Publications
72 results found
Salter TL, Watson JS, Sephton MA, 2023, Effects of minerals (phyllosilicates and iron oxides) on the responses of aliphatic hydrocarbon containing kerogens (Type I and Type II) to analytical pyrolysis, Journal of Analytical and Applied Pyrolysis, Vol: 170, Pages: 1-8, ISSN: 0165-2370
Organic matter in sediments is dominated by kerogen, a high molecular weight geomacromolecule. Kerogen can be subdivided into Types I to IV that provide paleoenvironmental and petroleum potential information. Kerogen typing can be performed by several chemical methods including elemental analysis (H/C and O/C), FTIR and pyrolysis-gas chromatography techniques. However, kerogens occur naturally within mineral matrices and these can influence the chemical responses. We have examined the effects of a range of minerals (namely kaolinite, lizardite, ripidolite, illite, montmorillonite, haematite, goethite, limonite and magnetite) on the responses of kerogen to pyrolysis-gas chromatography-mass spectrometry. We used aliphatic hydrocarbon containing kerogen Types I and II from Carboniferous Midland Valley shales of Scotland and the Jurassic Oxford Clay of southern England, respectively, as well as a pure synthetic aliphatic polymer, polyethylene. We find that the aliphatic organic matter in Type I kerogens is transformed by interaction with minerals during pyrolysis to give a signal incorrectly suggesting more contributions from land plant-containing kerogens, such as a large number of aromatic molecules. Pyrolysis with goethite, limonite and magnetite leads to almost complete destruction of the organic matter. Hence, the mineral composition of sedimentary rocks during pyrolysis should be considered when assigning kerogen types. Failure to consider the effects of minerals can lead to incorrect assignment of kerogen type and, therefore, erroneous interpretations of paleoenvironments and petroleum potential.
Sephton M, Chan Q, Watson J, et al., 2023, Insoluble macromolecular organic matter in the Winchcombe meteorite, Meteoritics and Planetary Science, ISSN: 1086-9379
The Winchcombe meteorite fell on 28th February 2021 in Gloucestershire, UK. As the most accurately recorded carbonaceous chondrite fall, the Winchcombe meteorite is an opportunity to link a tangible sample of known chemical constitution to a specific region of the solar system whose chemistry can only be otherwise predicted or observed remotely. Winchcombe is a CM carbonaceous chondrite, a group known for their rich and varied abiotic organic chemistry. The rapid collection of Winchcombe provides an opportunity to study a relatively terrestrial contaminant-limited meteoritic organic assemblage. The majority of the organic matter in CM chondrites is macromolecular in nature and we have performed non-destructive and destructive analyses of Winchcombe by Raman spectroscopy, online pyrolysis-gas chromatography (pyrolysis-GC-MS), and stepped combustion. The Winchcombe pyrolysis products were consistent with a CM chondrite, namely aromatic and polycyclic aromatic hydrocarbons, sulfur-containing units including thiophenes, oxygen containing units such as phenols and furans, and nitrogen-containing units such as pyridine; many substituted/alkylated forms of these units were also present. The presence of phenols in the online pyrolysis products indicated only limited influence from aqueous alteration, which can deplete the phenol precursors in the macromolecule when aqueous alteration is extensive. Raman spectroscopy and stepped combustion also generated responses consistent with a CM chondrite. The pyrolysis-GC-MS data is likely to reflect the more labile and thermally sensitive portions of the macromolecular materials while the Raman and stepped combustion data will also reflect the more refractory and non-pyrolyzable component, hence we accessed the complete macromolecular fraction of the recently fallen Winchcombe meteorite and revealed a chemical constitution that is similar to other meteorites of the CM group.
Royle S, Cropper L, Watson J, et al., 2023, Solid phase micro extraction for organic contamination control throughout assembly and operational phases of space missions, Astrobiology, Vol: 23, Pages: 127-143, ISSN: 1531-1074
Space missions concerned with life detection contain highly sensitive instruments for the detection of organics. Terrestrial contamination can interfere with signals of indigenous organics in samples and has the potential to cause false positive biosignature detections, which may lead to incorrect suggestions of the presence of life elsewhere in the Solar System. This study assessed the capability of solid phase micro extraction (SPME) as a method for monitoring organic contamination encountered by spacecraft hardware during assembly and operation. SPME-gas chromatography-mass spectrometry (SPME-GC-MS) analysis was performed on potential contaminant source materials, which are commonly used in spacecraft construction. The sensitivity of SPME-GC-MS to organics was assessed in the context of contaminants identified in molecular wipes taken from hardware surfaces on the ExoMars Rosalind Franklin rover. SPME was found to be effective at detecting a wide range of common organic contaminants that include aromatic hydrocarbons, non-aromatic hydrocarbons, nitrogen-containing compounds, alcohols and carbonyls. A notable example of correlation of contaminant with source material was the detection of benzenamine compounds in an epoxy adhesive analyzed by SPME-GC-MS and in the ExoMars rover surface wipe samples. The current form of SPME-GC-MS does not enable quantitative evaluation of contaminants, nor is it suitable for the detection of every group of organic molecules relevant to astrobiological contamination concerns, namely, large and/or polar molecules such as amino acids. However, it nonetheless represents an effective new monitoring method for rapid, easy identification of organic contaminants commonly present on spacecraft hardware and could thus be utilized in future space missions as part of their contamination control and mitigation protocols.
