Monitoring of Polycyclic Aromatic Hydrocarbons (PAHs) in Scottish Deepwater environments.

Polycyclic aromatic hydrocarbons (PAHs) were measured in environmental samples (sponges, fish and sediment) collected in 2014 and 2016 from the Faroe-Shetland Channel and Rosemary Bank Seamount. These data could be used to provide a baseline against which any changes can be assessed in the event of an oil spill and contribute to any environmental impact assessment. Concentrations in all samples were low, often below the detection limits, and were typical of reference sites. Sponges can be used as an alternative indicator species to mussels for monitoring PAHs in the marine environment as they can accumulate PAHs from both the dissolved and particulate phase. PAH concentrations in marine sponges from Scottish waters have not previously been reported. Concentrations were low, but contained a higher proportion of heavier 4- to 6-ring PAHs compared to the fish samples.

An assessment of persistent organic pollutants (POPs) in wild and rope grown blue mussels (Mytilius edulis) from Scottish coastal waters.

Farmed, rope grown mussels (Loch Etive and Loch Ewe, both on the west coast of Scotland) and wild mussels (Straad on the west coast and Shell Bay and Aberdeen Breakwater, both on the east coast of Scotland) were collected on a monthly basis and analysed for persistent organic pollutants (POPs) with the aim of assessing the status of Scottish mussels, with respect to concentrations of POPs, and investigating site-specific and seasonal differences. Samples were analysed for polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs) and chlorobiphenyls (CBs). Total PAH (2- to 6-ring parent and alkylated) concentrations in mussels from three pristine sites (ref. 1: ICES Marine Chemistry Working Group Report 2008, http://www.ices.dk/reports/MHC/2007/MCWG07.pdf) (Loch Etive, Loch Ewe and Straad) were significantly lower than in mussels from sites with greater coastal influences (Aberdeen Breakwater and Shell Bay). Seasonal trends in the PAH concentrations were evident at the pristine sites, with concentrations being significantly higher for samples collected between November and March compared to those collected between April and October. The PAH data was assessed using a recently proposed traffic light system, based on the assessment criteria adopted by OSPAR for use in the 2008 Coordinated Environmental Monitoring Programme (CEMP) assessment. Concentrations were compared to Background Assessment Concentrations (BAC; blue/green transition) and Environmental Assessment Concentrations (EACs; green/red transition). All sites were classed as 'green' for the PAHs analysed, being below EACs, where available. The pristine sites were also below BACs for some PAHs and therefore would be classed as 'blue' for these PAHs. CBs and PBDEs were measured in mussels collected between 2006 and 2008 inclusive. Concentrations for CB and PBDEs were significantly higher in the Aberdeen Breakwater mussels than for all other sites. Concentrations at all sites were low with many congeners being below the detection limits for both contaminant groups. No seasonal trends were observed in the CBs or PBDE concentrations or composition at any of the five sites. The green-red transition (described by the EACpassive) was exceeded for CB118 in mussels from Aberdeen Breakwater and surprisingly at the pristine site of Loch Etive. As such both sites were classed as 'red'. All other ICES7 CBs were below EACs and therefore classed as 'blue' or 'green'.

Preliminary assessment of polybrominated diphenyl ethers (PBDEs) in the Scottish aquatic environment, including the Firth of Clyde.

This paper presents preliminary data on polybrominated diphenyl ethers (PBDEs) in the Scottish aquatic environment. Sediment and biota (fish liver, fish muscle and mussels) from a number of locations around Scotland were analysed for PBDEs with samples being from both remote and from potentially contaminated areas such as the former sewage sludge dump site at Garroch Head in the Clyde. PBDEs were measured in both cultivated, rope grown mussels and wild mussels collected from 5 sites around Scotland in 2006. Total PBDE concentrations (sum of tri- to hepta-BDEs) ranged from

Composition and concentration of hydrocarbons in sediment samples from the oil producing area of the East Shetland Basin, Scotland.

