Papers by Christopher Vane
A B S T R A C T Polycyclic aromatic hydrocarbons (PAHs) are a group of organic compounds consisti... more A B S T R A C T Polycyclic aromatic hydrocarbons (PAHs) are a group of organic compounds consisting of two or more fused aromatic rings and are probably one of the most studied groups of organic chemicals in environmental research. PAHs originate mainly from anthropogenic processes, particularly from incomplete combustion of organic fuels. PAHs are distributed widely in particulate matter. Due to widespread sources and persistent characteristics, PAHs disperse through atmospheric transport and exist almost everywhere. Human beings are exposed to PAH mixtures in gaseous or particulate phases in ambient air. Long-term exposure to high concentrations of PAHs is associated with adverse health problems. This review identifies the main research and development themes in the measurement and occurrences of PAHs in dusts and particulates using a new approach to carrying out a literature review where many peer-review publications have been produced. The review extracts the most important research themes from a literature search using a combination of text mining and a more detailed review of selected papers from within the identified themes.
The existence of an extensive, prospective ViseaneNamurian Carboniferous petroleum system in and ... more The existence of an extensive, prospective ViseaneNamurian Carboniferous petroleum system in and around the hitherto under-explored Mid North Sea High is documented. Evidence is drawn from integrated analysis of over 50,000 line kilometres of seismic data and well data, together with regional source rock screening, reservoir analysis and basin modelling. Visean-Namurian marine and non-marine mudstones and coal source rocks are interbedded within fluvial and marine reservoir sandstones within a stacked succession up to 5 km thick. Source rocks are dominantly gas-prone with oil-prone intervals, and have reached oil to gas maturity levels dependent on location. Burial/thermal history modelling indicates a kitchen area on the southern margin of the Mid North Sea High with northwest and northeastwards migration of gas and oil during Mesozoic and Cenozoic times. A variety of structural and stratigraphic traps are possible, including intraformational Carboniferous traps, with a regional seal at Permian (Zechstein) level. Synthesis of many previously unpublished datasets demonstrates the ViseaneNamurian play south of the Mid North Sea High as part of an extensive petroleum system from the East Irish Sea, across onshore to offshore UK and into The Netherlands sector of the North Sea. The purpose of this synthesis is to highlight future exploration opportunities beneath and northwards of the productive Westphalian Southern North Sea gas basin, and to begin to de-risk the petroleum systems that are exemplified by the lower Carboniferous Breagh Field in a frontier area of the mature North Sea province.
A B S T R A C T Estuarine sediments can be a source of Phosphorus (P) to coastal waters, contribu... more A B S T R A C T Estuarine sediments can be a source of Phosphorus (P) to coastal waters, contributing to nutrient budgets and geochemical cycles. In this work, the concentration and speciation of P in 47 cores were examined from the inter-tidal mud flats of the tidal river Thames (~ 120 km). Results of P concentration and speciation were combined with published data relating to known sediment dynamics and water chemistry (salinity) within the estuary to produce a conceptual model of sediment-P behaviour. Results demonstrated significant P desorption occurring after sediment passed through the Estuarine Turbidity Maximum and when the salinity of the river water exceeded ~6 ppt. It was found that organic P was desorbed to a greater extent than inorganic P in the lower estuary. Models were used to identify those geochemical parameters that contributed to the Total P (R 2 = 0.80), oxalate extractable P (R 2 = 0.80) and inorganic P (R 2 = 0.76) concentrations within the Thames estuary.