Kumar P, Zavala-Reyes JC, Kalaiarasan G, et al., 2023, Characteristics of fine and ultrafine aerosols in the London underground., Science of the Total Environment, Vol: 858, ISSN: 0048-9697
Underground railway systems are recognised spaces of increased personal pollution exposure. We studied the number-size distribution and physico-chemical characteristics of ultrafine (PM0.1), fine (PM0.1-2.5) and coarse (PM2.5-10) particles collected on a London underground platform. Particle number concentrations gradually increased throughout the day, with a maximum concentration between 18:00 h and 21:00 h (local time). There was a maximum decrease in mass for the PM2.5, PM2.5-10 and black carbon of 3.9, 4.5 and ~ 21-times, respectively, between operable (OpHrs) and non-operable (N-OpHrs) hours. Average PM10 (52 μg m-3) and PM2.5 (34 μg m-3) concentrations over the full data showed levels above the World Health Organization Air Quality Guidelines. Respiratory deposition doses of particle number and mass concentrations were calculated and found to be two- and four-times higher during OpHrs compared with N-OpHrs, reflecting events such as train arrival/departure during OpHrs. Organic compounds were composed of aromatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) which are known to be harmful to health. Specific ratios of PAHs were identified for underground transport that may reflect an interaction between PAHs and fine particles. Scanning transmission electron microscopy (STEM) chemical maps of fine and ultrafine fractions show they are composed of Fe and O in the form of magnetite and nanosized mixtures of metals including Cr, Al, Ni and Mn. These findings, and the low air change rate (0.17 to 0.46 h-1), highlight the need to improve the ventilation conditions.
Chan QHS, Watson JS, Sephton MA, et al., 2023, The amino acid and polycyclic aromatic hydrocarbon compositions of the promptly recovered CM2 Winchcombe carbonaceous chondrite, Meteoritics and Planetary Science, ISSN: 1086-9379
The rapid recovery of the Winchcombe meteorite offers a valuable opportunity to study the soluble organic matter (SOM) profile in pristine carbonaceous astromaterials. Our interests in the biologically relevant molecules, amino acids—monomers of protein, and the most prevalent meteoritic organics—polycyclic aromatic hydrocarbons (PAHs) are addressed by analyzing the solvent extracts of a Winchcombe meteorite stone using gas chromatography mass spectrometry. The Winchcombe sample contains an amino acid abundance of ~1132 parts-per-billion that is about 10 times lower than other CM2 meteorites. The detection of terrestrially rare amino acids, including α-aminoisobutyric acid (AIB); isovaline; β-alanine; α-, β-, and γ-amino-n-butyric acids; and 5-aminopentanoic acid, and the racemic enantiomeric ratios (D/L = 1) observed for alanine and isovaline indicate that these amino acids are indigenous to the meteorite and not terrestrial contaminants. The presence of predominantly α-AIB and isovaline is consistent with their formation via the Strecker-cyanohydrin synthetic pathway. The L-enantiomeric excesses in isovaline previously observed for aqueously altered meteorites were viewed as an indicator of parent body aqueous processing; thus, the racemic ratio of isovaline observed for Winchcombe, alongside the overall high free:total amino acid ratio, and the low amino acid concentration suggest that the analyzed stone is derived from a lithology that has experienced brief episode(s) of aqueous alteration. Winchcombe also contains 2- to 6-ring alkylated and nonalkylated PAHs. The low total PAHs abundance (6177 ppb) and high nonalkylated:alkylated ratio are distinct from that observed for heavily aqueously altered CMs. The weak petrographic properties of Winchcombe, as well as the discrepancies observed for the Winchcombe SOM content—a low total amino acid abundance comparable to heavily altered CMs, and ye
King AJ, Daly L, Rowe J, et al., 2022, The Winchcombe meteorite, a unique and pristine witness from the outer solar system., Science of Advanced Materials, Vol: 8, Pages: 1-17, ISSN: 1947-2935
Direct links between carbonaceous chondrites and their parent bodies in the solar system are rare. The Winchcombe meteorite is the most accurately recorded carbonaceous chondrite fall. Its pre-atmospheric orbit and cosmic-ray exposure age confirm that it arrived on Earth shortly after ejection from a primitive asteroid. Recovered only hours after falling, the composition of the Winchcombe meteorite is largely unmodified by the terrestrial environment. It contains abundant hydrated silicates formed during fluid-rock reactions, and carbon- and nitrogen-bearing organic matter including soluble protein amino acids. The near-pristine hydrogen isotopic composition of the Winchcombe meteorite is comparable to the terrestrial hydrosphere, providing further evidence that volatile-rich carbonaceous asteroids played an important role in the origin of Earth's water.
Salter TL, Watson J, Waite JH, et al., 2022, Hydrothermal processing of microorganisms: Mass spectral signals of degraded biosignatures for life detection on icy moons, ACS Earth and Space Chemistry, Vol: 6, Pages: 2508-2518, ISSN: 2472-3452
Life detection missions to the outer solar system are concentrating on the icy moons of Jupiter and Saturn and their inferred sub-surface oceans. Access to evidence of habitability, and possibly even life, is facilitated by the ejection of subsurface material in plumes and outgassing fissures. Orbiting spacecraft can intersect the plume material or detect past sputtered remnants of outgassed products and analyse the contents using instruments such as mass spectrometers. Hydrothermalism has been proposed for the subsurface environments of icy moons and the organic remains of any associated life would be expected to suffer some degradation through hydrothermalism, radiolysis, or spacecraft flyby impact fragmentation. Hydrothermalism is treated here for the first time in the context of the Europa Clipper mission.To assess the influence of hydrothermalism on the ability of orbiting mass spectrometers to detect degrading signals of life, we have subjected Earth microorganisms to laboratory hydrothermal processing. The processed microorganism samples were then analysed using gas chromatography-mass spectrometry (GC-MS) and mass spectra were generated. Certain compound classes, such as carbohydrates and proteins are significantly altered by hydrothermal processing, resulting in small one-ring and two-ring aromatic compounds such as indoles and phenols. However, lipid fragments, such as fatty acids, retain their fidelity and their provenance is easily recognised as biological in origin. Our data indicate that mass spectrometry measurements in the plumes of icy moons, using instruments such as the MAss Spectrometer for Planetary Exploration (MASPEX) onboard the upcoming Europa Clipper mission, can reveal the presence of life even after significant degradation by hydrothermal processing has taken place.
