Chemical signatures of the Anthropocene in the Clyde Estuary, UK: sediment hosted Pb, 207/206 Pb, Total Petroleum Hydrocarbons (TPH), Polyaromatic Hydrocarbon (PAH) and Polychlorinated Bipheny (PCB) pollution records

The sediment concentrations of total petroleum hydrocarbons (TPHs), polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), Pb and 207/206Pb isotope ratios were measured in seven cores from the middle Clyde estuary (Scotland, UK) with an aim of tracking the late Anthropocene. Concentrations of TPHs ranged from 34 to 4386 mg kg−1, total PAHs from 19 to 16 163 μg kg−1 and total PCBs between less than 4.3 to 1217 μg kg−1. Inventories, distributions and isomeric ratios of the organic pollutants were used to reconstruct pollutant histories. Pre-Industrial Revolution and modern non-polluted sediments were characterized by low TPH and PAH values as well as high relative abundance of biogenic-sourced phenanthrene and naphthalene. The increasing industrialization of the Clyde gave rise to elevated PAH concentrations and PAH isomeric ratios characteristic of both grass/wood/coal and petroleum and combustion (specifically petroleum combustion). Overall, PAHs had the longest history of any of the organic contaminants. Increasing TPH concentrations and a concomitant decline in PAHs mirrored the lessening of coal use and increasing reliance on petroleum fuels from about the 1950s. Thereafter, declining hydrocarbon pollution was followed by the onset (1950s), peak (1965–1977) and decline (post-1980s) in total PCB concentrations. Lead concentrations ranged from 6 to 631 mg kg−1, while 207/206Pb isotope ratios spanned 0.838–0.876, indicative of various proportions of ‘background’, British ore/coal and Broken Hill type petrol/industrial lead. A chronology was established using published Pb isotope data for aerosol-derived Pb and applied to the cores

Clyde tributaries : report of urban stream sediment and surface water geochemistry for Glasgow

This report presents the results of an urban drainage geochemical survey carried out jointly by the British Geological Survey (BGS) and Glasgow City Council (GCC) during June 2003. 118 stream sediment and 122 surface water samples were collected at a sample density of 1 per 1 km2 from all tributaries draining into the River Clyde within the GCC administrative area. The study was carried out as part of the BGS systematic Geochemical Surveys of Urban Environments (GSUE) programme. Stream sediment and surface water samples underwent analysis for approximately 46 chemical elements including contaminants such as As, Al, Cd, Cu, Cr, Ni, Pb, Se, V and Zn according to standard GSUE procedures. In addition, parameters such as ammonium, asbestos and Hg as well as organic contaminants such as total petroleum hydrocarbons (TPH), polycyclic aromatic hydrocarbons (PAH), poly-chlorinated biphenyls (PCB) and organo-tin compounds were assessed. The aim of the project was to provide an overview of urban drainage geochemistry in Glasgow to link to an on-going sister project, which is investigating the geochemistry of the Clyde estuary. This report presents the initial findings of the Clyde tributaries survey but it is envisaged that the data will be interpreted in more detail as part of a wider Clyde basin study once the Clyde estuary survey is completed