Environmental Science & Technology, 2010
14 A fed state in vitro methodology capable of use in commercial testing laboratories has been 15... more 14 A fed state in vitro methodology capable of use in commercial testing laboratories has been 15 developed for measuring the human ingestion bioaccessibility of polyaromatic hydrocarbons 16 (PAHs) in soil (Fed ORganic Estimation human Simulation Test-FOREhST). The protocol 17 for measuring PAHs in the simulated gastro-intestinal fluids used methanolic KOH 18 saponification followed by a combination of polymeric sorbent solid phase extraction and 19 silica sorbent cartridges for sample clean-up and preconcentration. The analysis was carried 20 out using high pressure liquid chromatography with fluorescence detection. The repeatability of the method, assessed by the measurement of the bioaccessibility of 6 PAHs
Journal of the Marine Biological Association of the UK, 2005
This review provides insights into the distribution and impact of oestrogens and xeno-oestrogens ... more This review provides insights into the distribution and impact of oestrogens and xeno-oestrogens in the aquatic environment and highlights some signi¢cant knowledge gaps in our understanding of endocrine disrupting chemicals. Key areas of uncertainty in the assessment of risk include the role of estuarine sediments in mediating the fate and bioavailability of environmental (xeno)oestrogens (notably their transfer to benthic organisms and estuarine food chains), together with evidence for endocrine disruption in invertebrate populations.
We examined the use of d 13 C, TOC and C/N geochemistry of sedimentary organic matter to reconstr... more We examined the use of d 13 C, TOC and C/N geochemistry of sedimentary organic matter to reconstruct former sea levels and paleoenvironments in the absence of suitable microfossil data. The modern distribution of d 13 C, TOC and C/N of 33 vegetation and 74 surface sediment samples collected from four coastal wetlands in the Thames Estuary and Norfolk, UK are described. The d 13 C, TOC and C/N geochemistry of sediments varied in relation to the input of in situ vascular vegetation versus allochthonous particulate organic matter and algae, which was controlled primarily by tidal inundation. We reviewed published and unpublished studies to produce an English database of vegetation (n ¼ 257) and sediment (n ¼ 132) d 13 C, TOC and C/N geochemistry. Four elevation-dependent environments in the database had statistically distinct d 13 C, TOC and C/N values: (1) tidal flat/low marsh (d 13 C: À24.9 AE 1.2‰; TOC: 3.6 AE 1.7%; C/N: 9.9 AE 0.8); (2) middle marsh/high (d 13 C: À26.2 AE 1.0‰; TOC: 9.8 AE 6.7%; C/N: 12.1 AE 1.8); (3) reed swamp (d 13 C: À27.9 AE 0.7‰: TOC: 36.5 AE 11.5%; C/ N: 13.9 AE 1.2); and (4) fen carr (d 13 C: À29.0 AE 0.6‰; TOC: 41.6 AE 5.7%; C/N: 17.4 AE 3.1). The d 13 C, TOC and C/ N geochemistry database was applied to a Holocene sediment core collected from the Thames Estuary to produce three new sea-level index points and one limiting date, illustrating the utility of d 13 C, TOC and C/N values to reconstruct Holocene relative sea levels.
This review provides insights into the distribution and impact of oestrogens and xeno-oestrogens ... more This review provides insights into the distribution and impact of oestrogens and xeno-oestrogens in the aquatic environment and highlights some signi¢cant knowledge gaps in our understanding of endocrine disrupting chemicals. Key areas of uncertainty in the assessment of risk include the role of estuarine sedi- ments in mediating the fate and bioavailability of environmental (xeno)oestrogens (notably their transfer to benthic organisms and estuarine food chains), together with evidence for endocrine disruption in inver- tebrate populations. Emphasis is placed on using published information to interpret the behaviour and e¡ects of a small number of 'model compounds' thought to contribute to oestrogenic e¡ects in nature; namely, the natural steroid 17b-oestradiol (E2) and the synthetic hormone 17a-ethinyloestradiol (EE2), together with the alkyl- phenols octyl- and nonyl-phenol (OP, NP) as oestrogen mimics. Individual sections of the review are devoted to sources and concentra...
