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SPONSORSHIP BOGS 2015, Glasgow

BOGS meeting has been supported by our sponsors:

British Organic Geochemistry Society Meeting – 2015

Schedule for July 2nd & July 3rd

Day One – Thursday, July 2nd: Venue: John McIntyre Building, University Ave at the Main Gate, Room 201 8:30-9:00am Registration and coffee

9:00-9:15am Opening remarks

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Oral Session I: Applications to Palaeoclimatology Chair: Gordon Inglis

9:15-9:30 Preserved organic matter in the ancient oceanic region of the Alpine Tethys margin – Tsvetomila Mateeva 9:30-9:45 Collecting Biogeochemical data for the Plio-Pliocene– Benjamin Petrick 9:45-10:00 Constraints on TEX86 Sea Surface Temperatures across Oceanic Anoxic Event 2 from the Central North Atlantic – Jessica Whiteside 10:00-10:15 Descent towards the Icehouse: Eocene sea surface cooling inferred from GDGT distributions – Gordon Inglis 10:15-10:30 Reconstructing 17 million years of Surface Temperatures in the Japan Sea: Insights and implications using a biomarker approach – Fredericke Wittkopp

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10:30-11:00am COFFEE BREAK ~~~~~~~~~~~~~~~~~~~~~~

Oral Session II: Applications to Modern Problems

Chair: Laura Richards 11:00-11:15am BHT isomer extends the detection of anammox: evidence from Mediterranean sapropels – Darci Rush 11:15-11:30am Geochemical and thermal effects of diabase intrusions on the fine grain facies of the Parnaíba Basin, NE Brazil– Marwan Jaju 11:30-11:45am Comprehensive lipid profiling of soil – Ili S. Johari

11:45-12:00 Excitation emission matrix (EEM) fluorescence spectroscopy of DOC in arsenic-prone aquifers, Cambodia – Daniel Magnone 12:00-12:15pm Shifts in deep-sea food webs linked to climate and food supply – Rachel M. Jeffreys 12:15-12:30pm Removal of Metaldehyde From Drinking Water Using a Novel Treatment Process – M. Akmez Nabeerasool

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12:30-1:30pm LUNCH BREAK ~~~~~~~~~~~~~~~~~~~~~~

Oral Session III: Applications in the Recent Past

Chair: Darci Rush

1:30-1:45pm NAOSIPUK project: Understanding the NAO from Iberian and UK paleoclimate records. State of the art – Antonio Garcia-Alix 1:45-2:00pm Organic matter characterisation and paleoclimatic conditions from the central part of the Mexican Chihuahuan Desert over the last 27 ka cal BP – Claudia Chávez Lara 2:00-2:15pm The emergence of dairying in Neolithic Europe: A lipid residue and compound specific radiocarbon dating approach – Emmanuelle Casanova 2:15-2:30pm Do changes in plant functional diversity and imposed warming change the peat composition in a peatland? – Danielle Satterthwaite

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2:30-3:45pm POSTER SESSION 3:45-4:30pm COFFEE BREAK

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Plenary Speaker (4:30-5:30pm): Professor Wolfram Meier-Augenstein, Robert Gordon University

Public lecture: “CSI- Crime and Stable Isotopes” 5:30-7pm [SPAG Discussions held at the Hilton Grosvenor Hotel, Botanics Suite for heads of research groups, others welcome.] 7pm CONFERENCE DINNER AND CEILIDH DANCE at the Hilton Grosvenor Hotel, Botanics Suite.

Day Two – Friday, July 3rd: 8:45-9:00am Opening Remarks

~~~~~~~~~~~~~~~~~~~~~~ Oral Session IV: Applications in the Oils, Biofuels, and Coal Tras

Chair: Stephanie Turnbull 9:00-9:15am Ultrasound Spectrometry and Statistical Inference of Water-in-Oil Emulsions – Alex Svalova 9:15-9:30am Hydrothermal liquefaction of algal biomass to produce advanced biofuels – Mehmood Ali 9:30-9:45am The Bacterial Community Structure and Isotopic Composition of PAHs in coal tar: a study of the Intrinsic Biodegradation Potential – Fabrizio Colosimo 9:45-10:00am Environmental Forensics of Coal Tars – A Case Study – Christopher Gallacher

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10:00-10:30am COFFEE BREAK ~~~~~~~~~~~~~~~~~~~~~~

10:30-11:30am Real-world Advice: Panel on Careers, Life, and Academia 11:30-11:45am Conferring of the Archie Douglas Award for best student oral

presentation and Award for best student poster presentation 11:45-12:00 Closing remarks…