Peers De Nieuwburgh C, Watson J, Weiss D, et al., 2022, Environmental screening of water associated with shale gas extraction by fluorescence excitation emission matrix, Environmental Science: Water Research & Technology, Vol: 8, Pages: 2196-2206, ISSN: 2053-1400
The shale revolution has involved the production of oil and gas from shale reservoirs enabled by modern techniques such as horizontal drilling and hydraulic fracturing. Large volumes of water-based fluids are required for hydraulic fracturing, some of which return to the surface as produced water. The recycling and effective disposal of produced water reduces water demand and avoids environmental impacts, respectively. Yet risks of water quality degradation surrounding shale oil and gas extraction operations remain highest during produced water treatment and disposal. Risk assessments related to produced water use are difficult to generate due to a lack of standard monitoring methods to characterise produced water and a lack of baseline monitoring data of surrounding water resources. We have performed a study on laboratory shale leachates using fluorescence Excitation Emission Matrix (EEM) spectra and have demonstrated the utility of this spectroscopic technique as a standard method for environmental screening in which the chemical constitution of produced water is monitored. EEM spectra recorded in this work show that dissolved organic matter (DOM) in laboratory shale leachates contains chromophores such as humic acid-like and soluble microbial-like material. Short emission wavelengths (<380 nm) EEM spectra may indicate anthropogenic contamination incidents in future operations, especially as they correspond to fluorescence signatures of some injection fluid additives. Our simple fluorescence method requires little sample preparation and could be coupled with remote sensors for real time, in-situ monitoring of contamination incidents.
Royle SH, Salter TL, Watson JS, et al., 2022, Mineral matrix effects on pyrolysis products of kerogens infer difficulties in determining biological provenance of macromolecular organic matter at Mars, Astrobiology, Vol: 22, Pages: 1-21, ISSN: 1531-1074
Ancient martian organic matter is likely to take the form of kerogen-like recalcitrant macromolecular organic matter (MOM), existing in close association with reactive mineral surfaces, especially iron oxides. Detecting and identifying a biological origin for martian MOM will therefore be of utmost importance for life detection efforts at Mars. We show that Type I and Type IV kerogens provide effective analogues for putative martian MOM of biological and abiological (meteoric) provenances respectively. We analyse the pyrolytic breakdown products when these kerogens are mixed with mineral matrices highly relevant for the search for life on Mars. We demonstrate that, using traditional thermal techniques as generally used by the Sample Analysis at Mars and Mars Organic Molecule Analyser instruments, even the breakdown products of highly recalcitrant MOM are transformed during analysis in the presence of reactive mineral surfaces, particularly iron. Analytical transformation reduces the diagnostic ability of this technique, as detected transformation products of both biological and abiological MOM may be identical (low molecular weight gas phases and benzene) and indistinguishable. The severity of transformational effects increased through: calcite < kaolinite < haematite < nontronite < magnetite < goethite. Due to their representation of various habitable aqueous environments and the preservation potential of organic matter by iron, it is not advisable to completely avoid iron-rich strata. We conclude that haematite-rich localities, with evidence of extensive aqueous alteration of originally reducing phases, such as the Vera Rubin Ridge, may be relatively promising targets for identifying martian biologically-sourced MOM.
Royle S, Watson JS, Sephton M, 2021, Transformation of cyanobacterial biomolecules by iron oxides during flash pyrolysis: Implications for Mars life detection missions, Astrobiology, Vol: 21, ISSN: 1531-1074
Answering the question of whether life ever existed on Mars is a key goal of both NASA’s and ESA’s imminent Mars rover missions. The obfuscatory effects of oxidising salts, such as perchlorates and sulfates, on organic matter during thermal decomposition analysis techniques are well established. Less well studied are the transformative effects of iron oxides and (oxy)hydroxides, which are present in great abundances in the martian regolith. We examined the products of flash pyrolysis GC-MS, a technique analogous to the thermal techniques employed by past, current and future landed Mars missions, formed when the cyanobacteria Arthrospira platensis was heated in the presence of a variety of Mars-relevant 16iron bearing minerals. We found that iron oxides/(oxy)hydroxides have transformative effects on the pyrolytic products of cyanobacterial biomolecules. Both the abundance and variety of molecular species detected were decreased as iron substrates transformed biomolecules, by both oxidative and reductive processes, into lower fidelity alkanes, aromatic and aryl-bonded hydrocarbons. Despite the loss of fidelity, a suite containing mid-length alkanes and PAHs and/or aryl-bonded molecules in iron-rich samples subjected to pyrolysis, may allude to the transformation of cyanobacterially-derived mid-long chain length fatty acids (particularly unsaturated fatty acids) originally present in the sample. Haematite was found to be the iron-oxide with the lowest transformation potential and so, because this iron oxide has a high affinity forco-deposition of organic matter and preservation over geological timescales, sampling at Mars should target sediments/strata which have undergone a diagenetic history encouraging the dehydration, dehydroxylation and oxidation of more reactive iron-bearing phases to haematite by looking for (mineralogical) evidence of the activity of oxidising, acidic/neutral and either hot or long-lived fluids.
