Contrasting sewage, emerging and persistent organic pollutants in sediment cores from the River Thames estuary, London, England, UK.

Sedimentary organic pollution in the urban reaches of the Thames estuary is changing from fossil fuel hydrocarbons to emerging synthetic chemicals. De-industrialisation of London was assessed in three cores from Chiswick (Ait/Eyot) mud island using pharmaceuticals, faecal sterols, hydrocarbons (TPH, PAH), Black Carbon (BC) and organotins (TBT). These ranked in the order; BC 7590-30219 mg/kg, mean 16,000 mg/kg > TPH 770-4301, mean 1316 mg/kg > Σ16PAH 6.93-107.64, mean 36.46 mg/kg > coprostanol 0.0091-0.42 mg/kg, mean of 0.146 mg/kg > pharmaceuticals 2.4-84.8 µg/kg, mean 25 µg/kg. Hydrocarbons co-varied down-profile revealing rise (1940s), peak (1950s -1960s) and fall (1980s) and an overall 3 to 25-fold decrease. In contrast, antibiotics, anti-inflammatory (ibuprofen, paracetamol) and hormone (17ß-estradiol) increased 3 to 50-fold toward surface paralleling increasing use (1970s-2018). The anti-epileptics, carbamazepine and epoxcarbamazepine showed appreciable down-core mobility. Faecal sterols confirmed non-systematic incorporation of treated sewage. Comparison to UK sediment quality guidelines indicate exceedance of AL2 for PAH whereas TBT was below AL1.

Grain size and organic carbon controls polyaromatic hydrocarbons (PAH), mercury (Hg) and toxicity of surface sediments in the River Conwy Estuary, Wales, UK.

The Conwy estuary was evaluated for sediment quality. Microtox bioassay revealed 38 of 39 sites were non-toxic. Hg ranged from 0.001 to 0.153 µg kg-1, mean 0.026 mg kg-1, Σ16 PAH from 18 to 1578 µg kg-1, mean 269 µg kg-1, Σ22 PAH, 18 to 1871 µg kg-1 mean to 312 µg kg-1, two sites had high perylene relative to ΣPAH. Σ22PAH correlated positively with TOC, clay and silt (R2 0.89, 0.92, 0.90) and negatively with sand. Multivariate statistics, delineated four spatial (site) and five variable (measurements) clusters. Spatial clustering relates to sediment grain size, in response to hydrodynamic processes in estuary; fine (clay to silt) sized sediments exhibit the highest Hg and PAH content, because these components partitioned into the fine fraction. Comparison to national and international environmental standards suggests Hg and PAH content of Conwy sediments are unlikely to harm ecology or transfer up into the human food chain.

Organic pollutants, heavy metals and toxicity in oil spill impacted salt marsh sediment cores, Staten Island, New York City, USA.

Sediment cores from Staten Island's salt marsh contain multiple historical oil spill events that impact ecological health. Microtox solid phase bioassay indicated moderate to high toxicity. Multiple spikes of TPH (6524 to 9586 mg/kg) and Σ16 PAH (15.5 to 18.9 mg/kg) were co-incident with known oil spills. A high TPH background of 400-700 mg/kg was attributed to diffuse sources. Depth-profiled metals Cu (1243 mg/kg), Zn (1814 mg/kg), Pb (1140 mg/kg), Ni (109 mg/kg), Hg (7 mg/kg), Cd 15 (mg/kg) exceeded sediment quality guidelines confirming adverse biological effects. Changes in Pb206/207 suggested three metal contaminant sources and diatom assemblages responded to two contamination events. Organic and metal contamination in Saw Mill Creek Marsh may harm sensitive biota, we recommend caution in the management of the 20-50 cm sediment interval because disturbance could lead to remobilisation of pre-existing legacy contamination into the waterway.

Trends in heavy metals, polychlorinated biphenyls and toxicity from sediment cores of the inner River Thames estuary, London, UK.

River islands (Ait or Eyot) within the inner tidal Thames serve as unique recorders of current and historical estuarine chemical pollution. Sediment cores from Chiswick Ait were assessed for contamination using Microtox® solid phase bioassay, stable isotopes (δ13C, δ15N), heavy metals and polychlorinated biphenyls (PCBs). Microtox® classified these sediments as non-toxic to moderately toxic and bulk isotopes identified a change in organic input. Metals Cu, Zn, Cr, Ni, Cd, Hg and Ag showed parallel rise, peak and fall profiles which when allied to a 207/208Pb and 137Cs based chronology supported major changes in trace metal contributions corresponding to approximate input times of 1940 (rise), 1963 (peak) and 1985 (fall). Metals ranged from Cu 15 to 373 mg kg-1 (mean 141 mg kg-1), Zn 137 to 1331 mg kg-1 (mean 576 mg kg-1), Cr 14-351 mg kg-1 (mean 156 mg kg-1), Pb 10 to 1506 mg kg-1 (mean 402 mg kg-1), As 1 to 107 (mean 38 mg kg-1), Ni 11 to 113 mg kg-1 (mean 63 mg kg-1), Cd 0.2 to 53 mg kg-1 (mean 9 mg kg-1), Hg 1 to 8 mg kg-1 (mean 4.6 mg kg-1) and Ag from 0.7 to 50 mg kg-1 (mean 7.5 mg kg-1). Down core total PCBs ranged from 10.5 to 121 µg kg-1 and mean of 39 µg kg-1. The rise, peak and fall of Cu, Zn, Cr, Ni, Cd and Ag pollution matched local sewage works' treatment discharge records. Whereas the Hg, Pb and As profiles were disconnected, reflecting alternative historic sources and or partitioning behaviour. Comparison to marine sediment quality guidelines indicate that Zn, Pb, Ni, Cd and Hg exceed action level 2, whereas sedimentary Cu, Cr and As concentrations were above action level 1 (no action) but below action level 2 (further investigation required). The river islands of the tidal Thames capture a unique contaminant chemistry record due in part to their location in the tidal frame (salinity minimum) and close proximity to west London.

