into the Early Cambrian epoch. The demosponge steranes occur in strata that underlie the Marinoan cap carbonate (>635 Myr ago). They currently represent the oldest evidence for animals in the fossil record, and are evidence for animals pre-dating the termination of the Marinoan glaciation. This suggests that shallow shelf waters in some late Cryogenian ocean basins (>635 Myr ago) contained dissolved oxygen in concentrations sufficient to support basal metazoan life at least 100 Myr before the rapid diversification of bilaterians during the Cambrian explosion. Biomarker analysis has yet to reveal any convincing evidence for ancient sponges pre-dating the first globally extensive Neoproterozoic glacial episode (the Sturtian, ∼713 Myr ago in Oman).

Influence of biodegradation on crude oil acidity and carboxylic acid composition

Quantitative analysis of separated carboxylic acid fractions of 33 crude oils from the UK, Italy and California, showed that the carboxylic acid fraction is a major factor responsible for the acidity in these oils. It was apparent that biodegradation is the main process that produces high concentrations of carboxylic acids in these crude oils with the extent of biodegradation, as measured from their hydrocarbon compositions, being clearly correlated with their total acid number (TAN). Although probably not important in influencing oil TAN, the distribution of C30‐C32 hopanoic acids was also seen to be controlled by biodegradation, increasing in concentration for all but the most biodegraded oils. Hopanoic acids with the 17b(H),21b(H) stereochemistry were found in many of the biodegraded oils, and were thought to be mainly derived from the bacteria that were responsible for the biodegradation of the oil. This may have implications for the timing and mechanisms of the biodegradation involved. The role of C0‐C3 alkylphenols in determining oil acidity was investigated and shown not to be a significant factor in the sample set studied. However, a number of undegraded oils, with low carboxylic acid contents were seen to have relatively high acidities, showing that factors other than biodegradation, possibly related to high sulphur content can control oil acidity in certain oil types. # 2000 Elsevier Science Ltd. All rights reserved.

Analysis of conjugated steroid androgens: Deconjugation, derivatisation and associated issues

Gas chromatography/mass spectrometry (GC/MS) is the preferred technique for the detection of urinary steroid androgens for drug testing in athletics. Excreted in either the glucuronide or sulfated conjugated form, steroids must first undergo deconjugation followed by derivatisation to render them suitable for GC analysis. Discussed herein are the deconjugation and the derivatisation preparative options. The analytical challenges surrounding these preparatory approaches, in particular the inability to cleave the sulfate moiety have led to a focus on testing protocols that reply on glucuronide conjugates. Other approaches which alleviate the need for deconjugation and derivatisation are also highlighted.

Hydropyrolysis: Implications for radiocarbon pretreatment and characterization of black carbon

Charcoal is the result of natural and anthropogenic burning events, when biomass is exposed to elevated temperatures under conditions of restricted oxygen. This process produces a range of materials, collectively known as pyrogenic carbon, the most inert fraction of which is known as black carbon (BC). BC degrades extremely slowly and is resistant to diagenetic alteration involving the addition of exogenous carbon, making it a useful target substance for radiocarbon dating particularly of more ancient samples, where contamination issues are critical. We present results of tests using a new method for the quantification and isolation of BC, known as hydropyrolysis (hypy). Results show controlled reductive removal of non-BC organic components in charcoal samples, including lignocellulosic and humic material. The process is reproducible and rapid, making hypy a promising new approach not only for isolation of purified BC for 14C measurement but also in quantification of different labile and resistant sample C fractions.

The effect of water pressure on hydrocarbon generation reactions: some inferences from laboratory experiments

ABSTRACT For the last twenty-five years most petroleum geochemists and basin modellers have produced and used models for maturation and hydrocarbon generation reactions in geological basins that do not consider pressure as a primary control. These conclusions are based on extensive laboratory investigations mainly using pyrolysis. Chemical theory, however, indicates that endothermic volume expansion reactions, such as maturation and hydrocarbon generation, are controlled by both the system pressure and temperature, and geochemists and basin modellers may need to reconsider the importance of pressure on maturation and hydrocarbon generation reactions in geological basins. Unusual earlier studies (at least in terms of petroleum geochemical pyrolysis research) used a vessel in which the pressure is entirely derived from liquid water rather than both liquid water and vapour, as in hydrous pyrolysis experimentation. Results from these experiments showed that both total organic carbon (TOC) and hydrogen index (HI) were elevated in the pyrolysed kerogen residue, suggesting that hydrocarbon generation was being retarded by the effect of water pressure. This paper presents the results of an experimental investigation into the effects of water pressure and phase on hydrocarbon generation and expulsion from the Kimmeridge Clay Formation (KCF) in the temperature range 310–350°C and in the pressure range 0–500 bar, and presents quantitative results both for the amounts of gas and bitumen generated and the composition of the generated gas. The experimental results show that the water pressure retards both bitumen and gas generation, with gas generation being retarded more severely than bitumen generation.