Royle SH, Tan J, Watson JS, et al., 2021, Pyrolysis of carboxylic acids in the presence of iron oxides: implications for life detection on missions to Mars, Astrobiology, Pages: 1-19, ISSN: 1531-1074
The search for, and characterization of, organic matter on Mars is central to efforts in identifying habitable environments and detecting evidence of life in the martian surface and near surface. Iron oxides are ubiquitous in the martian regolith and are known to be associated with the deposition and preservation of organic matter in certain terrestrial environments, thus iron oxide-rich sediments are potential targets for life-detection missions. The most frequently used protocol for martian organic matter characterization (also planned for use on ExoMars) has been thermal extraction for the transfer of organic matter to gas chromatography-mass spectrometry (GC-MS) detectors. For the effective use of thermal extraction for martian samples, it is necessary to explore how potential biomarker organic molecules evolve during this process in the presence of iron oxides. We have thermally decomposed iron oxides simultaneously with (z)-octadec-9-enoic and n-octadecanoic acids and analyzed the products through pyrolysis-GC-MS. We found that the thermally driven dehydration, reduction, and recrystallization of iron oxides transformed fatty acids. Overall detectability of products greatly reduced, molecular diversity decreased, unsaturated products decreased, and aromatization increased. The severity of this effect increased as reduction potential of the iron oxide and inferred free radical formation increased. Of the iron oxides tested hematite showed the least transformative effects, followed by magnetite, goethite, then ferrihydrite. It was possible to identify the saturation state of the parent carboxylic acid at high (0.5 wt %) concentrations by the distribution of n-alkylbenzenes in the pyrolysis products. When selecting life-detection targets on Mars, localities where hematite is the dominant iron oxide could be targeted preferentially, otherwise thermal analysis of carboxylic acids, or similar biomarker molecules, will lead to enhanced polymerization, aromatiz
Montgomery W, Schofield E, Sephton MA, et al., 2021, The Preservation of English Oak in Marine Environments
<jats:p>This study compares the chemical integrity of English Oak (Quercus robur) samples with an age range of four centuries by analysing the lignin degradation. The samples were collected from four historic British vessels and thus represent samples of diverse ages which have nonetheless experienced similar non-arboreal environments. We conclude that the Mary Rose, the oldest vessel studied and the recipient of the most intensive conservation efforts, has been well-preserved through treatment with PEG, and we present a baseline for assessing whether a ship has been biologically degraded.</jats:p><jats:p>The work combines quantitative analytic chemistry techniques (e.g., THM-GC-MS) with the conservation of large historic artifacts.</jats:p>
Kirby M, Sonnenberg JL, Watson JS, et al., 2020, Prevention of UVI precipitation in alkaline aqueous solutions by the siderophore desferrioxamine B, Publisher: American Chemical Society (ACS)
In alkaline and saline solutions, uranium VI (UVI) forms uranyl salts, limiting its mobility in leachates released from nuclear waste repositories into groundwater. However, recent experimental and computational work suggested that natural organic molecules widely present in groundwater such as siderophores could potentially prevent solid precipitation because of the formation of stable UVI-siderophore complexes. It is important we assess the impact of siderophores on aqueous UVI chemistry as they could mobilise UVI from contaminated land and radioactive waste storage and disposal sites. Here we test this hypothesis by combining for the first time experimental studies on uranium precipitation in alkaline pH in the presence of desferrioxamine B (DFOB) and electron structure method calculation of uranyl – hydroxamate complexes to assess their stability. Stirred batch experiments containing 0 to 420 µM DFOB, 42 µM UVI and 0.1 M NaCl were conducted at pH 11.5. DFT was employed to explore the relative stability of different UVI-hydroxamate complexes, representative of the local binding mode of DFOB. During the stirred batch experiments, 5%, 11-12%, 41-53%, 95-96% and 100% of UVI passes through the filter membranes (0.2-1 µm pore diameter) after 24 hours when 0, 4.2, 42, 130 and 420 µM DFOB was added to solution. The DFT results suggest one hydroxamate functional group is most likely to complex with UVI with ∆rG calculated as +3 kJ/mol and -9 kJ/mol for [UO2(OH)3(Lmono)]2- and [UO2(OH)2(L)]- respectively. Conversion of the experimentally derived log β (-1.2 ± 0.3) through the equation ∆rG = -2.303RTlogβ provides ∆rG of +7 kJ/mol, similar to the ∆rG of these two complexes. The results of our study confirm that UVI precipitation could be hindered by the formation of a DFOB complex with UVI complexation through a single hydroxamate functional group as a likely mechanism. These results highlight the mobilising effect siderophores
Bullen JC, Torres-Huerta A, Salaün P, et al., 2020, Portable and rapid arsenic speciation in synthetic and natural waters by an As(V)-selective chemisorbent, validated against anodic stripping voltammetry, Water Research, Vol: 175, Pages: 1-11, ISSN: 0043-1354
Inorganic arsenic speciation, i.e. the differentiation between arsenite and arsenate, is an important step for any program aiming to address the global issue of arsenic contaminated groundwater, whether for monitoring purposes or the development of new water treatment regimes. Reliable speciation by easy-to-use, portable and cost-effective analytical techniques is still challenging for both synthetic and natural waters. Here we demonstrate the first application of an As(V)-selective chemisorbent material for simple and portable speciation of arsenic using handheld syringes, enabling high sample throughput with minimal set-up costs. We first show that ImpAs efficiently removes As(V) from a variety of synthetic groundwaters with a single treatment, whilst As(III) is not retained. We then exemplify the potential of ImpAs for simple and fast speciation by determining rate constants for the photooxidation of As(III) in presence of a TiO2 photocatalyst. Finally, we successfully speciate natural waters spiked with a mix of As(III) and As(V) in both Indian and UK groundwaters with less than 5 mg L−1 dissolved iron. Experimental results using ImpAs agreed with anodic stripping voltammetry (ASV), a benchmark portable technique, with analysis conditions optimised here for the groundwaters of South Asia. This new analytical tool is simple, portable and fast and should find applications within the overall multi-disciplinary remediation effort that is taking place to tackle this worldwide arsenic problem.