Bioaccumulation surveillance in Milford Haven Waterway

Biomonitoring of contaminants (metals, organotins, PAHs, PCBs) was carried out along the Milford Haven Waterway (MHW) and at a reference site in the Tywi Estuary during 2007-2008. The species used as bioindicators encompass a variety of uptake routes - Fucus vesiculosus (dissolved contaminants); Littorina littorea (grazer); Mytilus edulis and Cerastoderma edule (suspension feeders); and Nereis diversicolor (omnivore which often reflects contaminants in sediment). Differences in feeding strategy and habitat preference have subtle implications for bioaccumulation trends though, with few exceptions, contaminant body burdens in Milford Haven (MH) were higher than those at the Tywi reference site, reflecting inputs. Elevated concentrations of metals were occasionally observed at individual MH sites, whilst As and Se (molluscs and seaweed) were, for much of MHW, consistently at the higher end of the UK range. However, for the majority of metals, distributions in MH biota were not exceptional by UK standards. Several metal-species combinations indicated increases in bioavailability at upstream sites, which may reflect the influence of geogenic or other land-based sources – perhaps enhanced by lower salinity (greater proportions of more bioavailable forms). TBT levels in MH mussels were below OSPAR toxicity thresholds and in the Tywi were close to zero. Phenyltins were not accumulated appreciably in Mytilus, whereas some Nereis populations may have been subjected to localized (historical) sources. PAHs in Nereis tended to be evenly distributed across most sites, but with somewhat higher values at Dale for acenaphthene, fluoranthene, pyrene, benzo(a)anthracene and chrysene; naphthalenes tended to be enriched further upstream in the mid-upper Haven (a pattern seen in mussels for most PAHs). Whilst concentrations in MH mussels were mostly above reference site and OSPAR backgrounds, it is unlikely that ecotoxicological guidelines would be exceeded. PCBs in mussels were between upper and lower OSPAR guidelines and were unusual in their distribution in that highest levels occurred at the mouth of MH. Condition indices (CI) of bivalves (mussels and cockles) were highest at the Tywi reference site and at the seaward end of MH, decreasing upstream along the Waterway. There were a number of significant (negative) relationships between CI and body burdens and multivariate analysis indicated that a combination of contaminants could influence the pattern in condition (and sub-lethal responses such as MT and TOSC) across sites. Cause and effect needs to be tested more rigorously in future assessments

Organic geochemistry of Palaeozoic source rocks, central North Sea (CNS)

This report details a regional analysis of the source rock quality and potential of Palaeozoic rocks of the UK Central North Sea for the 21CXRM Palaeozoic project. The objective was to undertake a regional screening of all intervals to identify source rocks using new and legacy datasets of all Carboniferous and Devonian samples. In addition, a literature review (Appendix 1) summarises source and kerogen typing information from legacy reports. The background and stratigraphic nomenclature are given in Monaghan et al. (2016), details on individual well interpretations and stratigraphy are given in Kearsey et al. (2015). Geological context on the results of this work are included in basin modelling (Vincent, 2015) and were synthesised into a petroleum systems analysis in Monaghan et al. (2015). New and legacy Carboniferous and Devonian source rock geochemical data were examined per well using industry standard criteria to give an overview of the source rock quality, type (oil or gas prone) and maturity. The aims of this study were to classify the source rock quality of 33 wells, to examine if intervals were ‘gas-prone’ or ‘oil-prone’, and to ascertain the hydrocarbon generation stage of each well based on Rock-Eval pyrolysis, vitrinite reflectance (VR, where available) and total organic carbon (TOC) data. The term ‘gas prone’ was used to describe source rocks that have or could generate gas; ‘oil prone’ for source intervals that have or could generate oil. This study was a rapid screening exercise to identify intervals or areas of interest, and as such the data and inferences must be used concomitantly with other geological data to fully assess the source rock potential within the studied wells. It should be noted that the wells studied penetrate different parts of the geological succession and in many cases only small sections of the Devonian and Carboniferous interval. An initial sift through the wells with available geochemical data indicated that 33 wells had enough data to be usefully evaluated. Subsequently it was found that 8 of the 33 wells had incomplete, unreliable or otherwise poor source rock quality data sets and therefore were not analysed further; the reasons are detailed in this report. The remaining 25 wells selected for analysis were: 43/28-2, 26/07-1, 26/08-1, 36/13-1, 36/23-1, 38/16-1, 38/18-1, 39/07-1, 41/08-1, 42/10a-1, 42/10b-2ST, 42/09-1, 41/10-1, 42/10b-2, 41/15-1, 43/21-2, 41/01-1, 41/20-1, 41/14-1, 43/02-1, 43/17-2, 43/20b-2, 43/28-1, 43/28-2, 44/13-1, 44/16-1. Samples analysed from the majority of these wells were interpreted to be gas prone in the Carboniferous succession (Figure 1). 1. 41/10-1, 41/14-1 and 41/20-1 contained source rocks that were both gas window mature (e.g. VR >1.3) and can be regarded as excellent gas source. Strata in 43/17-2, 44/16-1 and 43/28-1 were also gas mature in all or parts of the section of interest, but with variable source rock quality. The six wells all had low S2 peaks: this may be due to either prior hydrocarbon generation and depletion or the initial presence of low amounts of non-inert kerogen. 2. 41/15-1, 42/10b-2 and 43/21-2 were also identified as possessing good gas-prone source rocks with elevated S2 values and also a high maturity attained by the source rocks. 41/01-1 was identified as a good for gas generation in the deeper section. 3. 26/07-1, 26/08-1, 36/13-1, 38/16-1, 39/07-1, 41/08-1, 42/10a-1, 42/10b-2ST, 42/09-1, 43/02-1, 43/20b-2, 43/28-2 and 44/13-1, contain good to excellent quality source rocks, but have not matured sufficiently to generate significant amount of gas, so these can be regarded as poor gas sources based on their current maturity. If present, in deeper basins some of these intervals will have generated significant quantities of gas