Diesel Injector Deposits - An Issue That Has Evolved with Engine Technology

Diesel engines have traditionally been favoured in heavy-duty applications for their fuel economy, robustness, reliability and relative lack of fuel sensitivity. Recently it has seen a growth in its popularity in light duty applications due particularly to its fuel efficiency. However, as the engine technology and particularly the fuel injection equipment has evolved to meet ever stricter emissions legislation the engines have become more sensitive to deposit formation resulting from changes in fuel quality. This paper reviews bouts of concern over diesel fuel injector deposits, possible causes for the phenomenon and test methods designed to screen fuels to eliminate problems.

Conjugated steroids: analytical approaches and applications

An introduction to conjugated steroids and the justification for their analysis is provided covering both environmental and biological samples. Determining conjugated steroids or indeed any organic chemical which is conjugated upon excretion from the body has relevance in diagnostic monitoring, forensic screening and environmental analysis (from the endocrine disrupter perspective). The various analytical approaches and the accompanying issues are application-dependent. There are numerous options at each stage of analysis, from extraction, hydrolysis, derivatisation, and detection, and advances can be confined to the specific application for which it was developed. Emphasis is placed on the choice of separation and how gas or liquid chromatography necessitates different preparative stages to enable conjugated steroid determination. Possible future directions and research for conjugated steroid analysis are discussed.

A Novel Technique for Investigating the Nature and Origins of Deposits Formed in High Pressure Fuel Injection Equipment

Recent developments in diesel fuel injection equipment coupled with moves to using ULSD and biodiesel blends has seen an increase in the number of reports, from both engine manufacturers and fleet operators, regarding fuel system deposit issues. Preliminary work performed to characterise these deposits showed them to be complicated mixtures, predominantly carbon like but also containing other possible carbon precursor materials. This paper describes the application of the combination of hydropyrolysis, gas chromatography and mass spectrometry to the analysis of these deposits. It also discusses the insights that such analysis can bring to the constitution and origin of these deposits.

Fate of Soil Organic Carbon and Polycyclic Aromatic Hydrocarbons in a Vineyard Soil Treated with Biochar

The effect of biochar addition on the levels of black carbon (BC) and polcyclic aromatic hydrocarbons (PAHs) in a vineyard soil in central Italy was investigated within a two year period. Hydropyrolysis (HyPy) was used to determine the contents of BC (BCHyPy) in the amended and control soils, while the hydrocarbon composition of the semi-labile (non-BCHyPy) fraction released by HyPy was determined by gas chromatography-mass spectrometry, together with the solvent-extractable PAHs. The concentrations of these three polycyclic aromatic carbon reservoirs changed and impacted differently the soil organic carbon over the period of the trial. The addition of biochar (33 ton dry biochar ha(-1)) gave rise to a sharp increase in soil organic carbon, which could be accounted for by an increase in BCHyPy. Over time, the concentration of BCHyPy decreased significantly from 36 to 23 mg g(-1) and as a carbon percentage from 79% to 61%. No clear time trends were observed for the non-BCHyPy PAHs varying from 39 to 34 μg g(-1) in treated soils, not significantly different from control soils. However, the concentrations of extractable PAHs increased markedly in the amended soils and decreased with time from 153 to 78 ng g(-1) remaining always higher than those in untreated soil. The extent of the BCHyPy loss was more compatible with physical rather than chemical processes.

Cryogenian evolution of stigmasteroid biosynthesis

Biosynthesis of C29 sterols, enhancing eukaryotic temperature resistance, evolved during the global Neoproterozoic glaciations. Sedimentary hydrocarbon remnants of eukaryotic C26–C30 sterols can be used to reconstruct early algal evolution. Enhanced C29 sterol abundances provide algal cell membranes a density advantage in large temperature fluctuations. Here, we combined a literature review with new analyses to generate a comprehensive inventory of unambiguously syngenetic steranes in Neoproterozoic rocks. Our results show that the capacity for C29 24-ethyl-sterol biosynthesis emerged in the Cryogenian, that is, between 720 and 635 million years ago during the Neoproterozoic Snowball Earth glaciations, which were an evolutionary stimulant, not a bottleneck. This biochemical innovation heralded the rise of green algae to global dominance of marine ecosystems and highlights the environmental drivers for the evolution of sterol biosynthesis. The Cryogenian emergence of C29 sterol biosynthesis places a benchmark for verifying older sterane signatures and sets a new framework for our understanding of early algal evolution.