Chemosphere, 2014
This research investigates the effect of nine physical treatment types comprising a serial combin... more This research investigates the effect of nine physical treatment types comprising a serial combination of three drying (air, freeze and oven) and two comminution (milling and sieving) methods on the quantification of PAH in a soil sample from a former gasworks. Results show that treatment type has a significant effect on PAH concentration (p⩽0.05). Naphthalene, 1-methylnaphthalene and 2-methylnaphthalene concentrations were significantly higher for air drying and freeze drying treatments than for oven drying. It is suggested that naphthalene and similarly volatile PAH losses were greater for oven drying due to the application of fanned warm air which is thought to cause volatilisation. Analytical precision was significantly improved for milled samples compared with sieved samples. The reason milling results in greater precision is assigned to the improved solvent extraction efficiency when natural grain size is altered due to crushing. The analytical data were compared to residentia...
Water Science & Technology, 2010
The ability of two differing marine sediments (one clayey, the other sandy) to attenuate the expl... more The ability of two differing marine sediments (one clayey, the other sandy) to attenuate the explosive 2,4,6-trinitrotoluene (TNT), dissolved in intertidal seawater from the eastern English coast of the North Sea, was examined using aerobic microcosms. Analysis of the seawater from the microcosms revealed an initial sharp decline in TNT concentration with clayey sediment in both sterilized (to prevent microbial activity) and unsterilized microcosms. This effect did not occur to such a marked extent in similar sterile and non-sterile sandy sediment microcosms and was attributed mainly to sorption of TNT to the fine clay particles of the clayey sediment. As time progressed, the attenuation of TNT in microcosms containing either type of sediment was found to be less in those that had been sterilized compared with those where microbial action proceeded unhindered. Feeding the microcosms, (i.e. supplying extra carbon sources for the microbial communities), appeared to have a small, but perceptible, enhancing effect upon TNT dissipation. The attenuation of TNT was also measured in large microcosms containing 2.5 L of seawater and no sediment. Analysis of the seawater revealed a gradual decline in TNT concentration in non-sterile and fed microcosms compared to their sterile counterpart. Overall, this laboratory study showed that the attenuation of TNT is slow (half-life in seawater ca.1900 days; half-life sand sediment <700 days; half life in clay sediment 130 days) under conditions commonly encountered in coastal waters of the North Sea.
Soil Use and Management, 2008
o r P e e r R e v i e w Soil organic carbon in UK urban areas 2
Rapid Communications in Mass Spectrometry, 2011
Stable isotope analysis of sedimentary carbon in lakes can help reveal changes in terrestrial and... more Stable isotope analysis of sedimentary carbon in lakes can help reveal changes in terrestrial and aquatic carbon cycles. A method based on a single, photosynthetic organism, where host effects are minimised, should offer more precision than carbon isotope studies of bulk lake sediments. Here we report the development of a systematic method for use on fossil lacustrine diatom frustules, adapted from previous studies in marine environments. A stepwise cleaning experiment on diatomaceous lake sediments from Lake Challa, near Mount Kilimanjaro, was made to demonstrate the necessary treatment stages to remove external sedimentary carbon. Changes in soluble carbon compounds during these cleaning experiments were measured using gas chromatography/mass spectrometry (GC/ MS). The mass spectrometry methods were refined to measure the small percentage of carbon in these samples and details of these methods are presented. Samples of cleaned diatoms containing <1% carbon yielded robust results. Carbon isotope analyses of diatom samples containing different species mixtures were performed and suggested that differences existed, although the effects lay within current experimental error and require further work. Unlike what was found in work on oxygen and silicon isotopes from diatom frustules, mineral contamination had no discernible impact on the diatom carbon isotope ratios from these sediments. The range of values found in the lakes investigated thus far can be interpreted with reference to the supply and nature of carbon from the catchment as well as to the demand generated from lake primary productivity.