~~~~~~~~~~~~~~~~~~~~~~ 12:00-1:00pm BUFFET LUNCH

~~~~~~~~~~~~~~~~~~~~~~

Plenary Speaker Professor Wolfram Meier-Augenstein

“CSI- Crime and Stable Isotopes”

Prof. Wolfram Meier-Augenstein is a Professor at the Robert Gordon University (Aberdeen); a registered forensic expert advisor with the UK’s National Policing Improvement Agency (NPIA as then was; now NCA); a former director of the Forensic Isotope Ratio Mass Spectrometry (FIRMS) Network and a former Council member of the British Association for Human Identification (BAHID). The underlying theme of his research is the elucidation of authenticity, provenance and (bio-)chemical pathways using stable isotope analytical techniques. With over 20 years of experience in the field of stable isotope technology his contributions to the field include the design of the first GC/(MS)-C-IRMS hybrid system (available from Thermo-Fisher) and the design of a patented multiple reference gas module for CF-IRMS (an integral part of SerCon’s 20-20 IRMS) as well as chapters to several textbooks on the subject of stable isotope analysis including its forensic applications. He has assisted various police forces (in the UK as well as abroad) in murder investigations as well as drug related crime by providing forensic intelligence on drug or human provenance based on Stable Isotope Profiles or ‘Signatures’. Stable isotope signatures can aid, even focus criminal investigations by provision of intelligence or establish a set of exclusion criteria to help e.g. with victim identification. He is the author of a textbook on "Stable Isotope Forensics" that has been published by John Wiley & Sons in 2010) and contributed a chaper on "Forensic Isotope Analysis" to the 2014 edition of The McGraw-Hill Yearbook of Science & Technology. Prof. Meier-Augenstein also featured as one of the forensic experts in the BBC One series “History Cold Case”.

The Archie Douglas Award

We are pleased to announce that from BOGS 2015 forward the prize for best student oral presentation will be given in honour of the late Dr. Archie Douglas.

Dr. Archie Douglas was not only a very serious scientist, he also liked to have fun!

In the photograph taken at one of the famous Newcastle Christmas parties, Archie is the one with the hat! He’s playing the spoons and is accompanied by Steve Larter FRS on Northumbrian bagpipes (now Calgary) and is one of Archie’s former PhD students and Chris Vane on bhodran (now at BGS), one of my former PhD students.

Archie contributed huge amounts to research in kerogen pyrolysis and was a recipient of the 2002 Alfred E. Treibs Award (highest accolade in Organic Geochemistry). In his later years, he was a very effective Editor in Chief for our journal Organic Geochemistry.

Contribution from: -Geoff Abbott (Newcastle University)


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IGI Ltd. is pleased to sponsor the BOGS 2015 Meeting

First Name Surname Email Address AffiliationMehmood Ali [email protected] University of GlasgowJoseph Armstrong [email protected] University of Aberdeen Marcus Badger [email protected] University of BristolMadeleine Brasier [email protected] University of LiverpoolCaroline Caroline [email protected] University of GlasgowEmmanuelle Casanova [email protected] University of BristolBianca Cavazzin [email protected] University of GlasgowClaudia Magali Chavez Lara [email protected] University of BristolMalu Cisneros [email protected] University of GlasgowFabrizio Colosimo [email protected] University of StrathclydeJohnny Coyle [email protected] University of GlasgowStewart Craig [email protected] Thermo ScientificRory Doherty [email protected] Queen's University, BelfastSharon Fraser [email protected] University of ManchesterChristopher Gallacher [email protected] University of StrathclydeAntonio Garcia Alix [email protected] University of GlasgowJo Hellawell [email protected] Nature Publishing GroupJens Holtvoeth [email protected] University of BristolGordon Inglis [email protected] University of BristolMarwan Jaju [email protected] University of Aberdeen Rachel Jeffreys [email protected] University of LiverpoolIli Syazana Johari [email protected] University of BristolKostas Kiriakoulakis [email protected] Liverpool John Moores UniversitySabine Lengger [email protected] University of BristolC. Anthony Lewis [email protected] Plymouth UniversityHelen Mackay [email protected] University of SouthamptonDaniel Magnone [email protected] University of ManchesterTsvetomila Mateeva [email protected] University of LiverpoolLaura McAnallen [email protected] Queen's University, BelfastLaura McGregor [email protected] Markes International LtdCatherine McIntyre [email protected] University of BristolWolfram Meier-Augenstein [email protected] Robert Gordon UniversityHeiko Moossen [email protected] University of BirminghamKatrina Pears [email protected] University of BristolJonathan Pemberton [email protected] University of BristolElsa Perruchini [email protected] University of GlasgowBenjamin Petrick [email protected] University of NewcastleLaura Richards [email protected] University of ManchesterGeorge Rowland [email protected] University of BristolSteven Rowland [email protected] Plymouth UniversityDarci Rush [email protected] University of NewcastleIoannis Sampsonidis [email protected] University of GlasgowKerry Simcock [email protected] University of NewcastleDavid Small [email protected] University of GlasgowAleksandra Svalova [email protected] University of NewcastleHelen Talbot [email protected] University of NewcastleJaime Toney [email protected] University of GlasgowStephanie Turnbull [email protected] University of GlasgowBart van Dongen [email protected] University of ManchesterJonathan Watson [email protected] Imperial College, LondonJames Williams [email protected] Markes International LtdFrederike Wittkopp [email protected] University of Birmingham

BOGS 2015 - Participants List

BOGS 2015, Glasgow

ABSTRACTS

Oral presentations

O1

Preserved organic matter in the ancient oceanic region of the Alpine Tethys margin

T. Mateeva1, N. Kusznir1, G. Wolff1, J. Wheeler1, G. Manatschal2

1Earth, Ocean and Ecological Sciences, University of Liverpool, Liverpool, L69 3BX, UK 2CNRS-EOST, Université de Strasbourg, 1 rue Blessig, F-67084 Strasbourg, France

Evidence from ocean ridge drilling and dredging and from the exhumed Tethyan continental margin in the Alps demonstrates that mantle serpentinization, a process deriving from the interaction of mantle rock and water, occurs at slow-spreading ocean ridges and magma-poor rifted continental margins. Observations at white smokers in modern ocean settings suggest that methane produced by serpentinization can support methanotrophic bio-systems, a system that uses methane as its only source of carbon and energy.

An important question is whether such bio-systems are more generally pervasive in their association with serpentinized mantle in the subsurface. This has important global implications for the importance of the hidden sub-surface bio-systems, the fate of methane and the carbon cycle. We examine whether serpentinized exhumed mantle at magma-poor rifted continental margins shows evidence for such a methanotrophic system.

The Totalp unit in the eastern Swiss Alps has been chosen for an initial study to investigate the presence or absence of methanotrophic biosystem within serpentinized exhumed mantle in the Alpine Tethyan margin. Totalp has undergone little Alpine deformation and only low grade metamorphism.

Samples were collected from the Totalp region, to determine the full range of biomarkers, show evidence of organic hydrocarbon in the form of alkanes. The majority of the samples contain n-alkanes in the range C20 - C32. Some sediments contain isoprenoids, for example pristane and phytane. The organic molecular distribution is consistent with the temperature history of the basin. Totalp samples are characterized by TC contents of 0.03% to 12.90% and TOC contents of 0.10% to 1.90%. This large range of values reflects the large lithological diversity of this area.

First results from Totalp show evidence for preservation of marine organic matter in the serpentinized mantle and overlying sediments of the ancient Tethyan OCT. More work is required to understand whether any of the organic matter is generated from methanotrophic bio-systems, and if so whether the methane originated from an organic or inorganic source. This will require compound specific isotopic analysis of the carbon in the isoprenoids.

O2

Collecting Biogeochemical data for the Plio-Pliocene

B. Petrick1, G. Haug1

1 Max Plank Institute of Chemistry, Mainz, Germany

There are problems with our understanding of biogeochemical cycles in the Pliocene. Data is currently scattered in numerous sources such as ODP/IODP reports and is not easily accessible. Other data has not been published, because it is not easy to publish some types of data such as basic carbonate data or TOC. However, even the most basic data such as % carbonate can provide a valuable resource. A global reconstruction may help refine the Boron CO2 proxy, which is one of a few methods for reconstructing past CO2. Therefore, it is necessary to collect and compile these existing biogeochemical data. For part of my postdoc I will be more working on reconstructing basic biogeochemical proxies such as % carbonate, phosphate, TOC, and pigment for the Plio-Pliocene on a global scale using existing data sets. While these are not in themselves glamorous records to measure and publish, they are critical for understanding biogeochemical cycles and so therefore are important to try to collect. These can then be coupled with more modern techniques such as advanced isotopic measures like neodymium and nitrogen isotopes. These data sets should help our understanding about how biogeochemical cycles operated in a warmer world and during the transition to a colder world.

O3

Constraints on TEX86 Sea Surface Temperatures across Oceanic Anoxic Event 2 from the Central North Atlantic

J. H. Whiteside1*, J. Sepúlveda2 , M. Schaller3 , P. Blum4, R. E. Summons5

1Ocean and Earth Science, National Oceanography Centre Southampton, University of Southampton, Waterfront Campus, European Way, SO14 3ZH, UK (*correspondence: [email protected] 2Geological Sciences and Institute of Arctic and Alpine Research, University of Colorado Boulder,

80309, USA 3Earth and Environmental Sciences, Rensselaer Polytechnic Institute, 110 8th Street, Troy, NY 12180,

USA 4IODP, Texas A&M University, 1000 Discovery Drive, College Station, TX 77845-9547, USA 5Earth, Atmospheric and Planetary Sciences, Massachusetts Institute of Technology, Cambridge, MA, 02139, USA

Transient episodes of extensive marine black shale deposition during the Mesozoic, such as Oceanic Anoxic Event 2 (OAE-2; ~93.5 Ma), illustrate the Earth system response to extreme greenhouse climatic perturbations. OAE-2 has been linked to Large Igneous Province volcanism, global warming, increased ocean stratification, and the onset of anoxia and euxinia. A thermally stratified ocean with sluggish circulation might have resulted from a markedly reduced latitudinal geothermal gradient, as suggested by TEX86-derived elevated SSTs (33-42°C) at midlatitudes (Sinninghe Damsté et al., 2010). However, these SSTs contradict Earth system models for greenhouse conditions (Hollis et al., 2012) in reconstructing too high values in O2-depleted settings, possibly because other variables affect this proxy (Schouten et al., 2012).

High-resolution (2-5 mm scale) TEX86-derived temperature estimates and GDGT distributions from sediment cores recovered from IODP Expedition 342 at Site U1407, South East Newfoundland Ridge (~32°N) indicate values of ~36°C during OAE-2. Notably, a large (~10-15°C) cooling trend was observed following OAE-2, but none during the event as previously reported (Sinninghe Damsté et al., 2010). However, the cooling trend is associated with a marked change in the distribution of isoprenoidal and other GDGTs, suggestive of differences in the sources of these biomarkers due to variations in water column redox conditions and terrestrial input, rather than SST. Our results implicate marked changes in oxygen-deficiency that affect the sources and distributions of GDGTs, thus altering TEX86-derived temperatures, consistent with modern observations in oxygen-depleted settings (Schouten et al., 2012). References Sinninghe Damsté, J.S. et al., 2010. A CO2 decrease-driven cooling and increased latitudinal

temperature gradient during the mid-Cretaceous Oceanic Anoxic Event 2. Earth and Planetary Science Letters 293, 97-103.

Hollis C.J. et al., 2012. Early Paleogene temperature history of the Southwest Pacific Ocean: Reconciling proxies and models. Earth and Planetary Science Letters 349-350, 53-66

Schouten, S. et al., 2012 Intact polar and core glycerol dibiphytanyl glycerol tetraether lipids in the Arabian Sea oxygen minimum zone: I. Selective preservation and degradation in the water column and consequences for the TEX86. Geochimica et Cosmochimica Acta 98, 228-243.

O4

First occurrence of archaeal tetraether lipids with 5 to 7 cyclopentane moieties in a mesophilic setting

G. N. Inglis1*, B. D. A. Naafs1, S. J. Feakins2, O. Lahteenoja3, C. Ponton2, M. E. Collinson4, M.

Rohrssen1, R. D. Pancost1

1 Organic Geochemistry Unit, School of Chemistry and Cabot Institute, University of Bristol, UK (*correspondance: [email protected])

2 Department of Earth Sciences, University of Southern California, USA 3 Department of Biology, University of Turku, Finland 4 Department of Earth Sciences, Royal Holloway University of London, Egham, UK

Isoprenoidal glycerol dialkyl glycerol tetraethers (isoGDGTs) are cell membrane-