The pharmacokinetics of anthocyanins and their metabolites in humans

Background and Purpose: Anthocyanins are phytochemicals with reported vasoactive bioactivity. However, given their instability at neutral pH, they are presumed to undergo significant degradation and subsequent biotransformation. The aim of the present study was to establish the pharmacokinetics of the metabolites of cyanidin-3-glucoside (C3G), a widely consumed dietary phytochemical with potential cardioprotective properties. Experimental Approach: A 500 mg oral bolus dose of 6,8,10,3′,5′-13C5-C3G was fed to eight healthy male participants, followed by a 48 h collection (0, 0.5, 1, 2, 4, 6, 24, 48 h) of blood, urine and faecal samples. Samples were analysed by HPLC-ESI-MS/MS with elimination kinetics established using non-compartmental pharmacokinetic modelling. Key Results: Seventeen 13C-labelled compounds were identified in the serum, including 13C5-C3G, its degradation products, protocatechuic acid (PCA) and phloroglucinaldehyde (PGA), 13 metabolites of PCA and 1 metabolite derived from PGA. The maximal concentrations of the phenolic metabolites (Cmax) ranged from 10 to 2000 nM, between 2 and 30 h (tmax) post-consumption, with half-lives of elimination observed between 0.5 and 96 h. The major phenolic metabolites identified were hippuric acid and ferulic acid, which peaked in the serum at approximately 16 and 8 h respectively. Conclusions and Implications: Anthocyanins are metabolized to a structurally diverse range of metabolites that exhibit dynamic kinetic profiles. Understanding the elimination kinetics of these metabolites is key to the design of future studies examining their utility in dietary interventions or as therapeutics for disease risk reduction

Organic geochemistry of Palaeozoic Source Rocks of the Irish Sea, UK

The East Irish Sea gas and oil fields (Triassic reservoir e.g. Morecambe, Lennox) are believed to be sourced from the underlying Carboniferous strata (e.g. Armstrong et al., 1997; Quirk et al. 1999 and references therein). This study undertook a systematic screening of Rock-Eval and vitrinite reflectance data extracted from released legacy well reports with the aim of providing a data based, regional overview of Carboniferous source rock intervals and their levels of maturity in the wider Irish Sea study area. The method and description of calculated parameters used are given in Vane et al. (2015). The Palaeozoic stratigraphy of the region is described in Wakefield et al. (2016b) and the regional petroleum systems analysis in Pharaoh et al. (2016). Released geochemical data from the Palaeozoic of the Irish Sea is sparse and a variety of stratigraphical units have been sampled, mostly from units other than the likely main source rock interval (Bowland Shale Formation and equivalents). Nine wells were evaluated: 110/02b-10, 110/07-2, 110/07b-6, 110/09a-2, 111/25-1A, 113/27-1, 113/27-2 and 113/27-3. Well 110/12a-1 was not assessed due to the absence of key maturity information. In these wells, the Pennine Lower Coal Measures, Millstone Grit Group and Bowland Shale Formation are mainly gas-prone strata of poor-fair generative potential remaining and mature to the gas window at the sampled intervals in Quadrants 110 and 113 (Figure 1). Within the limited well sample set examined, high Total Organic Carbon (TOC) coal intervals have the best generative potential remaining. The Cumbrian Coastal Group, Appleby Group and Carboniferous Limestone Supergroup present in two wells in Quadrant 111 are at oil to gas window maturity levels, but have low TOC and low residual hydrocarbon generative potential

Equal abundance of odd and even n-alkanes from cycad leaves: can the carbon preference index (CPI) faithfully record terrestrial organic matter input at low latitudes?