Kirby ME, Watson JS, Najorka J, et al., 2020, Experimental study of pH effect on uranium (UVI) particle formation and transport through quartz sand in alkaline 0.1 M sodium chloride solutions, Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol: 592, Pages: 1-11, ISSN: 0927-7757
A thorough understanding of the aqueous uranium VI (UVI) chemistry in alkaline, sodium containing solutions is imperative to address a wide range of critical challenges in environmental engineering, including nuclear waste management. The aim of the present study was to characterise experimentally in more detail the control of pH on the removal of UVI from aqueous alkaline solutions through particle formation and on subsequent transport through porous media. We conducted first static batch experiments in the pH range between 10.5 and 12.5 containing 10 ppm UVI in 0.1 M NaCl solutions and examined the particles formed using filtration, dynamic light scattering, transition electron microscopy and X-ray powder diffraction. We found that at pH 10.5 and 11.5, between 75 and 96 % of UVI was removed from the solutions as clarkeite and studtite over a period of 48 h, forming particles with hydrodynamic diameters of 640 ± 111 nm and 837 ± 142 nm, respectively and representing aggregates of 10′s nm sized crystals randomly orientated. At pH 12.5, the formation of particles >0.2 μm became insignificant and no UVI was removed from solution. The mobility of UVI in these solutions was further studied using column experiments through quartz sand. We found that at pH 10.5 and 11.5, UVI containing particles were immobilised near the column inlet, likely due physical immobilisation of the particles (particle straining). At pH 12.5, however, UVI quantitatively eluted from the columns in the filter fraction <0.2 μm. The findings of our study reinforce a strong control of solution pH on particle size and U removal in alkaline solutions and subsequently on mobility of U through quartz porous media.
Abubakar R, Muxworthy A, Fraser A, et al., 2020, Mapping hydrocarbon charge-points in the Wessex Basin using seismic, geochemistry and mineral magnetics, Marine and Petroleum Geology, Vol: 111, Pages: 510-528, ISSN: 1873-4073
This study reports a multidisciplinary approach to determining hydrocarbon charge-points and migration in the Wessex Basin, southern England. Geochemical analysis of reservoir core material (Bridport Sandstone and Inferior Oolite) using gas chromatography-mass spectrometry (GC-MS), suggests that the oil in the Wessex Basin is from a single source, and that small variations in environmentally sensitive biomarkers are likely due to small differences in maturity or depositional conditions during the formation of the oil over millions of years. Using seismic data, basin modelling revealed two potential hydrocarbon migration pathways from the hanging wall of the Purbeck fault into the Sherwood Sandstone reservoir at Wytch Farm. One of these potential pathways is represented by cores termed Creech and the other Bushey Farm. To try to distinguish between the two potential pathways, cores were studied using mineral magnetic techniques. The magnetic signature was characterised using low-temperature (<50 K) magnetic measurements; this is because much of the magnetic signature was dominated by nanoparticles < 30 nm, which are thermally activated at room temperature and magnetically “transparent”. Wells that contained considerable amounts of hydrocarbons were dominated by nanometric magnetite (<30 nm). Such particles are small enough to migrate with the oil, through pore spaces, which are of the order ~100 nm. Wells located at the fringes of large hydrocarbon accumulation had enhanced pyrrhotite-dominated magnetic signals. Of the two potential migration pathways, the mineral magnetic results suggest that the oil migrated through Creech rather than through Bushey Farm.
Royle S, Watson J, Zhang Y, et al., 2019, Solid Phase Micro Extraction: Potential for Organic Contamination Control for Planetary Protection of Life-Detection Missions to the Icy Moons of the Outer Solar System, Astrobiology, Vol: 19, Pages: 1153-1166, ISSN: 1531-1074
Conclusively detecting, or ruling out the possibility of, life on the icy moons of the outer solar system will require spacecraft missions to undergo rigorous planetary protection and contamination control procedures to achieve extremely low levels of organic terrestrial contamination. Contamination control is necessary to avoid forward contamination of the body of interest and to avoid the detection of false positive signals which could either mask indigenous organic chemistry of interest or cause an astrobiological false alarm. Here we test a new method for rapidly and inexpensively assessing the organic cleanliness of spaceflight hardware surfaces using solid phase micro extraction (SPME) fibres to directly swab surfaces. The results suggest that the method is both time and cost efficient. The SPME-gas chromatography mass spectrometry (GC-MS) method is sensitive to common mid-weight, non-polar contaminant compounds, e.g. aliphatic and aromatic hydrocarbons, which are common contaminants in laboratory settings. While we demonstrate the potential of SPME for surface sampling, the GC-MS instrumentation restricts the SPME-GC-MS technique’s sensitivity to larger polar and non-volatile compounds. Although not used in this study, to increase the potential range of detectable compounds, SPME can also be used in conjunction with high performance liquid chromatography/liquid chromatography-mass spectrometry systems suitable for polar analytes [Kataoka et al., 2000]. Thus, our SPME method presents an opportunity to monitor organic contamination in a relatively rapid and routine way that produces information-rich data sets.