The East Shetland Basin is one of the areas that the Fisheries Research Services (FRS) has concentrated on to assess the possible impacts of oil exploration and production on the marine environment. A stratified random survey of the sediment was carried out in 2002. TOCs were low across the basin and were positively correlated with grain size. The total PAH concentrations (2- to 6-ring parent and alkylated PAHs, including the 16 US EPA PAHs) were less than 150 microg kg(-1) dry weight and their composition indicated a predominantly pyrolytic input to the basin in 2002. Minor unresolved complex mixtures in the n-alkane profiles indicated a slight petrogenic input but further examination of the biomarkers (hopanes and steranes) showed a mixed North Sea and Middle Eastern source. The Middle Eastern source is likely due to inputs from shipping activity, as it is widely used as bunker fuel. Grid surveys were carried out in 1986, 1988-89 and 1994 and areas were selected for which there was data for all the historic grid surveys and the 2002 stratified random survey. Although referring to only a small part of the East Shetland Basin, comparison with these historic surveys shows clearly that the concentrations of Forties crude oil equivalents and total PAH concentrations were highest in 1988-89 and by 2002 had returned to concentrations the same as or less than observed in the original survey in 1986.

The effects of oil exploration and production in the Fladen Ground: composition and concentration of hydrocarbons in sediment samples collected during 2001 and their comparison with sediment samples collected in 1989.

Due to the potentially accumulative nature of the Fladen Ground, an area of intense oil activity in the North Sea, a survey was carried out in 1989 to map the distribution of contamination in relation to these oil activities. All the sediments collected were screened by ultraviolet fluorescence (UVF) for polycyclic aromatic hydrocarbons (PAHs) and selected samples were analysed for n-alkanes (by GC-FID), PAHs and biomarkers (by GC-MSD). This survey was repeated in 2001, with all the 1989 sites being resampled. All of these sediments were analysed for UVF oil equivalents, PAHs, n-alkanes and biomarkers. The concentrations of these parameters decreased between 1989 and 2001, with average decreases ranging from 43% to 88%. In addition, no significant difference was found, for all the parameters, between near field (<5 km from an oil installation) and far field (>5 km from an oil installation) sites in 2001 indicating that the Fladen Ground is approaching a 'steady state' or background concentration for contamination.

The polycyclic aromatic hydrocarbon and geochemical biomarker composition of sediments from sea lochs on the west coast of Scotland.

Sediments from twelve sea lochs on the west coast of Scotland were analysed for parent and branched 2- to 6-ring polycyclic aromatic hydrocarbons (PAHs), n-alkanes and geochemical biomarkers (triterpanes). Where possible at least fourteen sediment samples were collected at random from each sea loch. All sea lochs were remote, most had limited industrial and urban inputs, although all had fish farms. Four lochs had moderate total PAH concentrations and eight lochs had high total PAH concentrations. Total PAH concentration was related to organic carbon content and particle size distribution, with sandier sediments having lower PAH concentrations. The highest total PAH concentrations, normalised for organic carbon, were in Loch Linnhe and Ballachulish Bay (Loch Leven), close to an aluminium smelter. PAH concentration ratios showed that pyrolysis was the main source of PAHs in most lochs. Only sediments from Loch Clash showed evidence of petrogenic input based on their geochemical biomarker (triterpane and sterane) and n-alkane profiles. PAH profiles were similar across lochs apart from Loch Linnhe and Ballachulish Bay, which had a greater proportion of heavy parent PAHs. West coast sediments had a smaller proportion of heavy PAHs than sediments collected from voes in Shetland and a smaller proportion of alkylated PAHs relative to sediments collected from coastal waters around Orkney.

The polycyclic aromatic hydrocarbon composition of mussels (Mytilus edulis) from Scottish coastal waters.

