Characterisation of former manufactured gas plant soils using parent and alkylated polycyclic aromatic hydrocarbons and Rock-Eval(6) pyrolysis.

Soils sampled from 10 former manufactured gas plants (MGP) in the UK were investigated using gas chromatography mass spectrometry (GC-MS/MS) and Rock-Eval (6) Pyrolysis (RE). RE is a screening tool used to characterise bulk organic matter in soils via the release of carbon compounds during pyrolysis and oxidation. Both the distributions and concentrations of 30 parent and 21 alkylated polycyclic aromatic hydrocarbons (PAHs) and the parameters of RE were analysed to establish relationships between soils and the MGP processes history. Principal component analysis (PCA) using the PAHs distributions and RE parameters can assist with differentiating between MGP processes. MGP processes utilizing oil provided the clearest results, attributed to petrogenic signatures with high proportions of low molecular weight PAHs. Processes using lower temperature processes were distinguished by higher proportions of high molecular weight PAHs. RE parameters alone were unable to distinguish MGP processes but showed potential in estimating the lability and thus the amount of PAH that could be released from soils. This research provides new insights that may be useful in understanding and characterising the risks posed to human health from PAHs in soils.

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.

Health risk assessment of potentially harmful elements and dietary minerals from vegetables irrigated with untreated wastewater, Pakistan.

In the developing world, vegetables are commonly grown in suburban areas irrigated with untreated wastewater containing potentially harmful elements (PHEs). In Pakistan, there is no published work on the bioaccessibility aspect of PHEs and dietary minerals (DMs) in sewage-irrigated soil or the vegetables grown on such soils in Pakistan. Several industrial districts of Pakistan were selected for assessment of the risk associated with the ingestion of vegetables grown over sewage-irrigated soils. Both the total and bioaccessible fraction of PHEs (Cd, Co, Cr, Ni, and Pb) and DMs (Fe, Cu, Mn, Zn, Ca, Mg, and I) in soils and vegetable samples were measured. The concentrations of these PHEs and DMs in sewage-irrigated and control soils were below published upper threshold limits. However, compared to control soils, sewage irrigation over the years decreased soil pH (7.7 vs 8.1) and enhanced dissolved organic carbon (1.8 vs 0.8 %), which could enhance the phyto-availability of PHEs and DMs to crops. Of the PHEs and DMs, the highest transfer factor (soil to plant) was noted for Cd and Ca, respectively. Concentrations of PHEs in most of the sewage-irrigated vegetables were below the published upper threshold limits, except for Cd in the fruiting portion of eggplant and bell pepper (0.06-0.08 mg/kg Cd, dry weight) at three locations in Gujarat and Kasur districts. The bioaccessible fraction of PHEs can reduce the context of dietary intake measurements compared to total concentrations, but differences between both measurements were not significant for Cd. Since the soils of the sampled districts are not overly contaminated compared to control sites, vegetables grown over sewage-irrigated soils would provide an opportunity to harvest mineral-rich vegetables potentially providing consumers 62, 60, 12, 104, and 63 % higher dietary intake of Cu, Mn, Zn, Ca, and Mg, respectively. Based on Fe and vanadium correlations in vegetables, it is inferred that a significant proportion of total dietary Fe intake could be contributed by soil particles adhered to the consumable portion of vegetables. Faecal sterol ratios were used to identify and distinguish the source of faecal contamination in soils from Gujranwala, Gujarat, and Lahore districts, confirming the presence of human-derived sewage biomarkers at different stages of environmental alteration. A strong correlation of some metals with soil organic matter concentration was observed, but none with sewage biomarkers.

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.