Georgieva MN, Little CTS, Watson JS, et al., 2019, Identification of fossil worm tubes from Phanerozoic hydrothermal vents and cold seeps, Journal of Systematic Palaeontology, Vol: 17, Pages: 287-329, ISSN: 1477-2019
One of the main limitations to understanding the evolutionary history of hydrothermal vent and cold seep communities is the identification of tube fossils from ancient deposits. Tube-dwelling annelids are some of the most conspicuous inhabitants of modern vent and seep ecosystems, and ancient vent and seep tubular fossils are usually considered to have been made by annelids. However, the taxonomic affinities of many tube fossils from vents and seeps are contentious, or have remained largely undetermined due to difficulties in identification. In this study, we make a detailed chemical (Fourier-transform infrared spectroscopy and pyrolysis gas-chromatography mass-spectrometry) and morphological assessment of modern annelid tubes from six families, and fossil tubes (seven tube types from the Cenozoic, 12 Mesozoic and four Palaeozoic) from hydrothermal vent and cold seep environments. Characters identified from these investigations were used to explore for the first time the systematics of ancient vent and seep tubes within a cladistic framework. Results reveal details of the compositions and ultrastructures of modern tubes, and also suggest that two types of tubes from ancient vent localities were made by the annelid family Siboglinidae, which often dominates modern vents and seeps. Our results also highlight that several vent and seep tube fossils formerly thought to have been made by annelids cannot be assigned an annelid affiliation with any certainty. The findings overall improve the level of quality control with regard to interpretations of fossil tubes, and, most importantly, suggest that siboglinids likely occupied Mesozoic vents and seeps, greatly increasing the minimum age of the clade relative to earlier molecular estimates.
Zhang Z, Gora-Marek K, Watson JS, et al., 2019, Recovering waste plastics using shape-selective nano-scale reactors as catalysts, NATURE SUSTAINABILITY, Vol: 2, Pages: 39-42, ISSN: 2398-9629
Royle SH, Oberlin E, Watson JS, et al., 2018, Perchlorate‐driven combustion of organic matter during pyrolysis‐gas chromatography‐mass spectrometry: implications for organic matter detection on earth and mars, Journal of Geophysical Research: Planets, Vol: 123, Pages: 1901-1909, ISSN: 2169-9097
The search for life on Mars targets the detection of organic matter from extant or extinct organisms. Current protocols use thermal extraction procedures to transfer organic matter to mass spectrometer detectors. Oxidizing minerals on Mars, such as perchlorate, interfere with organic detection by thermal extraction. Thermal decomposition of perchlorate releases oxygen which promotes combustion of organic carbon. We have assessed the minimum mass ratio of organic carbon to perchlorate required to detect organic matter by thermal extraction and mass spectrometry. Locations on Mars with organic carbon to perchlorate ratios above 4.7-9.6 should be targeted. Because habitability is enhanced by the presence of liquid water and because perchlorate is a water soluble salt, locations on Mars with evidence of past or recent liquid water are high priority targets.
Lewis JMT, Najorka J, Watson JS, et al., 2018, The search for Hesperian organic matter on Mars: Pyrolysis studies of sediments rich in sulfur and iron, Astrobiology, Vol: 18, Pages: 454-464, ISSN: 1531-1074
Jarosite on Mars is of significant geological and astrobiological interest as it forms in acidic aqueous conditions that are potentially habitable for acidophilic organisms. Jarosite can provide environmental context and may host organic matter. The most common analytical technique used to search for organic molecules on the surface of Mars is pyrolysis. However, thermal decomposition of jarosite produces oxygen, which degrades organic signals. At pH values greater than 3 and high water to rock ratios jarosite has a close association with goethite. Hematite can form by dehydration of goethite or directly from jarosite under certain aqueous conditions. Goethite and hematite are significantly more amenable for pyrolysis experiments searching for organic matter than jarosite. Analysis of the mineralogy and organic chemistry of samples from a natural acidic stream revealed a diverse response for organic compounds during pyrolysis of goethite-rich layers but a poor response for jarosite-rich or mixed jarosite-goethite units. Goethite units that are associated with jarosite but do not contain jarosite themselves should be targeted for organic detection pyrolysis experiments on Mars. These findings are extremely timely as future exploration targets for Mars Science Laboratory include Hematite Ridge, which may have formed from goethite precursors.
Montgomery W, Sephton MA, Watson JS, et al., 2018, The role of minerals in hydrogen sulfide generation during steam-assisted recovery of heavy oil, Energy and Fuels, Vol: 32, Pages: 4651-4654, ISSN: 0887-0624
Heavy oil is recovered from reservoirs using steam-assisted technology, which can lead to H2S generation if the oil is relatively sulfur-rich. We have used laboratory aquathermolysis to simulate the steam-assisted gravity drainage process and have compared free heavy oil to that contained within the mineral matrix. The presence of a mineral matrix was found to affect the amount of H2S produced and the chemical properties of the oil generated. Our findings show that H2S production is initiated by the presence of naturally occurring minerals at specific temperatures and pressures and production techniques that avoid these conditions will minimize H2S production.