Quaternary Geochronology, 2012
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 2011
Organic Geochemistry, 2004
Analytical hydropyrolysis performed under high hydrogen gas pressure (> 10 MPa) has been demonstr... more Analytical hydropyrolysis performed under high hydrogen gas pressure (> 10 MPa) has been demonstrated to possess the unique ability to release high yields of biomarker hydrocarbons covalently bound within the non-hydrocarbon macromolecular fraction of crude oils and source rocks. This study describes the development of the experimental procedure for trapping the product oils (hydropyrolysates) on silica to facilitate more convenient recovery than conventional collection and to allow analysis by thermal desorption-GC-MS without any prior work-up. Conventionally, the trap has consisted of a stainless steel coil, cooled with dry ice from which the products are recovered in organic solvents. Replacing this with a system in which the hydropyrolysates are adsorbed on a small mass of silica greatly reduces the turn-around time between tests, and aids the recovery and separation of the products. This method has been developed using an oil shale and an oil asphaltene fraction, with the silica trap producing very similar biomarker profiles to that from the conventional trap. The quantitative recovery of hydrocarbons from a light crude oil desorbed from silica under hydropyrolysis conditions demonstrates no significant loss of the high molecular weight n-alkanes (> n-C 10 ) for both trapping methods. The use of liquid nitrogen as the trap coolant results in significantly improved recovery of the lower molecular mass constituents. The silica trapping method allows for the hydropyrolysates to be characterised by thermal desorption-GC-MS, which has been investigated both on-and off-line. The oils undergo relatively little cracking during desorption, with similar n-alkane and biomarker profiles being obtained as with normal work-up and GC-MS analysis. Thus, in terms of fingerprinting geomacromolecules, ''hypy-thermal desorption-GC-MS'' appears to have the potential to be developed as an attractive alternative to traditional py-GC-MS. #
Organic Geochemistry, 1999
Methoxyphenols can be used as proxies for terrestrial biomass when investigating the chemical cha... more Methoxyphenols can be used as proxies for terrestrial biomass when investigating the chemical changes in lignin during hydrothermal alteration. The closed system microscale pyrolysis of 2-methoxyphenol (2-MOP) and 2,6-dimethoxyphenol (2,6-DMP), in the presence of water vapour, has been studied in borosilicate glass vessels. 2-MOP was heated isothermally at temperatures of 330 C for 96 h and 2,6-DMP was heated isothermally at 300 C for 118 h. Pyrolysis of the model compound 2-MOP gave a simple product distribution which was composed mainly of 1,2dihydroxybenzene with lower amounts of 2-methylphenol and phenol. The prominent reaction products from heating 2,6-DMP were 1,2-dihydroxy-6-methoxybenzene and 2-methoxy-6-methylphenol, with minor amounts of 2-MOP, 1,2dihydroxybenzene and 2-methylphenol. The decreasing amounts of 2,6-DMP with heating time and the concomitant increase in the amounts of 1,2-dihydroxy-6-methoxybenzene suggested that demethylation had occurred. #
Marine Pollution Bulletin, 2008
Marine Pollution Bulletin, 2009
sediments. This is due to its toxic effect on marine invertebrates and tendency for the methyl-Hg... more sediments. This is due to its toxic effect on marine invertebrates and tendency for the methyl-Hg to bio-accumulate up trophic levels, where it can enter humans via the ingestion of fish and shellfish . The Mersey estuary (NW England, UK) has a highly industrialised and urbanised drainage basin of approximately 5000 km 2 . Elevated Hg concentrations (>2 mg/kg) in sediments from the Mersey estuary can be attributed in part to the high density of chemical factories in the Widnes-Runcorn area . In particular, the alkali, bleaching and detergents industries developed in this area in the mid-19 th century used the Castner-Kellner process for large-scale sodium hydroxide and bleach production. This process required a flowing liquid mercury cathode in an electrolytic reaction cell. Losses and discharges from such plants, plus releases from other industries and domestic coal-burning, will have released many tonnes of Hg to the estuary over several decades. In addition to their anthropogenic metal burden, Mersey estuary sediments are also contaminated with persistent organic pollutants (POPs) sourced from the dockyards, shipping, chemical works, oil refineries and