spanning lipids belonging to a diverse group of Archaea. IsoGDGTs bearing up to 4 cyclopentane moieties are common in non-extreme environments, whereas isoGDGTs bearing 5 to 8 cyclopentane moieties have only been reported in hot springs and cultures of Euryarchaeota and Crenarchaeota grown at temperatures above 45°C (pH <1.5) and 65°C (pH 2-5.5), respectively. This suggests that the ability to synthesise more than 4 cyclopentane moieties is a unique adapation of extremophiles. To explore this further, we report the distribution of isoGDGTs in a range of peat-forming environments from across the globe.

Our results demonstrate that high- and mid-latitude peats are dominated by GDGT-0 (typically > 80%). Smaller quantites of GDGTs 1 to 4 were also detected. In tropical peats, GDGTs 1 to 4 are more abundant (up to 60% of total isoGDGTs). Intriguingly, a number of ombrotrophic tropical peats contain isoGDGTs bearing up to 7 cyclopentane moieties. This is the first reported occurence of isoGDGTs bearing more than 4 cyclopentane moieties within a mesophilic setting. Their occurrence is likely driven by a combination of high mean annual temperatures (>25 °C) and low pH (3.5-4.0). The presence of isoGDGTs 0-5 within an early Eocene, ombrotrophic bog (Schoningen, NW Germany) also suggests that this signal is preserved in deep-time settings. Our results indicate that isoGDGTs with more than 4 cyclopentane rings are not unique to thermophilic settings and that these compounds are likely more widespread than previously thought.

O5

Reconstructing 17 million years of Surface Temperatures in the Japan

Sea: Insights and implications using a biomarker approach

F. Wittkopp1, M. Yamamoto 22, T. Dunkley-Jones1, K. E. Lee3, J. Bendle1, A. Henderson4, ODP Shipboard Scientific Party 127/128, IODP Shipboard Scientific Party 346

1 School of Geography, Earth and Environmental Science, University of Birmingham, Birmingham, United Kingdom 2 Faculty of Earth Science, Hokkaido University, Sapporo, Japan 3 Division of Marine Environment and Bioscience, Korea Institute of Geoscience and Mineral Resources, Busan, Republic of Korea 4 School of Geography, Politics and Sociology, Newcastle University, Newcastle, United Kingdom

Fossil remains, so called biomarker are used to reconstruct past climate events. Understanding these events, especially warming events is crucial, as humanity struggles with the ongoing climate change. Here, we present the first long-term sea surface temperature record from the Japan Sea, using TEXH

86. This extensive record shows a strong correlation with the δ18O record of benthic foraminfer (1). Sea surface temperatures peaked during the Mid-Miocene Climate Optimum (16-14.5 Ma), being 6°C warmer than compared to today. Temperatures have decreased steadily since then. The data provides insight into the impact and response of the Japan Sea to past global climate changes. Recent studies suggest that the Japan Sea is also sensitive to changes in orbital forcing (2). The generated records can also improve regional climate models to get a good estimation of potential impacts of the ongoing climate change on the region of SE-Asia. References Zachos J.C., Dickens G.R., Zeebe R.D., 2008. An early Cenozoic perspective on greenhouse warming

and carbon cycle dynamics. Nature 451, 279-283. Marzocchi A., Lunt D.J., Flecker R., Bradshaw C.D., Farnsworth A., Hilgen F.J., 2015. Orbital control

on late Miocene climate and the North African monsoon: insight and from an ensemble of sub-precessional simulations. Climate of the Past Discussion 11, 2181-2237.

O6

Bacteriohopanepolyols in Mediterranean sapropel events: indications for

tracing ancient anammox

D. Rush1, J.S. Sinninghe Damsté2, Ellen C. Hopmans2, H.M. Talbot1

1 School of Civil Engineering and Geosciences, Newcastle University, Newcastle-upon-Tyne 2 Department of Marine Organic Biogeochemistry, Netherlands Institute for Sea Research (NIOZ), Texel, Netherlands

Mediterranean sapropels are organic-rich sediment layers indicative of extensive redox transitioning. During these events, increased productivity and organic matter burial led to anoxic conditions (Rohling and Thunell, 1999). Modern sapropels (S1 – S5) were analysed for the presence of bacteriohopanetetrol stereoisomer (BHT isomer), a bacteriohopanepolyol recently linked to anaerobic ammonium oxidation (anammox) (Rush et al., 2014). However, non-marine, non-anammox bacteria have also been shown to synthesise BHT isomer (e.g. Rosa-Putra et al., 2001), and a link between BHT isomer and anammox in sapropelic conditions needed to be established first. Therefore, ladderane lipids, well-established biomarkers for anammox, were also analysed in these samples. Ladderane lipids were detected in the most recent sapropels (S1 and S3; 7 and 80 ka respectively), but had degraded in the older sapropels (>100 ka). However, BHT isomer was detected alongside ladderanes in the recent sapropels, and was still present in high concentration in ancient sapropel sediments (2.6 Ma), strengthening the potential of BHT isomer as a biomarker for past anammox. The oldest detection of anammox using ladderane lipids is 125 ka (Jaeschke et al., 2009). Thus, BHT isomer appears to have already extended the window of detection of anammox by 2.4 Million years, which will expand our understanding of the occurrence and importance of anammox in past nitrogen cycling. References Jaeschke, A., Ziegler, M., Hopmans, E.C., Reichart, G.J., Lourens, L.J., Schouten, S., Damste, J.S.S.,

2009. Molecular fossil evidence for anaerobic ammonium oxidation in the Arabian Sea over the last glacial cycle. Paleoceanography 24, PA2202, doi:10.1029/2008PA001712.

Rohling, E.J., Thunell, R.C., 1999. Five decades of Mediterranean palaeoclimate and sapropel studies. Marine Geology 153, 7-10.

Rosa-Putra, S., Nalin, R., Domenach, A.M., Rohmer, M., 2001. Novel hopanoids from Frankia spp. and related soil bacteria - Squalene cyclization and significance of geological biomarkers revisited. European Journal of Biochemistry 268, 4300-4306.

Rush, D., Sinninghe Damsté, J.S., Poulton, S.W., Thamdrup, B., Garside, A.L., Acuña González, J., Schouten, S., Jetten, M.S.M., Talbot, H.M., 2014. Anaerobic ammonium-oxidising bacteria: A biological source of the bacteriohopanetetrol stereoisomer in marine sediments. Geochimica Et Cosmochimica Acta 140, 50-64.

O7

Geochemical and thermal effects of diabase intrusions on the fine grain

facies of the Parnaíba Basin, NE Brazil

M. Jaju 1ª, D. MacDonald1a , H. Mort1b, and J. Parnelll2a

a School of Geosciences, University of Aberdeen. Meston Building, Aberdeen AB24 3UE, UK b Federal University of Pernambuco, Department of Geology, Brazil

This study is an investigation of the hydrothermal and geochemical effects induced by intruded Cretaceous sills and dykes on fine grain facies of the Paleozoic formations in the Parnaíba Basin, which has producing gas fields. Preliminary results suggest that these intrusions are an important heat source for maturation of organic matter.

Detailed sampling was performed on fine grained facies of the Pimenteiras (Devonian) and Pedra de Fogo (Permian) formations. Elemental analysis reveals an upward decrease of total organic carbon (TOC %). Maximum extractable organic matter (EOM, wt/g rock) and the saturated fraction increase upward in the stratigraphy. Gas chromatograms of the aliphatic hydrocarbon fractions reveal switching of isoprenoids and cyclic-dominated hydrocarbons to straight-chain components upwards. CPI values and OEP-1 decrease towards intrusive contacts. Taken together, these data suggest that the distribution of normal alkanes is skewed towards low molecular weight with increasing maturity. So called “synthesis gas” may have occurred within a short distance of volcanic intrusive contacts, this implies inefficiency of Rock Eval HI and OI data as reliable maturation indicators.

Maturation parameters based on hopane isomerization (22S/22S+22R), sterane (20S/20S+20R), Ts/(Ts+Tm), and Triaromatic steroids increase (suggesting increasing maturity) with decreasing distance from intrusive contacts. Epimers 22S-hopane and, to a lesser degree, 20S-sterane ratios show inversion after reach the equilibrium, probably reflecting the impacts of higher temperatures closer to intrusive contacts.

A new approach has been applied to calculation of the equivalent vitrinite reflectance (Ro) from the bitumen fractions, using the average of equivalent vitrinite reflectance values calculated from biological maturity parameters ratios. Geochemical and physical analysis reveal an upward increase of maturity induced by igneous intrusion. The oil window lies within 1,000 m of the surface. Volcanic intrusions in the study area have heated the source rocks both regionally and locally, which resulted in thermal overmaturity of organic matter in such places and were responsible for the maturity profile across the SE Parnaíba Basin. References Aarnes, I, Svensen, H., Connolly, J., and Podladchikov, Y.Y., 2010. How contact metamorphism can

trigger global climate changes: Modeling gas generation around igneous sills in sedimentary basins. Geochemica et Cosmochimica Acta 74, 7179-7195.

O8

Comprehensive lipid profiling of soil

I. S. Johari 1, P. J. Gates 1, I. D. Bull 1 School of Chemistry, University of Bristol, School of Chemistry, Cantock’s Close, Bristol, BS8 1TS

Wholesale interrogation of a complex mixture of lipids enables comprehensive, multivariate characterisation of targets, useful for sample differentiation and biomarker discovery. In the present research, we have conducted untargeted lipidomic profiling of soil using gas chromatography-mass spectrometry (GC-MS). This approach enables all GC amenable lipids in the soil extract to be analysed in a nonbiased manner. An initial method validation study was conducted, comprising two extraction techniques: microwave and ultrasonic assisted extraction. In addition, procedures involving saponification of either the soil or the total lipid extract (TLE) were compared. Ultrasonic assisted extraction combined with saponification of the TLE was chosen as the preferred methodology.

Thirty soils were collected from ten sites around Bristol and the South of England, chosen primarily for different vegetation cover and land use. Total organic carbon (TOC) was determined with results in the range of 2.28−46.11 %. Soil pH was shown to have a negative correlation with organic carbon content. All soils were extracted then analysed by GC-MS. The results obtained were transformed using MetAlign software to obtain baseline correction, data smoothing and peak alignment (De Vos et al., 2007). The transformed data were then further reduced and normalized using MATLAB software. Multivariate statistical analysis was conducted to compare the different soils, by virtue of their lipidome, and assess lipidomic characterization as a more robust means of soil differentiation and matching. References De Vos, R.C.H., Moco, S., Lommen, A., Keurentjes, J.J.b., Bino, R.J., 2007. Untargeted large-scale

plant metabolomics using liquid chromatography coupled to mass spectrometry. Nature Protocols 2, 778-791

O9

Excitation emission matrix (EEM) fluorescence spectroscopy of DOC in arsenic-prone aquifers, Cambodia

D. Magnone1, L. A. Richards 1, D. A. Polya1, D. C. Gooddy2, D. J. Lapworth2, P. J.Williams2, B. E. van Dongen1

1 School of Earth, Atmospheric and Environmental Sciences and Williamson Research Centre for Molecular Environmental Science, University of Manchester, Manchester, M13 9PL, UK 2 British Geological Survey, Crowmarsh Gifford, Wallingford, OX10 8BB, UK

High concentrations of arsenic in the aquifers of S & SE Asia are putting over 100 million

people at risk of developing serious health conditions and causing widespread early death (Ravenscroft et al., 2009). The contamination is widely accepted to be caused by microbially mediated reactions between organic material (OM) and arsenic-bearing Fe-oxide minerals (Islam et al., 2004). Whilst labile dissolved organic carbon (DOC) is widely recognised as an important source of OM (Harvey et al., 2002; Lawson et al., 2013) and studies of the composition of sedimentary OM have shown specific compounds to be readily degraded during arsenic release (Rowland et al., 2009) there are few studies of the DOC composition in arsenic-prone aquifers (e.g. Neumann et al., 2011; Pi et al., 2015).

Here, we report an excitation emission matrix (EEM) fluorescence spectroscopy study of DOC composition in an arsenic-prone Cambodian aquifer, located SE of Phnom Penh. EEM was used to quantify major classes of organic compounds producing a large and spatially constrained data set paired to an inorganic data set. Principal component and clustering analysis, as part of a multivariate statistical approach, suggests that individual components such as tyrosine-like compounds and fulvic fractions correlate and cluster more with arsenic than bulk DOC does, whilst tryptophan-like compounds appear less associated with arsenic. Unsurprisingly the fluorescence index, used as a proxy for microbial degradation (Lapworth et al., 2008; Pi et al., 2015), is also more associated with arsenic at the study site than bulk DOC. This is the first time such analysis has been reported for arsenic-prone Cambodian aquifers and will bring new insights to our understanding of the DOC associated with arsenic release. References & Acknowledgements Harvey, C.F., Swartz, C.H., Badruzzaman, A., Keon-Blute, N., Yu, W., Ali, M.A., Jay, J., Beckie, R., Niedan, V.,

Brabander, D., 2002. Arsenic mobility and groundwater extraction in Bangladesh. Science 298, 1602-1606. Islam, F.S., Gault, A.G., Boothman, C., Polya, D.A., Charnock, J.M., Chatterjee, D., Lloyd, J.R., 2004. Role of