Blue mussels (Mytilus edulis) were collected from coastal areas and voes in Shetland and Orkney during March and April 1998 and from various coastal locations around mainland Scotland and from the Islands during October and December 1999. The polycyclic aromatic hydrocarbon concentration and composition (2- to 6-ring parent and branched) were determined for all samples. Additional analysis, including sensory assessment and the determination of n-alkanes and geochemical biomarkers, was also undertaken on the Shetland and Orkney mussels collected in 1998. Mussels from Shetland and Orkney exhibited a wide range of total PAH concentration (14.7 to 7,177 ng g(-1) wet weight). Those mussels collected in 1999 exhibited a narrower concentration range. The lowest value (mussels from Loch Kentra) was 8.4 ng g(-1) wet weight while the maximum concentration was 344.1 ng g(-1) wet weight and was determined in mussels from Granton East in the Firth of Forth. The PAH concentration ratios in mussels from Dury Voe (Grunna), Long Hope and Kirkwall Bay were consistent with a predominately petrogenic source for these contaminants. This was supported by both the sensory assessment and the n-alkane and triterpane profiles. Comparisons of the PAH concentrations in mussels with sediments collected from the same locations around Shetland and Orkney showed that in areas of high sediment PAH concentration the bioavailability of these contaminants was limited.

The polycyclic aromatic hydrocarbon and geochemical biomarker composition of sediments from voes and coastal areas in the Shetland and Orkney Islands.

Marine sediments from coastal areas and voes in the Shetland and Orkney Islands were analysed for parent and branched 2- to 6-ring polycyclic aromatic hydrocarbons (PAHs) and geochemical biomarkers. Where possible 14 sediment samples were collected at random from each of 17 Shetland and 9 Orkney sites. The wide range of total PAH concentrations in sediments (i.e., < LOD up to 22619 ng g(-1) dry weight) was indicative of a variety of anthropogenic activities and different sediment types associated with the specific locations. Low PAH concentrations were determined in sandy sediments from areas of limited boat activity. The highest PAH concentrations were found in muddy sediment close to a boat repair yard. PAH concentration ratios were consistent with the main source of these compounds, in most areas, being pyrolysis. Geochemical biomarker (triterpane and sterane) profiles from the sediment were indicative, for some areas, of limited petrogenic input. Punds Voe was the only voe to show evidence of North Sea oil. PAH profiles were similar across sites within each island group, with any differences attributable to known local sources of PAHs. However, there was a clear difference in the PAH profiles of Shetland and Orkney sediments, with Orkney sediments having a higher proportion of the lighter alkylated PAHs.

Analysis of sediments from Shetland Island voes for polycyclic aromatic hydrocarbons, steranes and triterpanes.

A few days after the grounding of the oil tanker Braer on 5 January 1993, an Exclusion Zone was designated by Order under the Food and Environment Protection Act 1985, prohibiting the harvesting of farmed or wild shellfish within the Zone to prevent contaminated products reaching the market place. The order was progressively lifted for species that were found to be free of petrogenic taint and for which the polycyclic aromatic hydrocarbon (PAH) levels were within the range for reference samples. This Order, however, still remains in place for mussels (Mytilus edulis) as the PAH levels are higher than in reference mussels. To investigate the possible source of PAHs found in these mussels, sediments were collected from three reference and three Zone sites and their hydrocarbon compositions studied using the n-alkane composition and concentration, PAH composition and concentration and the sterane and triterpane composition. The reference site at Olna Firth was found to have the highest levels of 2-6-ring parent and branched PAHs, the highest concentration in one of the pooled sediments being 4,530 ng g(-1) dry weight. Values in the other two reference sites (Vaila Sound and Mangaster Voe) ranged from 248.7 to 902.2 ng g(-1) dry weight. PAH concentrations at the Zone sites (Sandsound Voe, Stromness Voe and Punds Voe) ranged from 641.0 to 2,766 ng g(-1) dry weight. The PAH data were normalised to the percentage of organic carbon and log-transformed prior to being analysed using principal component analysis. The mean total PAH concentrations for Zone sites were found not to be significantly different from the reference sites. The PAH concentration ratios were consistent with the main source of PAHs being pyrolysis. However, there was a petrogenic contribution, suggested by the presence of alkylated PAHs, with Punds Voe having the largest petrogenic hydrocarbon content. This was supported by the triterpane profiles and the presence of a UCM in the aliphatic chromatograms from Punds Voe sediments.