Shale gas reserve evaluation by laboratory pyrolysis and gas holding capacity consistent with field data.

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.

Petroleomic depth profiling of Staten Island salt marsh soil: 2ω detection FTICR MS offers a new solution for the analysis of environmental contaminants.

Staten Island is located in one of the most densely populated regions of the US: the New York/New Jersey Estuary. Marine and industrial oil spills are commonplace in the area, causing the waterways and adjacent marshes to become polluted with a range of petroleum-related contaminants. Using Rock-Eval pyrolysis, the hydrocarbon impact on a salt marsh was assessed at regular intervals down to 90 cm, with several key sampling depths of interest identified for further analysis. Ultrahigh resolution data are obtained by direct infusion (DI) atmospheric pressure photoionization (APPI) on a 12 T solariX Fourier transform ion cyclotron resonance mass spectrometer (FTICR MS) allowing trends in the compositional profile with depth to be observed, such as changes in the relative hydrocarbon intensity and the relative contributions from oxygen- and sulfur-containing groups. These trends may correlate with the timing of major oil spills and leaks of petroleum and other industrial chemicals into the waterways. The use of gas chromatography (GC) coupled to a 7 T solariX 2XR FTICR MS equipped with an atmospheric pressure chemical ionization (APCI) ion source offers retention time resolved and extensive compositional information for the complex environmental samples complementary to that obtained by DI-APPI. The compositional profile observed using GC-APCI FTICR MS includes contributions from phosphorous-containing groups, which may be indicative of contamination from other anthropogenic sources.

Carbon isotope alteration during the thermal maturation of non-flowering plant species representative of those found within the geological record.

RATIONALE: The carbon isotope (δ13 C value) composition of fossil plant material is routinely used as a proxy of past climate and environment change. However, palaeoclimate interpretation requires assumptions about the stability of δ13 C values in plant material during its decomposition and incorporation into sediments. Previous work on modern angiosperm species shows δ13 C changes of several per mille during simulated decomposition experiments. However, no such tests have been undertaken on non-flowering plants, which are found extensively within the geological record. These plants have distinctly different cellulose-to-lignin ratios from those of their angiosperm counterparts, potentially creating hitherto unknown variations in the original to fossil δ13 C signatures. METHODS: To test the extent of δ13 C change during decomposition we have subjected a number of plants, representing more basal, non-flowering plant lineages (cycads, ferns, horsetails and dawn redwood), to artificial decay using a hydrothermal maturation technique at two temperatures over periods of up to 273 hours. Subsamples were extracted every 12-16 hours and analysed for their δ13 C and %C values using a Carlo Erba 1500 elemental analyser, and VG TripleTrap and Optima mass spectrometers. RESULTS: The %C values increased for all samples through the maturation process at both temperatures with the largest increases observed within the first 24 hours. Decreases in δ13 C values were observed for all plants at 300°C and for two of the species at the lower temperature (200°C). The maximum shift in the δ13 C value related to experimental decomposition was -0.90‰ (horsetail), indicating a preferential loss of 13 C during thermal maturation. CONCLUSIONS: The reduction in the δ13 C value potentially suggests a preferential loss of isotopically heavier cellulose in relation to the isotopically lighter lignin component during maturation. The isotopic offset observed here (<0.9‰) means that palaeoclimatic interpretation of δ13 C values from non-flowering plant material within the geological record remains robust, but only where interpretations are based on variations in δ13 C values greater than 1‰. Copyright © 2016 John Wiley & Sons, Ltd.

Sedimentary transport and fate of polycyclic aromatic hydrocarbons (PAH) from managed burning of moorland vegetation on a blanket peat, South Yorkshire, UK.

This study reports the concentrations of 18 polycyclic aromatic hydrocarbons (PAH) from managed burning of moorland vegetation and compares them to PAH in catchment vegetation, underlying peats, head water suspended sediment (HSS), stream water and reservoir sediment cores. Total PAH ranged from 203 to 11,112 µg/kg in the blanket peats, 101-290 µg/kg in the fresh moorland vegetation, 4186 µg/kg at the burnt site, 17,439 µg/kg in the HSS, 56 ng/L in the stream water and 987 to 7346 µg/kg in the reservoir sediments. No total or individual PAH concentrations exceeded the published sediment quality guidelines. The perylene content of selected moorland vegetation (sphagnum, heather and bilberry) ranged from 10 to 18% as compared to only 2% for the sediment hosted PAH. A comparison of whole and <250 µm fractions from the burnt surface layer revealed a near threefold increase in PAH concentration in the fine fraction and a change in the PAH distribution such that naphthalene>>phenanthrene>2-methylnaphthalene. Elevated total PAH contents were observed close to the blanket peat sediment surface (0-10 cm) and then declined at greater depths. The high PAH content of the HSS was attributed to the high sorption capacity of the organic-rich particles (TOC 25.8% (wt/wt)). The distribution of individual PAH in reservoir cores and HSS was consistent and the results of the principal component analysis and isomeric ratios suggest mainly pyrolytic inputs, from either vegetation burning and coal combustion. A comparison of the reservoir core PAH profiles shows that the source(s) have remained largely unchanged since the reservoir construction in 1929A.D. reflecting consistent moorland management practices.