metal-reducing bacteria in arsenic release from Bengal delta sediments. Nature 430, 68-71. Lapworth, D.J., Gooddy, D., Butcher, A., Morris, B., 2008. Tracing groundwater flow and sources of organic

carbon in sandstone aquifers using fluorescence properties of dissolved organic matter (DOM). Applied Geochemistry 23, 3384-3390.

Lawson, M., Polya, D.A., Boyce, A., Bryant, C., Mondal, D., Shantz, A., Ballentine, C.J., 2013. Pond derived organic carbon driving changes in arsenic hazard found in Asian groundwaters. Environmental Science & Technology 47, 7085-7094.

Neumann, R.B., St. Vincent, A.P., Roberts, L.C., Badruzzaman, A.B.M., Ali, M.A., Harvey, C.F., 2011. Rice field geochemistry and hydrology: an explanation for why groundwater irrigated fields in Bangladesh are net sinks of arsenic from groundwater. Environmental Science & Technology 45, 2072-2078.

Pi, K., Wang, Y., Xie, X., Huang, S., Yu, Q., Yu, M., 2015. Geochemical effects of dissolved organic matter biodegradation on arsenic transport in groundwater systems. Journal of Geochemical Exploration 149, 8-21.

Ravenscroft, P., Brammer, H., Richards, K., 2009. Arsenic Pollution: a global synthesis. Wiley-Blackwell. Rowland, H., Boothman, C., Pancost, R., Gault, A., Polya, D., Lloyd, J., 2009. The role of indigenous

microorganisms in the biodegradation of naturally occurring petroleum, the reduction of iron, and the mobilization of arsenite from West Bengal aquifer sediments. Journal of Environmental Quality 38, 1598-1607.

This research was funded by a NERC Standard Research Grant (NEJ023833) to DP, BvD and C. J. Ballentine and an NERC PhD studentship (NE/L501591/1) to DM.

O10

Shifts in deep-sea food webs linked to climate and food supply.

R. M. Jeffreys1*, D. S. M. Billett2, G. A. Wolff 1

1School of Environmental Sciences, University of Liverpool, Liverpool, UK. 2Deep Seas Environmental Solutions Ltd., 132 Woodlands Road, Ashurst, SO40 7AP, UK

Shifts in deep-sea benthic communities detected in time-series data (> 20 years) in the NE Atlantic (Porcupine Abyssal Plain, PAP) have been linked to climate-driven variation in particulate organic matter (POM) fluxes (Billett et al., 2010). Iken et al. (2001) revealed through stable isotope analyses that the benthic community at PAP is dominated by deposit feeders (Iken et al., 2001), and identified an overlap in food sources and competition for resources between consumers. The effect of climate-driven variation in POM flux on food web dynamics over decades in the deep sea is unclear. We investigated the trophic structure of the megafaunal benthic food web at the PAP from 1989-2005. We determined stable nitrogen isotopic composition (d15N) of bulk tissues in 3 deposit-feeding holothurians, Amperima rosea, Oneirophanta mutabilis, Pseudostichopus aemulatus and the mud-ingesting asteroid Hyphalaster inermis. Bulk d15N isotopic compositions ranged from 7.8‰ in A. rosea to 16.3‰ in H. inermis and revealed clear differences between the species, reflecting differences in feeding strategies. A. rosea feeds on the freshest POM, while H. inermis feeds on the most refractory organic matter. Significant inter-annual differences were noted for A. rosea, P. aemulatus and H. inermis. The d15N composition of A. rosea was significantly depleted in 2002 and 2005 (mean d15N = 8.0 ± 0.48 ‰) compared to previous years (9.0 ± 0.43‰) suggesting a change in either the quality of organic matter or d15N composition of POM at this time. The shift in d15N of A. rosea followed a very high flux of POM to PAP during 2001 (Billett et al., 2010). P. aemulatus and H. inermis were significantly enriched in d15N in 1989 (mean d15N = 16.2‰ for both), compared to 2005 (d15N = 14.8 ± 0.68‰ and 12.4 ± 0.31‰ for H. inermis and P. aemulatus, respectively). This may reflect changing competition for resources or differences in organic matter quality. The d15N composition of O. mutabilis did not change with time (d15N = 11.05 ± 0.53‰), suggesting that its feeding strategy allows it to consistently exploit relatively fresh organic matter. Our initial results show that climate-driven variation in the POM flux does influence the dynamics of deep-sea food webs. References Billett, D.S.M., Bett, B.J., Reid, W.D.K., Boorman, B., Priede, I.G., 2010. Long-term change in the

abyssal NE Atlantic: The “Amperima Event” revisited. Deep-Sea Research Part II 57, 1406–1417. Iken, K., Brey, T., Wand, U., Voigt, J., Junghans, P., 2001. Food web structure of the benthic

community at the Porcupine Abyssal Plain (NE Atlantic): a stable isotope analysis. Progress in Oceanography 50, 383–405.

O11

Removal of Metaldehyde From Drinking Water Using a Novel Treatment Process

M. A. Nabeerasool 1, D. A. Polya 1, A. K Campen 2, N. W. Brown2, B .E. van Dongen1

1 School of Earth Atmospheric and Environmental Sciences and Williamson Research Centre for Molecular Environmental Science , University of Manchester, Manchester, M13 9PL, UK 2 ArviaTM Technology, The heath Business and Technical Park, Runcorn, Cheshire, WA7 4EB, UK

The presence of pesticides in drinking water sources is hazardous and could pose a problem for safe drinking water provision. Metaldehyde is a selective pesticide extensively used in agriculture for the control of snails and slugs. When application rates are high metaldehyde may find its way into water courses, some of which used as drinking water supplies. The limit of metaldehyde in drinking water is 0.1 ppb and water companies in the UK have been required by the Drinking Water Inspectorate (DWI) to conform to this by 2015 (DWI, 2013). This represents a real challenge as current water treatment processes are ineffective for reducing metaldehyde to the regulatory limit of 0.1 ppb and levels up to 8 ppb have been observed (Marshall, 2013). Here, we present experiments on a novel technology (Mohammed et al., 2011; Asghar et al., 2012) capable of removing metaldehyde from water using standard conditions and meeting the regulatory limit. We showed that metaldehyde is removed/destroyed using this novel technology under laboratory based conditions and low concentration tests (starting concentration of 10 ppb) showed that metaldehyde is removed/destroyed to below the regulatory limit of 0.1 ppb within 4 treatment cycles with successive spiking experiments showing that the process is repeatable. Large scale treatment experiments have shown that metaldehyde can be removed during a single pass to below the regulatory limit. References Asghar, H.M.A., Roberts, E.P.L., Hussain, S.N., Campen, A.K., Brown, N.W., 2012. Wastewater

treatment by adsorption with electrochemical regeneration using graphite-based adsorbents. Journal of Applied Electrochemistry 42, 797-807.

DWI, 2013. DWI PR14 Guidance – Pesticides including Metaldehyde. DWI. February 2013. Version 1.1 3pp.

Marshall, J., 2013. Briefing paper on metaldehyde on drinking water sources. Water UK Briefing Paper. 5pp. http://www.water.org.uk/home/policy/positions/metaldehyde-briefing/water-uk-policy-briefing-metaldehyde-13-aug 2013.pdf. Last updated 13th August 2013.

Mohammed, F.M., Roberts, E.P.L., Hill, A., Campen, A.K., Brown, N.W., 2011. Continuous water treatment by adsorption and electrochemical regeneration. Water Research 45, 3065-3074.

O12

NAOSIPUK project: Understanding the NAO from Iberian and UK

paleoclimate records. State of the art.

A., Garcia-Alix 1, J. L. Toney1, G. Jiménez Moreno2, R.S. Anderson3

1 School of Geographical & Earth Sciences, University of Glasgow, Glasgow, UK 2 Departamento de Estratigrafía y Paleontología, Universidad de Granada, Granada, Spain 3 School of Earth Sciences and Environmental Sustainability, Northern Arizona University, Flagstaff, USA

The North Atlantic Oscillation (NAO) is primary climate mode which influences climate patterns across Europe, with economic and societal impacts (Hurrell, 1995). Because of its importance, we need to increase our understanding of the relationship between the NAO and anthropogenic and natural climate change to be able to project future scenarios. Understanding these interactions is the main goal of the NAOSIPUK Project, funded by the Marie Curie Actions of the European Commission. This project compares paleoclimate records from two climate-sensitive regions with opposite responses to the NAO modes: centre-northern UK and southern Iberia. We are studying the organic and inorganic geochemistry, pollen and charcoal remains, and in some cases, geophysical lake sediment profiles from Holocene records. Our study sites in southern Iberia include four high elevation records (lakes and bogs around 3000 masl) and a low elevation bog (720 masl). Certain of these records contain alkenones and/or diols, which can be used as a paleothermometer of past climates. These data along with in situ temperature measurements will allow us to calibrate those paleotemperature proxies. Moreover, after a survey studying the organic signature of lake surface sediments in UK, we selected three sites: Esthwaite Water (EW, English Lake District), Loch Lomond (LL) and Dubh Lochan (DL) (both southern Scotland). LL and EW showed evidence of alkenones, which can be calibrated with continuous temperature measurements in those sites (UKLEON). A 8.6m long sediment core was collected in EW. The cores from LL and DL will be retrieved in June and October 2015, respectively.

References Hurrell, J.W., 1995. Decadal Trends in the North Atlantic Oscillation: Regional Temperatures and

Precipitation. Science 269, 676-679. NAOSIPUK. http://www.naosipuk.org. Last access: 1st June. UKLEON. http://www.data.ecn.ac.uk/ukleon/. Last access: 1st June.

O13

Organic matter characterisation and paleoclimatic conditions from the

central part of the Mexican Chihuahuan Desert over the last 27 ka cal BP

C. M. Chávez Lara1, J. Holtvoeth1, R. D. Pancost1, P. D. Roy2. 1 Organic Geochemistry Unit at the University of Bristol, Bristol, UK 2 Geological Institute at the National Autonomous University of Mexico, Mexico City, Mexico

The paleolake Santiaguillo (Durango State) is located in the central part of the Chihuahuan Desert (Mexico; 24°30’-25°00’ N, 104°40’-105°00’ W). This lacustrine basin covers an area of approximately 1,964 km2 and is surrounded by mountains up to ca. 2,700 masl. The basin was formed by tectonic processes and the basement is formed by volcanic felsic rocks of Tertiary age. A 3 m sediment core was obtained from the western part of the basin to reconstruct hydrological and climate variability during the late Pleistocene and Holocene. The age model was constructed from 8 AMS radiocarbon dates and the sediment core represents the last 27 cal ka BP. In this work, we present initial results of organic matter characterization by lipid biomarker analysis from this sedimentary archive. Sediment samples were freeze-dried, homogenized and then solvent-extracted using a microwave-assisted extraction system. Total lipid extracts (TLEs) were analysed by gas chromatography-mass spectrometry (GC-MS). In general, the TLEs show high proportions of fatty acid methyl esters (FAMEs). Mono-unsaturated fatty acids (MUFAs) are the second-most abundant compounds while less abundant compound classes include hydroxy acids, methyl ketones and sterols. Relatively low abundance or even absence of n-alkanes is observed; however, the amount of n-alkanes appears to increase significantly with depth. Most sediments show bimodal or trimodal FAME chain-length distributions, with short-chain FAMEs (C16-C20) being the major compounds and further maxima at 22.77 and 7.92 µg/gsed. C18:1 (cis, trans) is the prominent MUFA. One limitation is the low lipid concentration in sediments from paleolake Santiaguillo (32.39 – 0.78 µg/gsed). Initial results from TLE analysis of sediments samples from two other paleolakes in the Chihuahuan Desert show much higher lipid concentrations and diversity and will be analysed as part of the North American Monsoon path reconstruction project.

O14

The emergence of dairying in Neolithic Europe: A lipid residue and

compound specific radiocarbon dating approach

E. Casanova1, M. Roffet-Salque1, R. P. Evershed1 1 Organic Geochemistry Unit, Bristol, UK

The project aims to investigate the emergence of dairying in the first Neolithic farming communities characterised by the Linearbandkeramic culture, using biomarkers and carbon isotope analyses of organic residues preserved in pottery vessels, together with other lines of archaeological evidence. Such vessels provide a wealth of information regarding past diet and specific aspects of food procurement and processing. Organic residues recovered from archaeological potsherds are dominated by degraded animal fats identified by their high contents of palmitic (C16:0) and stearic (C18:0) acids (Evershed et al., 2002). Based on their δ13C values ruminant adipose, non-ruminant adipose and milk fats can be discriminated (Copley et al., 2003). The use of lipids trapped in pottery vessel is also of promise for radiocarbon analysis of pottery vessels and hence the dating archaeological sites and phases (Berstan et al., 2008). Compound-specific radiocarbon dating uses preparative capillary gas chromatography to isolate individual fatty acids for analysis by accelerator mass spectrometry. Such an approach will allow the use of pottery to be directly linked to their determined calendrical dates. The removal of exogenous contaminants is a potential advantage of the compound-specific dating approach. However, the method needs to be fully developed and its ability to provide robust calendrical dates demonstrated before it can be used routinely. Pottery assemblages from Alsacian Neolithic sites which have been the object of intense seriation and dating studies (Lefranc, 2007) and have been shown to preserve abundant lipids, will be used to validate this methodology. References Berstan, R., Stott, A. W., Minnitt, S., Bronk Ramsey, C., Hedges, R. E. M., Evershed, R. P., 2008.