Journal of Quaternary Science, 2012
We investigated use of d 13 C in bulk organic sediment to define the botanical origin of samples ... more We investigated use of d 13 C in bulk organic sediment to define the botanical origin of samples preserved in coastal sediment as a means to reconstruct relative sea level in New Jersey, USA. Modern transects at three sites demonstrated that low and high salt-marsh floral zones dominated by C 4 species (Spartina alterniflora and Spartina patens) were associated with sediment d 13 C values between À18.9% and À15.8% and occurred from mean tide level (MTL) to mean higher high water (MHHW). Brackish transitional settings vegetated by Phragmites australis with Iva fructescens and Typha sp. (C 3 species) and freshwater upland samples (C 3 species) were characterized by bulk sediment d 13 C values of À27.0% to À22.0% and existed above MHHW. Parallel transects at one site suggested that intra-site variability was not discernible. The utility of d 13 C values for reconstructing relative sea level in New Jersey is limited by an inability to differentiate between brackish sediments related to sea level and freshwater upland samples. To facilitate this distinction in a 4.4 m core, we used a multi-proxy approach (d 13 C values with presence or absence of agglutinated foraminifera) to recognize indicative meanings for four sample types. Sediment with d 13 C values greater than À18.9% was derived from a vegetated salt-marsh and formed between MTL and MHHW. Sediment with d 13 C values less than À22.0% and containing agglutinated foraminifera formed in a brackish transitional zone between MHHW and highest astronomical tide (HAT). This is the narrowest elevational range of the four sample types and most precise sea-level indicator. Sediment with d 13 C values less than À22.0% and lacking foraminifera can only constrain the upper bound of former sea level. Samples with intermediate values (À22.0% to À18.9%) formed between MTL and HAT. Using these indicative meanings and radiocarbon dates, we suggest that a transition from brackish to salt-marsh d 13 C values recorded in the core took approximately 350 years (from 1800 to 1450 cal. a BP).
Journal of Analytical and Applied Pyrolysis, 2001
Pyrolysis-gas chromatography-mass spectrometry, in the presence of tetramethylammonium hydroxide ... more Pyrolysis-gas chromatography-mass spectrometry, in the presence of tetramethylammonium hydroxide (TMAH), was used in the molecular characterisation of lignin in wheat straw during its fungal degradation by Agaricus bisporus. The decayed wheat straw had a lower proportion of syringyl to guaiacyl derived moieties than its native counterpart. The ratio of methyl 3,4-dimethoxybenzoate to 3,4-dimethoxybenzaldehyde increased from 1.0 in native wheat straw to 6.4 following fungal degradation. Similarly the ratio of methyl 3,4,5-trimethoxybenzoate to 3,4,5-trimethoxybenzaldehyde increased from 1.6 in native wheat straw to 3.1 upon decay. The increase in both guaiacyl and syringyl acid to aldehyde ratios indicated that A. bisporus induces oxidative cleavage of lignin at the Ca Cb bonds. Both the threo-and erythro-isomers of 1-(3,4-dimethoxyphenyl)-1,2,3-trimethoxypropane decreased in intensity relative to other thermochemolysis products in degraded wheat straw. The increase in the ratio of methyl 3,4,-dimethoxybenzoate to the sum of 1-(3,4dimethoxyphenyl)-1,2,3-trimethoxypropane (threo-and erythro-isomers) from 1.0 in native wheat straw to 10.9 in A. bisporus decayed wheat straw confirmed that the fungus had cleaved alkyl side chains. Pyrolysis-gas chromatography-mass spectrometry in the presence of TMAH provides a sensitive method for tracking the oxidative degradation of lignin during the fungal decay of wheat straw.
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Papers by Christopher Vane