Zafar R, Watson JS, 2017, Adsorption of tetradecanoic acid on kaolinite minerals: Using flash pyrolysis to characterise the catalytic efficiency of clay mineral adsorbed fatty acids, Chemical Geology, Vol: 471, Pages: 111-118, ISSN: 0009-2541
The clay mineral kaolinite is one of the major inorganic constituents of sedimentary rocks. Kaolinite-carboxylic acid interactions are of considerable importance from the geochemical perspective. The two-fold aim of this study was to quantify the adsorption of tetradecanoic acid on kaolinite and then the flash pyrolysis of adsorbed fatty acids-kaolinite samples to understand the transformation of adsorbed fatty acids on kaolinite. Adsorption of tetradecanoic acid on kaolinite results in an s-isotherm which reflects the multilayer adsorption. Adsorption of tetradecanoic acid on kaolinite involves its both functionalities i.e. siloxane (tetrahedral face) and hydroxyl surface (octahedral face) as indicated from the pyrolysis results. Flash pyrolysis of tetradecanoic acid adsorbed kaolinite mainly yielded saturated/unsaturated hydrocarbons, aromatic hydrocarbons, and ketones while pure tetradecanoic acid generated saturated/unsaturated hydrocarbons and a series of unsaturated and saturated low molecular weight fatty acids. We have successively tested an empirical approach to identify organic compounds formed from fatty acid adsorbed kaolinite to the organic compounds obtained from fatty acid adsorbed alumina and silica. Kaolinite mainly reflects the transformation of carboxylic acids into hydrocarbons and ketones via hydroxyl surface (octahedral face). Ketonisation is mainly observed at multilayer adsorption of tetradecanoic acid on kaolinite. The major implication of the work is the understanding of fatty acids adsorption on kaolinite via both surfaces of the mineral which is helpful to understand the fate of fatty acids as they pass into the geosphere during diagenesis.
Stucky de Quay G, Roberts GG, Watson J, et al., 2017, Incipient mantle plume evolution: constraints from ancient landscapes buried beneath the North Sea, Geochemistry, Geophysics, Geosystems, Vol: 18, Pages: 973-993, ISSN: 1525-2027
Geological observations that constrain the history of mantle convection are sparse despite its importance in determining vertical and horizontal plate motions, plate rheology, and magmatism. We use a suite of geological and geophysical observations from the northern North Sea to constrain evolution of the incipient Paleocene-Eocene Icelandic plume. Well data and a three-dimensional seismic survey are used to reconstruct a 58–55 Ma landscape now buried ∼1.5 km beneath the seabed in the Bressay region. Geochemical analyses of cuttings from wells that intersect the landscape indicate the presence of angiosperm debris. These observations, combined with presence of coarse clastic material, interpreted beach ridges, and a large dendritic drainage network, indicate that this landscape formed subaerially. Longitudinal profiles of palaeo-rivers were extracted and inverted for an uplift rate history, indicating three distinct phases of uplift and total cumulative uplift of ∼350 m. Dinoflagellate cysts in the surrounding marine stratigraphy indicate that this terrestrial landscape formed in <3 Ma and was rapidly drowned. This uplift history is similar to that of a slightly older buried landscape in the Faeroe-Shetland basin ∼400 km to the west. These records of vertical motion are consistent with pulses of anomalously hot asthenosphere spreading out from the incipient Icelandic plume. Using simple isostatic calculations we estimate that the maximum thermal anomaly beneath Bressay was 50–100◦C. Our observations suggest that a thermal anomaly departed the Icelandic plume around 57.4±2.2 Ma at the latest, and travelled with a velocity >∼150 km/Ma.
Zafar R, Watson JS, Weiss DJ, et al., 2016, Organic compound-mineral interactions: using flash pyrolysis to monitor the adsorption of fatty acids on calcite, Journal of Analytical and Applied Pyrolysis, Vol: 123, Pages: 184-193, ISSN: 1873-250X
Fatty acids are near ubiquitous organic compounds in living organisms in the Earth’s biosphere. Following death of an organism in the marine environment its fatty acids may survive descent to the sea bed where they can be juxtaposed with minerals. The aim of this study was to investigate the interaction of fatty acids with the common marine mineral calcite. Adsorption of tetradecanoic acid (C14) on calcite results in a sigmoidal or “s” isotherm. Flash pyrolysis experiments were conducted on samples of fatty acid adsorbed onto calcite and were compared with similar experiments on pure fatty acid and on salts of a fatty acid. Flash pyrolysis of pure tetradecanoic acid generated unsaturated and saturated hydrocarbons and a series of unsaturated and saturated low molecular weight fatty acids. Flash pyrolysis of free tetradecanoic acid salt produced saturated and unsaturated hydrocarbons, an aldehyde and a homologous series of saturated and unsaturated ketones, one of which was a symmetrical mid chain ketone (14-heptacosanone). Flash pyrolysis data from adsorbed tetradecanoic acid samples suggested that adsorption is analogous to the formation of the calcium salt of tetradecanoic acid. A key characteristic of the flash pyrolysis products of adsorbed fatty acids and fatty acid salts was the production of ketones with higher molecular weights than the starting fatty acids. Ketonisation was not observed from the flash pyrolysis of pure acid which implied the catalytic significance of the calcite mineral surface. The abundance of hydrocarbons relative to ketones in the pyrolysates negatively correlated with the proportion of fatty acids adsorbed to the surface of calcite. The ability to use flash pyrolysis to diagnose the nature of fatty acid interactions with mineral surfaces provides a valuable tool for monitoring the fate of these important lipids at the Earth’s surface as they pass into the geosphere and are subjected to diagenetic processes.