Direct dating of pottery from its organic residues: new precision using compound-specific carbon isotopes. Antiquity, 82(317): 702-713.

Copley, M.S., Berstan, R., Dudd, S. N., Docherty, G., Mukherjee, A. J., Straker, V., Payne, S., Evershed, R. P., 2003. Direct chemical evidence for widespread dairying in prehistoric Britain. Proceedings of the National Academy of Sciences, 100(4): 1524-1529.

Evershed, R.P. Dudd, S. N. , Copley, M. S., Berstan, R., Stott, A. W., Mottram, H., Buckley, S. A., Crossman, Z., 2002. Chemistry of archaeological animal fats. Accounts of Chemical Research 35, 660-668.

Lefranc, P., 2007. La céramique du Rubané en Alsace. Contribution à l'étude des groupes régionaux du Néolithique ancien dans la plaine du Rhin supérieur. Université Marc-Bloch, Strasbourg.

O15

Do changes in plant functional diversity and imposed warming change

the peat composition in a peatland?

D. Satterthwaite1, R. Bardgett1, F. de Vries1, B. van Dongen2

1 Faculty of Life Sciences, University of Manchester, Manchester, UK 2 School of Earth, Atmospheric and Environmental Sciences and Williamson Research Centre for molecular Environmental Science, University of Manchester, Manchester, UK

Organic soils of montane and peatland ecosystems represent a vast carbon sink, holding up to 30% of terrestrial carbon while only covering 3% of the terrestrial surface (Limpens et al., 2008). Due to climate change there is the risk that these ecosystems will become carbon sources. The primary abiotic effects of climate change alter plant functional diversity in these ecosystems, and recent studies show that this has cascading effects on belowground microbial communities (Ward et al. 2013). However, the consequences for biogeochemical processes and carbon cycle feedbacks are less known. We hypothesise that the effects of climate change on belowground communities are largely indirect, and that changes in microbial communities associated with vegetation change have consequences for key processes involved in carbon cycling, potentially altering source-sink dynamics. To test this, samples were collected from a long-term vegetation and climate manipulation experiment at Moor House, North Pennines. Alongside biological analyses, the composition of the peat below the different treatments will be analysed using (TMAH enhanced) pyrolysis GC/MS. During this presentation, preliminary data from TMAH pyrolysis GC/MS analysis from this site will be presented, and future work will be discussed. References Limpens, J., Berendse, F., Blodau, C., Canadell, J.G., Freeman, C., Holden, J., Roulet, N., Rydin, H.,

Schaepman-Strub, G., 2008. Peatlands and the carbon cycle: From local processes to global implications – A synthesis. Biogeosciences 5, 1475-1491.

Ward, S.E., Ostle, N.J., Oakley, S., Quirk, H., Henrys, P.A., Bardgett, R.D., 2013. Warming effects on greenhouse gas fluxes in peatlands are modulated by vegetation composition. Ecology Letters 16, 1285-1293.

O16

Ultrasound Spectrometry and Statistical Inference of Water-in-Oil Emulsions

A. Svalova1, N. G. Parker2, G. D. Abbott1

1School of Civil Engineering and Geosciences, Drummond Building, Newcastle University, Newcastle upon Tyne, NE1 7RU, UK 2School of Mathematics and Statistics, Newcastle University, Newcastle upon Tyne, NE1 7RU, UK

Water-in-oil emulsions (WOEs) are highly viscous and stable mixtures occurring during crude oil production and spills (Sjoblom et al., 2003). It is accepted that asphaltene aggregation is critical to WOE stability (Sjoblom et al., 2003). Emul-sion stability is also influenced by crude oil geochemistry, such as resin abun-dance (Sjoblom et al., 2003) and biodegradation degree (Aske et al., 2002).

Asphaltene aggregation and clustering will be investigated using ultrasound spectrometry (Abbott and Povey, 2012). This method is also particularly appli-cable to WOEs as ultrasound can propagate through optically opaque substan-ces (Povey, 1997). It provides access to volume fractions, density and adiabatic compressibility without perturbing the sample structure. Ultrasound allows the droplet size distribution (DSD) to be determined which is critical to emulsion stability (Challis, 2005).

The DSD growth is statistically modelled in order to estimate the onset of WOE phase separation (Svalova et al., 2015). This will help in the optimisation of remediation strategies following large oil spills such as Deepwater Horizon. References Abbott G.D, Povey M.J.W., 2012. The acoustic spectroscopy of asphaltene aggregation in petroleum.

IOP Conference Series: Materials Science and Engineering 42, 012022. Aske, N., Kallevik, H., Sjoblom J., 2002. Water-in-crude Oil Emulsion Stability Studied by Critical Field

Electric Measurements. Correlation to Physico-chemical parameters and Near-infrared Spectroscopy. Journal of Petroleum Science and Engineering 36, 1-17.

Challis, R., Povey, M., Mather, M., Holmes, A., 2005. Ultrasound Techniques for Characterising Colloidal Dispersions. Reports on Progress in Physics 68, 1541-1637.

Povey, M., 1997. Ultrasound Techniques for Fluid Characterisation, Academic Press, San Diego. Sjoblom, J., Aske N., Auflem, I.H., Brandal, O., Harve, E.T., Saether, O. Westvikb, A., Johnsenb, E. E.,

Kallevikb, H., 2003. Our Current Understanding of Water-in-Oil Crude Oil Emulsions: Recent Characterisation Technogies and High Pressure Performance. Advances in Colloid and Interface Science 100-102, 399-473.

Svalova, A., Abbott, G.D., Parker, N.G., Vane, C.H., 2015. Droplet Size Distribution of Crude Oil Emulsions: Stochastic Differential Equations and Bayesian Modelling. EAGE Petroleum Geostatistics, In Press.

O17

Hydrothermal liquefaction of algal biomass to produce advanced biofuels

M. Ali1, 3, I. A. Watson2*, J. Toney3

1 Systems, Power and Energy Research Division, School of Engineering, University of Glasgow, Glasgow, UK 2 Biomarkers for Environmental and Climate Science Research Group, School of Geographical and Earth Sciences, University of Glasgow, Glasgow, UK 3 Environmental Engineering Department, NED University of Engineering and Technology, Karachi, Pakistan. *Corresponding author e-mail: ian.watson.glasgow.ac.uk

The potential of microalgae as a feedstock has been realised in recent years due to its high growth rate and lipid productivity, which is estimated to be ~300 times greater than conventional vegetable crops [1]. However, to produce 10 billion gallons of biofuel from algae requires 33 billion gallons of water, 6 million metric tons of nitrogen and up to 2 million tons of phosphorus for its growth [2]. Microalgae can capture CO2 emitted by anthropogenic sources, helping CO2 sequestration (Ali & Watson, 2015) and their biofuel derivatives have a higher energy density compared to those from other crops. Hydrothermal liquefaction is a thermo-chemical process, with rapid heating of water between 200 and 350oC, the biomass is broken into smaller molecules which are reactive and re-polymerize into bio-crude oil (Biller & Ross, 2011), the water phase contains nutrients that can be recycled for algae growth (Biller et al., 2012). The current investigation investigated hydrothermal liquefaction processing of Chlorella vulgaris, at temperatures between 200-350oC for 30 and 60 min. The physical and chemical properties of the bio-crude oil yield and its end products were analysed; including nitrogen, phosphorous, organic carbon contents and higher heating values. The bio-crude oil has long chain fatty acids (C14-C18) which can be readily used in boilers and heavy engines and can be thermally upgraded to obtain gasoline, diesel and jet fuels. The recycling of organic carbon and nutrients (N and P) helps in improving carbon efficiency (biomass yield) and algal growth respectively. References Ali, M., Watson, I.A., 2015. Microwave treatment of wet algal paste for enhanced solvent extraction of

lipids for biodiesel production. Renewable Energy 76(0), 470-477. Biller, P., Ross, A. B., 2011. Potential yields and properties of oil from the hydrothermal liquefaction of

microalgae with different biochemical content. Bioresource Technology 102(1), 215-225. Biller, P., Ross, A. B., Skill S. C., Lea-Langton, A., Balasundaram, B., Hall, C., Riley, R.,Llewellyn,

C.A., 2012. Nutrient recycling of aqueous phase for microalgae cultivation from the hydrothermal liquefaction process. Algal Research 1(1), 70-76.

[1] http://www.biofuelstp.eu/advancedbiofuels.htm last accessed on 25 May 2015. [2] http://biofuel.org.uk/advanced-biofuels.html last accessed on 25 May 2015.

O18

The Bacterial Community Structure and Isotopic Composition of PAHs in coal tar: a study of the Intrinsic Biodegradation Potential

F. Colosimo1, C. Boothman2, R. Lord1, R. Thomas3, J. Lloyd2, R. Kalin1

1 University of Strathclyde, Glasgow, United Kingdom 2 The University of Manchester, Manchester, United Kingdom 3 Parsons Brinckerhoff Ltd. (PB), Bristol, United Kingdom

Dense non-aqueous phase liquids (DNAPLs) such as coal tar represent a class of persistent subsurface contaminants composed of thousands of organic and inorganic compounds (D’Affonseca, et al., 2008). Due to high hydrophobicity, coal tar tends to interact with non-aqueous phases and soil organic matter; as a consequence, coal tar becomes potentially unavailable for microbial degradation (Birak & Miller, 2009). Nevertheless, the presence of hydrocarbon-degrading bacteria has been described in several DNAPLs-contaminated environments such as soils, sediments and groundwaters. Whereas several reviews focussed on the bacterial community composition of these environments, this study developed methodologies for the microbial characterisation of pure coal tar DNAPLs, with emphasis on both the molecular characterisation and physico-chemical factors influencing the analyses of this complex substrate. A pyrosequencing-based assessment of the 16S rRNA gene was carried out to identify bacterial diversity and community structure in seven DNAPLs. The operational taxonomy units (OTUs) sequences were analysed using a sequencing database of known 16S rRNA gene sequences to identify nearest neighbours. The phylogenetic affiliations were confirmed by analyses of all related species recognised by the taxonomic and classification hierarchy done with the NCBI Taxonomy database. Furthermore, the seven coal tars were studied to evaluate the applicability of Compound Specific Isotope Analyses (CSIA) as a tool to determine the intrinsic biodegradation potential of polycyclic aromatic hydrocarbons (PAHs). The isotopic composition of PAHs suggests that the isotope fractionations observed could be related to established biochemical degradation mechanisms, each involving a C-H bond cleavage. The narrow range of carbon stable isotope ratios (δ13C) did not demonstrate significant fractionation. In contrast, a strong 2H enrichment was detected for Naphthalene, Phenanthrene, Anthracene and Fluorene. This wide range of hydrogen stable isotope ratios (δ2H), together with the δ13C, reveals a considerable potential for hydrogen isotope analysis to assess microbial degradation of PAHs. The combined application of metagenomics analysis and CSIA, as two independent tools to monitor and trace biodegradation, could potentially lead to an improved evaluation of natural attenuation in situ. References

D’Affonseca, F., Blum, P., Finkel, M., Melzer, R., Grathwohl, P., 2008. Field scale characterization and modeling of contaminant release from a coal tar source zone. Journal of Contaminant Hydrology 102, 120-139.

Birak, P. S., Miller, C.T., 2009. Dense non-aqueous phase liquids at former manufactured gas plants: Challenges to modeling and remediation. Journal of Contaminant Hydrology 105, 81-98.

O19

Environmental Forensics of Coal Tars – A Case Study

C. Gallacher 1, R. Kalin 2, R. Thomas 3 1 University of Strathclyde, Glasgow UK 2 University of Strathclyde, Glasgow UK

3 Parsons Brinckerhoff, Bristol, UK

Coal tar waste is a hazardous by-product of manufactured gas plants (MGP) and due to poor handling in the past coal tar contamination is a common occurrence at former MGP sites. Coal tars are a complex mixture of organic and inorganic compounds, of which many can be toxic or carcinogenic and pose a complex challenge for remediation. The work focuses on the use of state of the art Two-dimensional gas chromatograph coupled to a time-of-flight mass spectrometer (GCxGC-TOFMS) to establish the chemical fingerprint of the tar samples.

GCxGC-TOFMS allows for the identification of thousands of individual compounds within a single sample, which can be used to identify the production process used to produce the tars as well as the possible environmental risks from the tars. Powerful statistical techniques including Principle component analysis and Hierarchical cluster analysis are used to identify if samples are coal tar and to provide important information such as the production process used to produce the tars and possible environmental risks associated with the tars. These techniques have been applied to several case study samples to demonstrate the power of GCxGC-TOFMS as a tool for Environmental Forensic analysis.

BOGS 2015, Glasgow

ABSTRACTS

Posters

P1

Application of biomarkers to paleolimnological reconstruction : a lake survey of Southern Alaska and Colorado

M. Cornet1, J. Toney², R. S. Anderson3

1 ENS de Lyon, Lyon, France ² University of Glasgow (BECS), Glasgow, Scotland 3 School of Earth Sciences & Environmental Sustainability, Northern Arizona University, Flagstaff, United States