Long chain n-alkanes from the leaves of thirteen extant cycad species within the Cycadacaea, Stangeriaceae, Zamiaceae families were measured by gas chromatographymass spectrometry (GC-MS). Cycad n-alkane patterns ranged from nC10-nC37, were unimodal in distribution, maximised at nC27-nC33 and gave average chain length (ACL) values of 23.9 to 31.0. Low carbon preference indices (CPI) in the range of 0.88 to 2.70 were observed which is atypical of lipids from the leaves of terrestrial plants. Analysis of variance between the three families of true cycads showed that there were no significant differences between CPI values. The unusually low CPI values (<1.5) in nine of the thirteen cycad species analysed suggests that caution needs to be exercised in the use of n-alkanes distibutions as a chemical marker of terrestrial plant input in sediments from tropical and sub-tropical regions

Organic geochemistry of Palaeozoic Source Rocks, Orcadian Study Area, North Sea, UK

A systematic screening of TOC, Rock-Eval and vitrinite reflectance data extracted from released legacy well reports was undertaken with the aim of providing a data based, regional overview of source rock intervals and their levels of maturity. Released, publicly available data is sparse; much of the data for the Devonian of the Orcadian Basin is contained with confidential commercial reports (see Greenhalgh (2016) for a literature review of available information with regards to source rocks and migrated Palaeozoic oils in this area). The regional screening approach used and technical parameters are described in Vane et al. (2015). The detailed stratigraphy is presented in Whitbread and Kearsey (2016; see Figure 2) and this regional screening is incorporated into the basin modelling work of Vincent (2016) and petroleum systems synthesis of Monaghan et al. (2016)

UK Geoenergy Observatories, Glasgow environmental baseline soil chemistry dataset

This report describes the environmental baseline topsoil chemistry dataset collected in February-March 2018 (03-18) as part of the United Kingdom Geoenergy Observatories (UKGEOS) project. Ninety, samples were collected from the shallow coal-mine Glasgow Geothermal Energy Research Field Site (GGERFS). The report accompanies the GGERFS Soil Chemistry03-18 dataset. It provides valuable information on soil chemistry prior to installation of the GGERFS-facility boreholes, against which any future change during the development/ running of the facility can be assessed. This information is necessary to help understand and de-risk similar shallow geothermal schemes in the future, provide public reassurance, and inform sustainable energy policy

Polycyclic aromatic hydrocarbons (PAH) and polychlorinated biphenyls (PCB) in urban soils of Greater London, UK

Surface soils from a 19 km2 area in east London, UK were analysed for polycyclic aromatic hydrocarbons (PAH) and polychlorinated biphenyls (PCB) (n = 76). ∑16 PAH ranged from 4 to 67 mg/kg (mean, 18 mg/kg) and ∑50 PAH ranged from 6 to 88 mg/kg (mean, 25 mg/kg). ∑7 PCB ranged from 1 to 750 μg/kg (mean, 22 μg/kg) and ∑tri-hepta PCB ranged 9 to 2600 μg/kg (mean, 120 μg/kg). Compared to other international cities concentrations were similar for PAH but higher for PCB. Normal background concentrations (NBC) were calculated and compared to risk-based human health generic assessment criteria (GAC). Benzo[a]pyrene NBC for urban (6.9 mg/kg), semi-urban (4.4 mg/kg) and urban + semi urban (6 mg/kg) domains exceed residential (1 mg/kg) and allotment (2.2 mg/kg) LQM/CIEH GAC (at 6% SOM) and the Indeno[1,2,3-cd]pyrene NBC for urban (6.8 mg/kg) and urban + semi-urban (5.2 mg/kg) domains exceed the residential (4.2 mg/kg) LQM/CIEH GAC (at 6% SOM). Capsule Abstract: Normal background concentrations of polycyclic aromatic hydrocarbons and polychlorinated biphenyls are elevated in east London soils and in some cases exceed regulatory assessment criteria