Henry DG, Watson JS, John CM, 2016, Assessing and calibrating the ATR-FTIR approach as a carbonate rock characterization tool, SEDIMENTARY GEOLOGY, Vol: 347, Pages: 36-52, ISSN: 0037-0738
Montgomery WB, Watson JS, Potiszil C, et al., 2016, Sporopollenin, a natural copolymer, is robust under high hydrostatic pressure, Macromolecular Chemistry and Physics, Vol: 217, Pages: 2494-2500, ISSN: 1521-3935
Lycopodium sporopollenin, a natural copolymer, shows exceptional stability underhigh hydrostatic pressures (10 GPa) as determined by in situ high pressuresynchrotron source FTIR spectroscopy. This stability is evaluated in terms of thecomponent compounds of the sporopollenin: p-coumaric acid, phloretic acid, ferulicacid, and palmitic and sebacic acids, which represent the additional n-acid and ndiacidcomponents. This high stability is attributed to interactions between thesecomponents, rather than the exceptional stability of any one molecular component.We propose a biomimetic solution for the creation of polymer materials that canwithstand high pressures for a multitude of uses in aeronautics, vascular autografts,ballistics and light-weight protective materials.
Watson JS, Sephton MA, 2015, Heat, clay and aromatic units: a mechanism for making macromolecules in the early solar system, Astrobiology, Vol: 15, Pages: 787-792, ISSN: 1557-8070
The major organic component in carbonaceous chondrites is ahighly aromatic macromolecular material. Aromatic organic matter andphyllosilicates are co-located in these meteorites and it is possible that thephysical association represents a synthetic chemical relationship. To explore thepotential reactions that could take place to produce the aromatic macromolecularmaterial we heated various simple aromatic units in the presence ofmontmorillonite with different exchanged cations. The majority of cationexchanged montmorillonites tested, sodium-, aluminium-, iron-, nickel- andcobalt-rich montmorillonites, do not produce polymerisation products. By contrastFe3+ cation exchanged montmorillonite readily facilitates addition reactionsbetween aromatic hydrocarbons. A feasible mechanism for the process isoxidative coupling which involves a corresponding reduction of the Fe3+ cation to its Fe2+ counterpart. A similar reduction process for the other metal cations does not take place highlighting the importance of iron. This simple process is a feasible mechanism for the addition to the aromatic macromolecules such as thosefound in carbonaceous chondrites. The search for a relationship between Fe3+-richphyllosilicates and aromatic organic structures (particularly dimers, trimers and more polymerised forms) in carbonaceous chondrites would represent an effective test for constraining the role of clay catalysis in the early solar system.
Abubakar R, Muxworthy AR, Southern P, et al., 2015, Formation of magnetic minerals in hydrocarbon-generation conditions, Marine and Petroleum Geology, ISSN: 1873-4073
In this paper, we report the pyrolysis and formation of magnetic minerals in three source rock samples from the Wessex Basin in Dorset, southern England. The experimental conditions in the laboratory recreated the catagenesis environment of oil source rocks. Magnetic analysis of both the heated and the unheated samples at room temperature and at very low temperatures (5 K), coupled with transmission electron-microscopy imaging and X-ray analysis, revealed the formation of nanometre-sized (<10 nm), magnetic particles that varied across the rock samples analysed, but more importantly across the pyrolysis temperature range. Magnetic measurements demonstrated the formation of these magnetic minerals peaked at 250 °C for all rock samples and then decreased at 300 °C before rising again at 320 °C. The newly formed magnetic minerals are suggested to be primarily pyrrhotite, though magnetite and greigite are also thought to be present. The sizes of the magnetic minerals formed suggest a propensity to migrate together with oil potentially explaining the magnetic anomalies observed above and within oil fields.
Mustafa KA, Sephton MA, Watson JS, et al., 2015, Organic geochemical characteristics of black shales across the Ordovician-Silurian boundary in the Holy Cross Mountains, Central Poland, Marine and Petroleum Geology, Vol: 66, Pages: 1042-1055, ISSN: 1873-4073
Black shales in the Holy Cross Mountains area of Poland provide a record of environmental change across the Ordovician-Silurian boundary. The changing depositional conditions have generated a variation in organic matter contents above and below the boundary. Investigating the organic constitution of these black shales has the potential to reveal how their organic matter contents were generated and how suitable these rocks and their lateral equivalents may be for exploitation as shale gas reservoirs. One outcrop at the Holy Cross Mountains with a continuous section across the Ordovician-Silurian boundary occurs near the village of Bardo Stawy in the Kielce region, and contains sandy-silty mudstones, as well as grey and black shales. Organic geochemical analyses of samples at Bardo Stawy reveals low Total Organic Carbon (TOC) contents for Ordovician samples and higher TOC values for Silurian samples. Organic biomarkers indicate that the Ordovician rocks were deposited in a shallow-marine shelf setting, while the Silurian rocks were deposited in a deeper marine environment. The progressive increase in TOC from the uppermost Ordovician to the lowermost Silurian rocks reflects increasingly oxygen-poor depositional conditions during the post-glacial transgression. Following the deposition and preservation of organic matter in the Ordovician and Silurian rocks, these rocks were buried and subjected to thermal maturation. Rock Eval and biomarker thermal maturity parameters all indicate that the organic matter is mature and lies within the oil window. The Ordovician and Silurian shales have direct relevance to recent attempts to discover and exploit shale gas reservoirs in Poland. Our data and interpretations suggest that the relatively low TOC values (<2%) and low maturities for gas generation render these rocks unsuitable for commercial shale gas production. The progressive improvement in conditions for preserving organic matter across the Ordovician-Silurian boundary d
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