Molecular organic geochemical proxies are widely used in paleoceanographic research, but their application to lacustrine environments needs additional study in order to get a deeper knowledge of their conditions of formation and paleoenvironmental signicance. Indeed, the large range of chemical and physical properties of lakes considerably complicates the application of these proxies to paleolimnological records. This research reports a survey of 19 lakes from Alaska and Colorado in the Western US in order to describe the biomarkers that can be found within the top-core sediments. This will allow us to obtain more information about the potential for biomarkers that could be found in the deeper sediments of those lakes, in order to realise information suitable for further paleolimnological study of selected lakes (those which contain exploitable biomarkers). Indeed, the two locations chosen are very sensitive to climate changes because of their high latitude and high altitude (respectively), which makes their sediments very interesting sources of data for paleoclimatologic reconstructions.The results mainly focus on the description of the aliphatic hydrocarbons and n-alknoic acids. The identication of alkenones, which are rare but very useful biomarkers, is also one of the purposes of this research.

P2

Tracing Polycyclic Aromatic Hydrocarbon (PAH) Sources in Luce Bay by

Intertidal Sediment Analysis.

J. Coyle 1, J. Toney 1, C. Engelke 2, C. Gauchotte-Lindsay

1 University of Glasgow, Glasgow, UK 2 Scottish Environment Protection Agency (SEPA), Glasgow, UK

Polycyclic Aromatic Hydrocarbons (PAH) are a group of several hundred complex chemicals built from two or more aromatic (benzene rings) occur in most abundance in soils and sediments (CCME 2010; SHER, 2011). These chemicals occur naturally (due to incomplete combustion of organic matter, Latimer & Zheng, 2003) and through petrogenic processes in the crust (CCME, 2010). It is generally accepted that levels of PAH in the environment increase as a result of anthropogenic activity given their formative conditions and the elevated synonymous with proximity to purogenic and petrogenic pollution sources (Transport links; Ravinda et al., 2008, Oil Related Industry; Bellas et al., 2008 and Marine Ports; Latimer & Zheng, 2003). These compounds are of an interest to environmental managers and regulators given their potential harmful and mutagenic properties to marine and terrestrial biota (Bellas et al., 2008) and their possible carcinogenic properties in humans due to their persistence and longevity in sediments and biota.

In 2014, the Food Environment Research Agency (FERA) found elevated levels of the PAH benzo[a]pyrene (5.82 ± 0.99 µg/kg, FERA, 2014) in a Razor clam sample from Luce bay, exceeding regulation, and representing a significant risk to human health (FERA, 2014). Although, a repeat sample, several months later, found concentrations of PAH to be within safe levels, it is still recognised that there is a contamination issue in the marine environment of Luce bay. With no obvious pollutant sources present, little is known about the potential source PAH in the area. As a result, SEPA has requested that these, as yet, unexplained elevated concentrations of PAH in Razor shells in the area be investigated to identify potential point sources of the hydrocarbons References; Bellas, J., Saco-Álvarez, L., Nieto, Ó., Beiras, R., 2008. Ecotoxicological evaluation of polycyclic aromatic

hydrocarbons using marine invertebrate embryo–larval bioassays. Marine pollution bulletin 57, 493-502. CCME, 2010. Canadian Soil Quality Guidelines CARCINOGENIC AND OTHER POLYCYCLIC AROMATIC

HYDROCARBONS (PAHs) (Environmental and Human Health Effects). Canadian Council of Ministers of the Environment, Toronto.

FERA, 2014. Chemical Contaminant Sampling and Analysis of Shellfish from Classified Harvesting Areas (2014). Report to the Food Standards Agency In Scotland, York. Crown copyright.

Latimer, J. S., Zheng, J., 2003. The Sources, Transport & Fate of PAH in the marine environment. In PAHs: an ecotoxicological perspective, Wiley & Sons.

Ravindra, K., Sokhi, R., Van Grieken, R., 2008. Atmospheric polycyclic aromatic hydrocarbons: source attribution, emission factors and regulation. Atmospheric Environment 42, 2895-2921.

SCHER (Scientific Committee on Health and Environmental Risks) 2011. Opinion on draft environmental quality standards under the Water Framework Directive – polyaromatic hydrocarbons. European Commission, Brussels

P3

Pottery Sherds from the Middle East

S. Fraser1,2, B. van Dongen1, S. Campbell2

1 School of Earth Atmospheric and Environmental Sciences and Williamson Research Centre for Molecular Environmental Science, The University of Manchester, Manchester, UK 2 Archaeology, School of Arts, Languages and Cultures, The University of Manchester, Manchester, UK

Many archaeological pottery sherds have been excluded from organic residue analysis because of the non optimal conditions in which they have been collected and/or stored (e.g. washed at site and stored in plastic bags), or because their function was not obviously for cooking and therefore it has been assumed that organic residues will not have been absorbed into the fabric of the pottery. This severely limits the range of questions that can be posed. This study has shown that by using an adapted version of the recent acid extraction method as described by Correa-Ascencio and Evershed (2014), it is possibly to extract appreciable amounts of organic material from sherds that are Late Neolithic in age (early 6th Millennium BC), that were excavated between 1999 and 2004 site of Domuztepe, Turkey. Many of the sherds were washed before being stored in plastic bags. Sherds from a Bronze Age site in Iraq (~ 1500 BC) have been studied as a comparison as they have been excavated recently, were not washed and have been stored wrapped in foil. However many of these sherds are from pots that are unlikely to have been used for cooking, but instead for storage or serving food. Initial analyses indicate that lipids, including fatty acids, can be extracted from these sherds, although in substantially lower amounts than the amounts extracted from those pots that have been identified as cooking pots.

By showing that samples that are generally seen as not ideal for analysis can in fact provide useful information, suggests that sherds stored and forgotten about can now bring new insights to their function and the cultures/societies that used them. References Correa-Ascencio, M., Evershed, R. P., 2014. High throughput screening of organic residues in

archaeological potsherds using direct acidified methanol extraction. Analytical Methods 6, 1330-1340.

P4

High proportions of terrestrial biomarkers in sediments of the tropical

Atlantic – evidence for African dust supply?

J. Holtvoeth1, C. B. Egan1, S. Blackbird2, G. Rowland3, H. C. Ng3, M. P. S. Badger1, L. F. Robinson3, R. D. Pancost1

1Organic Geochemistry Unit, School of Chemistry, University of Bristol, Bristol, UK 2School of Environmental Sciences, University of Liverpool, Liverpool, UK 3School of Earth Sciences, University of Bristol, Bristol, UK

In 2013, RRS James Cook cruise 94, targeting tropical Atlantic seamounts, collected surface sediment and shallow sediment cores (ROV push cores, multi-corer and box core samples) along a transect across the tropical Atlantic, starting south of the Cape Verde Islands at ~10°N and finishing west of the mid-Atlantic Ridge at about 15°N, 50°W. We present results from elemental (TOC, TOC/TN, CaCO3) and lipid biomarker analyses (lipid composition, chain-length distributions) of surface and box core samples (2 – 12 cm) in order to asses main organic matter (OM) sources and early OM diagenesis.

The investigated sediments consist mainly of carbonate (~ 80 %). Concentrations of total organic carbon (TOC) are generally very low (TOC: 0.2-0.8 %) as are the 230Th-normalised fluxes of TOC (0.1-0.3 mg m-2 d-1) calculated for some of the investigated sites. TOC is the only variable showing a weak longitudinal trend, with slightly higher concentrations in the east. Concentrations of lipids are very low, ranging from 2.4 – 8.2 mg/gSed in the surface samples and varying around 2 mg/gSed in box core S0153.

TOC concentrations at S0153 decrease between 2 and 12 cm b.s.f. while TOC/TN ratios increase, with both measures showing a distinct shift at ~ 5 cm that is not reflected in biomarker composition. A steady decrease in carbonate concentration in S0153 suggests either top down dissolution of carbonate due to a recent decrease in bottom-water pH or increasing deposition of non-carbonate (dust?) material.

A consistent feature in all subsurface samples of S0153 is the high proportion of long-chain (terrestrial) fatty acids (>C25, av.: 23 %lipids), n-alkanes (>C26, av.: 16 %lipids) and n-alcohols (>C25, av.: 10 %lipids). Surface samples generally show higher proportions of (labile) mono-unsaturated fatty acids (mainly C18:1 and C22:1) and sterols (mainly sitosterol). Unusual findings include high proportions of odd-numbered C19 and C17 w-hydroxy acids. We also recorded a range of, so far, unidentified compounds (mass spectra on poster, suggestions greatly appreciated).

P5

High temperature gas chromatography coupled to mass spectrometry for

analysis of large polar compounds

S. K. Lengger 1, P. A. Sutton2, I. D. Bull1, D. J. Rush3, S. J. Rowland2, H. M. Talbot3, R. D. Pancost1

1 Organic Geochemistry Unit and The Cabot Institute, School of Chemistry, University of Bristol, Bristol, UK. [email protected] 2 Petroleum and Environmental Geochemistry Group, Biogeochemistry Research Centre, University of Plymouth, Plymouth, UK. 3School of Civil Engineering and Geosciences, Newcastle University, Newcastle upon Tyne, UK.

Large polar compounds such as glycerol dialkyl glycerol tetraether lipids (GDGTs) or (amino-)bacteriohopanepolyols (BHPs) are widely used as biomarkers for organisms or biogeochemical processes. Due to their high molecular weight (600 to > 1300 Da), chemical degradation needs to be employed in order to make them amenable to gas chromatography, resulting in loss of structural complexity and, as such, biomarker specificity. Recently, high temperature (up to 430¹C) gas-chromatography mass spectrometry (HTGC-MS) has been shown to result in superior separation and spectra of high boiling compounds.

Here, we employed this method for analysis of environmental samples: a mat from a Black Sea methane seep, marine sediment, peat, and biomass of a methanotrophic bacterium. This allowed us to structurally identify isoprenoidal GDGTs (GDGT-0, GDGT-1, GDGT-2, GDGT-3, Crenarchaeol) and branched GDGTs, as well as BHPs (bacteriohopanetetrol and -pentol, aminobacteriohopanetriol and -tetrol) and separate some of their isomers in biomass and environmental samples. Our results agreed with those achieved via traditional methods (liquid chromatography-mass spectrometry). The high retention times and generally baseline-separated peaks also allowed for absolute quantification via HTGC-FID, a method that potentially avoids the complications caused by ionization differences when quantifying by mass spectrometric methods. We show that HTGC-MS could be applied to environmental samples and allowed for superior separation, identification and quantification of BHPs and GDGTs, enabling a number of exciting applications in biogeochemistry and geochemistry.

P6

Dissolved Organic Phosphorus: From Sources to Watercourses

C. A. McIntyre1, R. P. Evershed1, P. J. Johnes2

1 Organic Geochemistry Unit, School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS 2 School of Geographical, University of Bristol, University Road, Bristol BS8 1SS

Phosphorus (P) is a macronutrient of global environmental and economic importance. It is increasingly becoming a cause for concern, as the P cycle has been altered to a dangerous level by anthropogenic activity (Steffen et al., 2015). P leaching from agricultural land and waste discharges to freshwaters causes eutrophication and damages ecosystems. Despite wide use of inorganic phosphate as an indicator of water quality, very little is known about the composition and contribution of organic P (Po) to productivity and pollution in freshwaters. This project aims to characterise DOP on a molecular level using high resolution mass spectrometry (HRMS) and nuclear magnetic resonance (NMR). To date, NMR is the foremost method of characterisation of Po. However, the resolution of the technique and the complexity of environmental samples is such that Po is characterised to a compound class (Turner, 2008) level only. HRMS has the capability to identify tens of thousands of compounds in a single sample (Osborne et al., 2013). Using HRMS in conjunction chromatographic techniques and NMR, point sources of Po – such as manures – can be characterised. Incubation experiments can be set up to determine the biotic and abiotic transformation process that Po undergoes in the environment. Lysimeter experiments will help identify the transport and transformation processes that affect Po in soils and ultimately lead to its contamination of freshwaters. The results of the project will inform better management of P sources and reduce the loading of P to freshwaters. References Osborne, D.M., Podgorski, D.C., Bronk, D. a, Roberts, Q., Sipler, R.E., Austin, D., Bays, J.S., Cooper,

W.T., 2013. Molecular-level characterization of reactive and refractory dissolved natural organic nitrogen compounds by atmospheric pressure photoionization coupled to Fourier transform ion cyclotron resonance mass spectrometry. Rapid Communications in Mass Spectrometry 27, 851-858. doi:10.1002/rcm.6521

