Organic G 13 C and C/N analyses of estuarine deposits provide proxies for changes in the source of organic matter, which can be driven by fluctuations in relative sea level, river discharge, and catchment disturbance. Here we present the results of a comprehensive vegetation and sediment G 13 C and C/N survey of Welwich Marsh (outer Humber Estuary, UK), together with high-resolution G 13 C and C/N analyses of

Editorial handling by M. Kersten a b s t r a c tSurface soils from a 19 km 2 area in east London, UK were analysed for polycyclic aromatic hydrocarbons (PAH) and polychlorinated biphenyls (PCB) (n = 76).P 16 PAH ranged from 4 to 67 mg/kg (mean, 18 mg/ kg) and P 50 PAH ranged from 6 to 88 mg/kg (mean, 25 mg/kg).P 7 PCB ranged from 1 to 750 lg/kg (mean, 22 lg/kg) and P tri-hepta PCB ranged 9 to 2600 lg/kg (mean, 120 lg/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.

The sediment concentrations of total petroleum hydrocarbons (TPHs), polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), Pb and 207/206 Pb 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 mg kg −1 and total PCBs between less than 4.3 to 1217 mg kg −1 . Inventories, distributions and isomeric ratios of the organic pollutants were used to reconstruct pollutant histories. Pre-Industrial Revolution and modern nonpolluted 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 207/206 Pb 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.

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Tropical peatland ecosystems are a significant component of the global carbon cycle and feature a range of distinct vegetation types, but the extent of links between contrasting plant species, peat biogeochemistry and greenhouse gas fluxes remains unclear. Here we assessed how vegetation affects small scale variation of tropical peatland carbon dynamics by quantifying in situ greenhouse gas emissions over 1 month using the closed chamber technique, and peat organic matter properties using Rock-Eval 6 pyrolysis within the rooting zones of canopy palms and broadleaved evergreen trees. Mean methane fluxes ranged from 0.56 to 1.2 mg m −2 h −1 and were significantly greater closer to plant stems. In addition, pH, ranging from 3.95 to 4.16, was significantly greater closer to stems. A three pool model of organic matter thermal stability (labile, intermediate and passive pools) indicated a large labile pool in surface peat (35–42%), with equivalent carbon stocks of 2236–3065 g m −2 . Methane fluxes were driven by overall substrate availability rather than any specific carbon pool. No peat properties correlated with carbon dioxide fluxes, suggesting a significant role for root respiration, aerobic decomposition and/or methane oxidation. These results demonstrate how vegetation type and inputs, and peat organic matter properties are important determinants of small scale spatial variation of methane fluxes in tropical peatlands that are affected by climate and land use change. Electronic supplementary material The online version of this article (10.1007/s10533-018-0531-1) contains supplementary material, which is available to authorized users.

Exploration for shale gas occurs in onshore basins, with two approaches used to predict the maximum gas in place (GIP) in the absence of production data. The first estimates adsorbed plus free gas held within pore space, and the second measures gas yields from laboratory pyrolysis experiments on core samples. Here we show the use of sequential high-pressure water pyrolysis (HPWP) to replicate petroleum generation and expulsion in uplifted onshore basins. Compared to anhydrous pyrolysis where oil expulsion is limited, gas yields are much lower, and the gas at high maturity is dry, consistent with actual shales. Gas yields from HPWP of UK Bowland Shales are comparable with those from degassed cores, with the ca. 1% porosity sufficient to accommodate the gas generated. Extrapolating our findings to the whole Bowland Shale, the maximum GIP equate to potentially economically recoverable reserves of less than 10 years of current UK gas consumption.

The depositional history of peat dominated wetlands can be used to understand palaeoclimate and paleohydrology, and also constrain the impacts of future climate change. However, in chalkland valleys seasonal water table fluctuations and a high alkalinity have decimated key environment indicators such as pollen and there is a need for alternative investigative techniques. The method of Rock-Eval pyrolysis can track changes in organic matter source and degradation, potentially relating to historic changes in vegetation cover. This was piloted on cores from a groundwater dependent riparian chalk valley wetland combined with radiocarbon dating. The dating showed that the cores represented approximately 4000 years of depositional history. Rock-Eval demonstrated significant changes in the normal alkane composition of the peat indicating shifts of around 500 to 1000 years between terrestrial and more aquatic species, relating to periods of climate wetness. These climatic shifts are broadly consistent with other evidence from ombrotrophic peatland and lacustrine sediments across northwest Europe. However, the connection between climate wetness and groundwater dependent chalkland wetlands is complicated by external anthropogenically-driven factors relating to land-use and vegetation cover changes in the catchment. Nonetheless this study suggests that Rock-Eval pyrolysis is a useful and cost-effective tool that can provide evidence for long-term Holocene groundwater fluctuations.

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