Steffen, W., Richardson, K., Rockstrom, J., Cornell, S.E., Fetzer, I., Bennett, E.M., Biggs, R., Carpenter, S.R., de Vries, W., de Wit, C.A., Folke, C., Gerten, D., Heinke, J., Mace, G.M., Persson, L.M., Ramanathan, V., Reyers, B., Sorlin, S., 2015. Planetary boundaries: Guiding human development on a changing planet. Science 347, doi:10.1126/science.1259855.

Turner, B.L., 2008. Soil organic phosphorus in tropical forests: an assessment of the NaOH–EDTA extraction procedure for quantitative analysis by solution 31 P NMR spectroscopy. European Journal of Soil Science 59, 453-466.

P7

Recent environmental change deduced from biomarkers in Borreguiles

de la Caldera, a high-elevation wetland in Sierra Nevada, Southern Spain

S. Pauchet1, A., Garcia-Alix2, J. L. Toney2, G. Jiménez Moreno3, R. S. Anderso43

1 ENS de Lyon, Lyon, France 2 School of Geographical & Earth Sciences, University of Glasgow, Glasgow, UK 3 Departamento de Estratigrafía y Paleontología, Universidad de Granada, Granada, Spain 4 School of Earth Sciences and Environmental Sustainability, Northern Arizona University, Flagstaff, USA

Biomarkers (such as n-alkanes, alkenones, alcohols, fatty acid) and isotopic records (such as δ13C total organic carbon (TOC), and atomic C/N ratios) have great potential for the reconstruction of the past environmental and climate change. Lakes provide high resolution record about paleoclimatic and paleoenvironmental changes on continents with local and regional responses to the climate change, used to reconstruct natural and human-induced changes in the ecosystems. The Holocene, usually considered as a stable period in terms of climate conditions, has been pointed by recent studies to have important variations in term of climate change. Moreover, high mountain lakes and peat bog in formerly glaciated terrain have been shown to be ideal locations for recovering records and to reconstruct the most recent climate change in the Iberian Peninsula. The study site (Borreguiles de la Caldera) is one of those high-elevation wetlands in the Sierra Nevada, southern Spain. This region is influenced by a complex climatology, which lead to highly sensitive high-elevation wetlands environment to the regional climate change. In order to study the climate change over the last 550 cal yr BP, n-alkanes proxies (CPI, ACL and Paq) have been calculated from 20 samples sediments, analyzed following the BECS protocol and measured using GC-FID and GC-MS. These proxies and isotopic records, compared to those of Borreguiles de la Virgen, have recorded relatively wet conditions in the Borreguiles de la Caldera record from 550 to 310 cal yr BP after a temporary arid event at 450 cal yr BP. This wet condition could be caused by relatively humid climate conditions during the first part of the LIA in southern Spain, which could have led to an increase in the water availability in the basin (without the development of a true lake at this period). From 310 to 60 cal yr BP, the record points to the continuation of bog conditions with a human impact in the most recent part of the record (for the last 60 years). This study will become part of a larger synthesis of sites across Sierra Nevada, helping to determine influence of climate on ecosystem response.

P8

Establishing a method for the application of 15N enriched compounds to

white clover (Trifolium repens) in rhizotrons

K. Pears1,2, I. Bull1, J. Dungait2, R. Evershed1, P. Murray2

1 Organic Geochemistry Unit, School of Chemistry, University of Bristol, Cantock’s Close, Bristol, BS8 1TS, UK. 2 Rothamsted Research North Wyke, Okehampton, Devon, EX20 2SB, UK.

The world’s population is predicted to be 9.5 billion by 2050. This will put increasing pressure on already stretched food supplies. Previously, food supply has been increased by the use of synthetic fertilisers, particularly focusing on nitrogen (N). However, fertilizers provide an unsustainable source of N, due to high energy demands for production, over-application and inadequate matching of fertiliser application to crop demand (synchrony). One solution to this is the use of legumes such as clover, which are capable of fixing atmospheric N. Nitrogen can be provided to the main crop through exudation or decomposition. However, a lack of understanding of the pathway of N and synchrony between clover and ryegrass has limited their use.

An initial experiment was performed in order to develop a method for introducing a 15N label to white clover (Trifolium repens) growing within a rhizotron and when sampling should occur. Ammonium nitrate (15NH4

15NO3) solution was applied to the roots or the shoots and, subsequently, leaves were analysed to determine the change in δ15N values with time. Rhizotrons were deconstructed at the end of the experimental period and plant parts separated. Results reveal increased δ15N values over the 361 hour time period when15NH4

15NO3 is applied to the roots and when applied to the shoots the uptake is slower but gives a more uniform distribution of the 15N label throughout the whole plant, which may provide the best method for applying compounds to rhizotrons. Amino acids in the roots were analysed by gas chromatography (GC) and gas chromatography-combustion-isotope ratio-mass spectrometry (GC-C-IRMS) to investigate whether the different methods of 15NH4

15NO3 derived label incorporation influenced the distribution of 15N label within the pool of amino acids and, by extension the plant exudate.

P9

Top down approaches to the molecular level characterisation of dissolved organic matter in river systems

J.Pemberton1, R.P.Evershed1, P.Johnes2

1 Organic Geochemistry Unit, University of Bristol, Bristol, United Kingdom 2 School of Geographical Sciences, University of Bristol, Bristol, United Kingdom

Rivers are the main transport mechanism for terrestrial derived organic matter and provide our drinking water. The dissolved organic matter (DOM) in rivers derives from both anthropogenic and natural sources and is a complex mixture of organic compounds, which can comprise over 10,000 different compounds.1 DOM is in a constant state of flux as compounds are photo-degraded, transported, used by the biota and react with other compounds in the river. The structural determination of compounds within DOM has up to now been limited to selected classes of compounds, i.e. pesticides2, detergents3 and pharmaceuticals4, which are known to have negative impacts on the environment.5

This project aims to further our understanding of the composition of DOM by use of high resolution mass spectrometry (HRMS) using a top down approach. HRMS has revolutionised the analysis of complex mixtures, since the precise determination of the masses of ions mass can be used to determine their molecular formulae and resolve molecular species that would be isobaric on earlier generations of MS instruments. Resolution of complex mixtures is further aided by the use of advanced separation techniques of liquid and gas chromatography, which can be coupled to HRMS gives further insights into the composition of complex mixtures. Adding tandem mass spectrometry allows determination of the structures of individual components of such mixtures.1

A major aim of this project is to investigate source contributions to DOM by sampling up and down stream of point sources and assessing differences in composition using high resolution mass spectra and chemometric algorithms. Determining the structure of individual components of DOM will allow chemical signatures of DOM to be developed as a basis for further investigation and monitoring of source contributions to overall DOM. Determining the dispersion and the degradation of DOM compounds will allow their lifetimes and fates to be mapped spatially and temporally.

The project will evaluate critical methodological aspects of DOM analysis using HRMS, including: methods for sampling and preserving a DOM, the physico-chemical effects of filtering, temperature and light exposure. These abiotic factors can all effect the composition of DOM in the time between sampling and analysis. In addition, biotic factors will be considered to assess the rates and patterns of biodegradation of DOM components by the biota present within the water column.

References 1. Minor, E.C., Swenson, M.M., Mattson, B.M., Oyler, A.R., 2014. Structural characterization of dissolved

organic matter: a review of current techniques for isolation and analysis. Environmental Science-Processes & Impacts 16, 2064-2079.

2. Ferrer, I., Barcelo, D., 1998. LC-MS methods for trace determination of pesticides in environmental samples. Analusis 26, M118-M122.

3. Goel, G., Kaur, S., 2012. A Study on Chemical Contamination of Water Due to Household Laundry Detergents. Journal of Human Ecology 38, 65-69.

4. Santos, L., Gros, M., Rodriguez-Mozaz, S., Delerue-Matos, C., Pena, A., Barcelo, D., Montenegro, M., 2013. Contribution of hospital effluents to the load of pharmaceuticals in urban wastewaters: Identification of ecologically relevant pharmaceuticals. Science of the Total Environment 461, 302-316.

5. Weston, D.P., Schlenk, D., Riar, N., Lydy, M.J., Brooks, M.L., 2015. Effects of pyrethroid insecticides in urban runoff on chinook salmon, steelhead trout and their invertebrate prey . Environmental Toxicology and Chemistry 34, 649-657.

P10

Development of a derivatization method using fluoro-tagged agents to improve chromatographic separation and detection characteristics of

lipids using 1-octadecanol as model

C. Poplawski1, B. J. Keely1

1 Department of Chemistry, University of York, Heslington, York YO10 5DD, U.K

Mass spectrometry has become a crucial technique in detection and analysis of lipids. Often it offers the only means of detection for compounds inactive under UV and fluorescence detection modes or which give poor response in alternative detection techniques including evaporative light scattering or refractive index detectors. Although, the combination of analyte retention time and unique mass to charge ratio (m/z) allows relatively easy identification of the many components, quantification is problematic owing variable and often poor ionisation efficiencies. The introduction of chromophore or fluorophore groups into lipid molecules has been explored previously through derivatization (Fitzpatrick and Siggia, 1973), however the use of hazardous reagents, long and complex derivatization protocols and variable conversion efficiencies limit their widespread application. Here we studied application of N-9-fluorenylmethyloxycarbonyl based derivatizing agents for alcohols, using 1-octadecanol as a model compound. The modification of the model compound via the Steglich esterification method (Neises and Steglich, 1978) under mild conditions gave esters in excellent yields in reactions carried under 90 min. The main advantages of this approach are the use of inexpensive derivatizing agents, simple reaction work up procedures and the resulting ester derivatives being readily amenable for UV, fluorescence and MS detection following chromatographic separation. References Fitzpatrick, F.A., Siggia, S., 1973. High resolution liquid chromatography of derivatized nonultraviolet

absorbing hydroxy steroids. Analytical Chemistry 45, 2310-2314. Neises, B., Steglich, W., 1978. Simple Method for the Esterification of Carboxylic Acids. Angewandte

Chemie International Edition in English 17, 522-524.

P11

Lipid biomarker distributions in Paleogene lignites from India

M. Rohrssen1, P. K. Singh2, M. P. Singh2, R. D. Pancost1

1 Organic Geochemistry Unit, School of Chemistry, The Cabot Institute, University of Bristol, UK 2 Coal and Organic Petrology Lab, Banaras Hindu University, India

Lignite and coal deposits in northern India provide snapshots of Paleogene-age (~23 to 65 Ma) tropical terrestrial ecosystems. We examined lipid biomarker proxies for thermal maturity, source organisms, and depositional conditions in a suite of 30 early Eocene to Oligocene-age lignite and coal samples from the Assam, Gujarat, Meghalaya, Nagaland, and Rajasthan regions in northern India.

Coals in the Meghalaya, Nagaland, and Assam regions of northeastern India exhibit mature hydrocarbon profiles, with low carbon preference indices and mature hopane distributions. Lignites in Gujarat and Rajasthan, northwestern India, have more complex hydrocarbon profiles, with abundant plant-derived terpanes, hopanes and hopenes, which differ markedly between forest-swamp and reed-marsh peat forming environments identified through organic petrography (Singh et al., 2010). Diverse hydrocarbon profiles among sites reflect large temporal and spatial variability in organic matter sources and preservation. References Singh, P.K., Singh, M.P., Singh, A.K., 2010. Petro-chemical characterization and evolution of Vastan

Lignite, Gujarat, India. International Journal of Coal Geology 82, 1-16.

P12

Fingerprinting of coal tar produced during Underground Coal

Gasification using GCxGC-TOFMS

I. Sampsonidis1, P. Younger2, C. Gauchotte-Lindsay1

1 Infrastructure and Environment Research Division, School of Engineering, University of Glasgow, Rankine Building, Oakfield avenue, Glasgow G12 8LT, UK 2 Systems Power and Energy Research Division, School of Engineering, University of Glasgow, James Watt Building, Glasgow G12 8QQ, UK

Although originally conceived more than a century ago, underground coal gasification (UCG) has been receiving increased attention in the past years. Technological advances in directional drilling, the possibility to couple the technology with carbon capture and storage (CCS) as well as its economical attractiveness have led to UCG consideration for widespread use (Couch, 2009, Paul et al., 2010). The process has a number of by-products, such as coal tar, the characterisation of which is necessary in order to access their environmental impact.

Coal tar has been analysed in the past using a number of methods including pressurised liquid extraction (PLE) followed by comprehensive two-dimensional gas chromatography coupled with time of flight mass spectrometry (GCxGC-TOFMS) (Paul et al., 2010). It was previously shown that the superior resolving power of GCxGC is suitable for analysing and classifying complex samples (McGregor et al., 2011). In this study we employ a previously developed PLE followed by GCxGC-TOFMS method to analyse coal tar derived from UCG.

Coal tar samples were taken every 24 hours of a 7 day in-situ gasification experiment conducted at the experimental mine “Barbara” in Katowice, Poland. In short, fingerprinting analysis showed that coal tar from UCG appears to be highly complex with several compound groups being identified such as polycyclic aromatic hydrocarbons (PAHs), phenols, heterocyclic compounds and their alkylated derivatives. A number of compositional differences had also been observed between the samples. References Couch, G.R., 2009. Underground Coal Gasification, Clean Coal Centre. London. Paul, Y., Gluyas, J., Cox, M., Roddy, D., 2010. Underground coal gasification. Ingenia 43-45. McGregor, L.A., Gauchotte-Lindsay, C., Daéid, N.N., Thomas, R., Daly, P., Kalin, R.M., 2011. Ultra

resolution chemical fingerprinting of dense non-aqueous phase liquids from manufactured gas plants by reversed phase comprehensive two-dimensional gas chromatography. Journal of Chromatography A 1218, 4755-4763.

P13

The effect of water table fluctuations on the carbon stocks in a northern

peatland (Butterburn Flow, northern England).

K. L. Simcock1, C. H. Vane2, G. D. Abbott1

1School of Civil Engineering and Geosciences, Drummond Building, Newcastle University, Newcastle Upon Tyne, UK, NE1 7RU 2British Geological Survey, Environmental Science Centre, Nicker Hill, Keyworth, Nottingham, UK, NG12 5GG

Northern peatlands are a major terrestrial carbon sink storing ~ 547 (473-621) Gt of Corg as waterlogged peat (> 60% of atmospheric carbon pool) which has important implications for the global carbon cycle (Yu et al., 2010). Global warming is expected to intensify the global hydrological cycle (Durack et al., 2012). It is essential that we understand how these ecosystems will react in response to climatic changes and the impact an intensified hydrological cycle will have on below ground carbon stocks. We have previously investigated the effect of water table fluctuations on the biogeochemistry of peat cores collected in the boreonemoral zone of central Sweden (Abbott et al., 2013). Butterburn Flow is the largest of 58 mires situated on the border of Cumbria and Northumberland and is a Site of Special Scientifc Interest (SSSI). This northern peatland has therefore been chosen as a representative study site in the UK. The aim of the project is to test whether fluctuations in water table will significantly influence the carbon storage capacity and organic geochemistry of the peat by i) exploring water table fluctuations using self-logging pressure transducers; ii) measuring the densities and Corg contents in the unsaturated, seasonally and permanently saturated layers of the peat; iii) exploring the molecular compositions in these three peat layers. References Abbott, G.D., Swain, E.Y., Muhammad, A.B., Allton, K., Belyea, L.R., Laing, C.G., Cowie, G.L., 2013.

Effect of water-table fluctuations on the degradation of Sphagnum phenols in surficial peats. Geochimica et Cosmochimica Acta 106, 177-191

Durack, P.J., Wijffels, S.E., Matear, R.J., 2012. Ocean salinities reveal strong global water cycle intensification during 1950 to 2000. Science 336, 455-458.

Yu, Z., Loisel, J., Brosseau, D.P., Beilman, D.W., Hunt, S.J., 2010. Global peatland dynamics since the Last Glacial Maximum Geophysical Research Letters 37, L13402.

P14

Chemosynthetic vs. photosynthetic contributions to particulate organic matter of contrasting Cold Water Coral ecosystems in the NE Atlantic.

E. Smith1, N. Dempster1, J. M. Roberts2, S. Hennighe2, G. A. Wolff3, K. Kiriakoulakis1

1 School of Natural Sciences and Psychology, Liverpool John Moores University, Byrom Street, Liverpool, L3 3AF, UK 2 School of Life Sciences, Heriot-Watt University, Edinburgh, EH14 4AS, UK 3 Earth, Ocean and Ecological Sciences Department, School of Environmental Sciences, University of Liverpool, Liverpool, L69 3GP, UK.

This study investigates the origin and nutritional quality of suspended particulate organic matter (sPOM) that reaches cold-water coral (CWC) ecosystems from two contrasting oceanographic settings of the N. E. Atlantic by carrying molecular (lipid) and stable isotopic analyses. These are the shallow (~150m) Mingulay Reef on the NW Scotland shelf vs the deeper (~700m) Logachev Mounds on the eastern slope of the Rockall Bank. sPOM is typically considered the sole energy source of CWCs (Roberts et al. 2009; Kiriakoulakis et al. 2005), although reliance on chemosynthetic sources has also been proposed (Hovland & Thomsen 1997; Becker et al. 2009). The study of sPOM in the vicinity of CWCs in relation to specific biogeochemical and oceanographic regimes can help to understand the sources, nutritional requirements and energy flow of these ecosystems.

Initial results show significant differences in the δ15N and δ13C values of sPOM between the two areas, indicating differences in trophic dynamics and sPOM re-working between locations and potential chemosynthetic contributions to sPOM in the Logachev Mounds. In addition preliminary lipid results show higher contributions of bacterial lipids and hydrocarbons in sPOM from the Logachev Mound province, an area where hydrocarbon-seep related contributions to CWC formation has been debated (Kiriakoulakis et al. 2006). This is the first study to our knowledge that suggests chemosynthetic contributions to sPOM in the vicinity of CWCs with important implications to their functioning. References Becker, E.L. Cordes, E.E., Macko, S. A., Fisher, C.R., 2009. Importance of seep primary production to Lophelia

pertusa and associated fauna in the Gulf of Mexico. Deep-Sea Research Part I: Oceanographic Research Papers 56, 786-800.

Hovland, M. & Thomsen, E., 1997. Cold-water corals—are they hydrocarbon seep related? Marine Geology 137, 159-164.

Kiriakoulakis, K. Fisher, E., Wolff, G.A., Freiwald, A., Grehan, A., Roberts, J.M., 2005. Lipids and nitrogen isotopes of two deep-water corals from the North-East Atlantic: initial results and implications for their nutrition. In A. Freiwald & J. M. Roberts, eds. Cold-water Corals and Ecosystems. Berlin: Springer-Verlag, pp. 715–729.

Kiriakoulakis, K., Freiwald, A., Fisher, E., 2006. Organic matter quality and supply to deep-water coral/mound systems of the NW European Continental Margin. International Journal of Earth Sciences 96, 159-170.

Roberts, J.M. et al., 2009. Mingulay reef complex: an interdisciplinary study of cold-water coral habitat, hydrography and biodiversity. Marine Ecology Progress Series 397, 139-151.

P15

Do oceanic particle collection techniques collect the same particles?

C. E. Smith1, G. Wolff1, C. Mahaffey1, K. Kiriakoulakis2

1 University of Liverpool, Liverpool, UK 2 Liverpool John Moores University, Liverpool, UK

Particulate organic material is of key importance for describing the distribution of key chemical elements such as carbon and nitrogen in the oceanic system. The accurate determination of particulate matter in the water column and a clear understanding of which particles are collected by different techniques is, therefore, key to understanding the cycling of nutrients within the oceanic system. Until now, it has been assumed that different methods of particle collection, namely in situ pumps - Stand Alone Pumps (SAPs), large volume bottles - Marine Snow Catchers (MSC) and small volume bottles - CTD Niskin bottles all collect the same particles, however, this may well not be the case. To assess this, each of the collection methods was deployed in collecting samples from the Shelf Sea Biogeochemistry Celtic Sea cruise during summer 2014 in order to determine elemental (carbon and nitrogen) and biomarker (lipid) composition. Initial analyses suggest that the three techniques do in fact collect different fractions of the particulate pool. Particulate organic carbon (POC) concentrations from four stations were found to be 3.47±1.34 µmol POC l-1 for the SAPs, 1.04±0.5 µmol POC l-1 for the MSC suspended particles fraction, 1.06±0.16 µmol POC l-1 for the MSC slow sinking particle fraction, and 0.58±0.09 µmol POC l-1 for the CTD - a value six times smaller than the SAPs technique. Therefore, future studies need to carefully consider and evaluate the collection technique used in relation to the questions they are asking.

P16

LCMS analysis of bacteriohopanepolyols without derivatisation

H. M. Talbot, F. R. Sidgwick

School of Civil Engineering and Geosciences, Newcastle University, Newcastle upon Tyne, UK

Traditional methods of analysis of bacteriohopanepolyols (BHPs; a type of membrane lipid) have typically relied on a derivatisation step, usually acetylation with acetic anhydride and pyridine, prior to analysis (e.g. Talbot et al., 2003). However, modern chromatographic techniques should be able to separate complex BHP mixtures without derivatisation. To that end a number of different protocols were investigated including various types of Hydrophilic interaction chromatography (HILIC) and reversed phase chromatography with volatile solvent modifiers to test their ability to separate BHP mixtures. HILIC chromatography using a Waters HILIC Amide column proved effective in separating a range of BHPs which contain a primary amine, however, other BHPs in the same mixture which did not carry and amine were not observed at high or low pH conditions with either electrospray (ESI) or atmospheric pressure chemical ionisation (APCI) in positive or negative ionisation mode. The presence of the terminal amine in many of these molecules also causes difficulties during traditional reversed phase chromatography due to interaction of the amine base with the silica support, therefore a highly base deactivated sorbent is required. Two of the leading reversed phase column types, Waters BEH C18 and ACE C18 were tested using a simple ternary solvent gradient identical to that used for acetylated BHPs (Talbot et al., 2003) but with 0.1% formic acid as a solvent modifier. Here we will show that the ACE column produced superior separation for both amine-containing and non amine BHPs and will compare data from UPLC-MS-MS and HPLC-MSn to demonstrate significant differences in ionisation and mass spectral signatures. References Talbot, H.M., Rohmer, M., Farrimond, P., 2007. Rapid structural elucidation of composite bacterial

hopanoids by atmospheric pressure chemical ionisation liquid chromatography/ion trap mass spectrometry. Rapid Communications in Mass Spectrometry 21, 880-892.

P17

Position Specific Isotope Analysis as a method of elucidating the

biodegradation mechanisms of contaminants in complex site samples.

S. M. Turnbull 1, B. White 2, C. Gauchotte-Lindsay 1

1 Division of Infrastructure and Environment, School of Engineering, University of Glasgow, Glasgow, Scotland, G12 8LT 2 Cedar Court, Grove Park Business Est. White Waltham, Maidenhead, Berks, SL6 3LW

Position specific isotope analysis (PSIA) is a developing area of isotope research which identifies the intramolecular distribution of isotopes at specific positions in a compound (Corso & Brenna,1997). We are currently developing a second generation on-line PSIA system based on Gauchotte et al. (2009).

The method uses gas chromatography (GC) as an on-line separation technique to separate a sample before it is introduced into a GC isotope ratio mass spectrometer (IRMS). A sample is separated on a capillary column in the initial GC, then an individual compound is separated via a valve system. Allowing different compounds within a sample to be directed to a flame ionisation detector (FID) for quantification or to a pyrolysis furnace for subsequent isotope analysis.

A process of on-line pre-concentration in the initial GC is currently being developed using a cryotrap system. The cryotrap is cooled to -10°C and contains a Tenax® sorbent phase, allowing for multiple injections of a selected isomer to accumulate on the cryotrap before being transferred to a GC IRMS.

Preliminary research focuses on the analysis of two isomers of methylnaphthalene. Methylnaphthalene’s are found naturally in fossil fuels and are used frequently in many manufacturing processes (Jia & Batterman, 2010), thus associated contamination can be an environmental problem.

Ultimately, the system will develop so that a selected isomer can sent to a pyrolysis furnace (Somers et al., 2007). The pyrolysates will be collected on the cryotrap before reinjection into the GC IRMS using a heated transfer system. Consequentially, the pyrolysis, collection and transfer system in the initial GC prior to the GC IRMS will outline the δ13C values of the different pyrolysates contained in an isomer of methylnaphthalene. Quantifying the isotopic ratio of an isomer at an intramolecular level. References Corso, T.N., Brenna, J.T.,1997. High-precision position-specific isotope analysis. Proceedings of the

National Academy of Sciences 94, 1049-1053. Gauchotte, C., O'Sullivan, G., Davis, S., Kalin, R.M., 2009. Development of an advanced on‐line

position‐specific stable carbon isotope system and application to methyl tert‐butyl ether. Rapid Communications in Mass Spectrometry 23, 3183-3193.

Jia, C., Batterman, S., 2010. A critical review of naphthalene sources and exposures relevant to indoor and outdoor air. International journal of environmental research and public health 7, 2903-2939.

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