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ABSTRACT: As an alternative procedure to conventional water quality assessment, the presence and combined toxicity of dissolved organic contaminants in water at five sites in the Forth estuary and the Firth of Forth, Scotland, United Kingdom was investigated using silicone rubber passive sampling devices (SR-PSDs) and an algal growth inhibition bioassay. SR-PSDs were deployed in water at the five sites for ~2months. Following retrieval, extracts from the deployed SR-PSDs were assessed for both algal growth inhibition and the occurrence of a wide range of organic contaminants, including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and a variety of plant protection products (PPPs; commonly referred to collectively as 'pesticides'). The 72h algal growth inhibition test was performed using a native marine phytoplankton (Diacronema lutheri) in 24 well microplates. Freely dissolved (e.g. bioavailable) concentrations of PAHs and PCBs were determined using performance reference compounds (PRCs). The algal toxicity tests exhibited varied effects at the five sites indicating the presence of, and exposure to, phytotoxic compounds and their potential toxicity in the Forth. The individual and total dissolved concentrations of 40 PAHs and 32 PCBs measured in the study were relatively low and showed input of petrogenic, atmospheric and sewage related sources. Several pesticides of diverse polarities were identified in the water suggesting sources from both riverine input and direct discharges. The study thus illustrates the value of combining bioassays and chemical analysis (with effective sampling technique) for a realistic and rapid assessment of organic contaminants in the aquatic environment.
Science of The Total Environment 05/2013; 461-462C:230-239. · 3.29 Impact Factor
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ABSTRACT: Salmon fish farming is a major, and expanding, contributor to the economy in remote coastal areas of Scotland, employing over 2100 people in 2011. Most farms are located in sheltered, otherwise pristine, fjordic sealochs. As well as the final product, outputs from salmon farming include consented discharges of material such as faeces, excess feed pellets, nitrogenous wastes, antifoulants, and veterinary medicines. Salmon feed contains a high proportion of marine-sourced lipid and protein and is a potential bioaccumulation/biomagnification route for hydrophobic persistent organic pollutants (POPs), such as PCBs; hence waste excess feed and faecal material may present a source of such contaminants to the marine environment. To prevent significant biofouling, marine structures such as salmon farms may be treated with Cu or Zn-based antifoulants, which together with Zn from galvanised metal structures, can also be lost to the environment. To investigate the significance of such inputs, we measured concentrations of POPs and metals in sediments, biota and water from Scottish sealochs containing salmon fishfarms. We found that environmental concentrations of these contaminants were only locally elevated compared to background and do not present significant environmental risk.
23rd Annual meeting of the Society of Environmental Toxicology and Chemistry (SETAC), 12-16 May 2013, Glasgow, UK; 05/2013
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23rd Annual Meeting of the Society of Environmental Toxicology and Chemistry (SETAC) Europe, 12-16th May 2013, Glasgow, UK, Glasgow, UK; 05/2013
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ABSTRACT: This study evaluates the potential of silicone rubber passive sampling devices (SR-PSDs) as a suitable alternative to automatic water samplers (autosamplers) for the preliminary identification of a wide range of organic contaminants in freshwater systems. The field performance of SR-PSDs deployed at three sites on two streams of an agricultural catchment area in North East (NE) Scotland, United Kingdom (UK) was assessed concurrently with composite water samples collected from two of the sites using autosamplers. The analytical suite consisted of selected plant protection products (PPPs; commonly referred to collectively as 'pesticides'), including 47 pesticides and a separate sub-category of 22 acid/urea herbicides. Of these, a total of 54 substances, comprising 46 pesticides and 8 urea herbicides were detected in at least one of the SR samplers. All but 6 of these SR-PSD detected substances were quantifiable. By comparison, a total of 25 substances comprising 3 pesticides and 22 acid/urea herbicides were detected in the composite water samples, of which only 8 acid/urea herbicides were quantifiable. The larger number and chemical classes of compounds detected and quantified via passive sampling reflect the lower limits of detection achieved by this device when compared to autosamplers. The determination of dissolved concentrations of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) added to the information on contaminant pressures at each site, allowing assessment of the reliability of SR-PSDs in freshwater systems and the identification of possible contaminant sources. The study demonstrated the utility of SR-PSDs for detecting and semi-quantifying low concentrations of analytes, including those which hitherto have not been measured in the catchment area and also some pesticides that are no longer approved for agricultural use in the UK and EU. The SR-PSD approach can thus provide a better understanding and clearer picture of the use and presence of organic contaminants within catchments.
Science of The Total Environment 01/2013; 445-446C:261-272. · 3.29 Impact Factor
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ABSTRACT: We investigated the feasibility of coupling passive sampling and in vitro bioassay techniques for both chemical and ecotoxicological assessment of complex mixtures of organic contaminants in water. Silicone rubber passive sampling devices (SR-PSDs) were deployed for 8-9weeks in four streams and an estuary of an agricultural catchment in North East (NE) Scotland. Extracts from the SR-PSDs were analysed for freely dissolved hydrophobic organic contaminants (HOCs) and screened for wide range of pesticides. The total concentrations of dissolved PAHs (∑PAH(40), parent and branched) in the water column of the catchment varied from 38 to 69ngL(-1), whilst PCBs (∑PCB(32)) ranged 0.02-0.06ngL(-1). A number and level of pesticides and acid/urea herbicides of varying hydrophobicity (logK(OW)s ∼2.25 to ∼5.31) were also detected in the SR extracts, indicating their occurrence in the catchment. The acute toxicity and EROD induction potentials of SR extracts from the study sites were evaluated with rainbow trout liver (Oncorhynchus mykiss; RTL-W1) cell line. Acute cytotoxicity was not observed in cells following 48h exposure to the SR extracts using neutral red uptake assay as endpoint. But, on a sublethal level, for every site, statistically significant EROD activity was observed to some degree following 72h exposure to extracts, indicating the presence of compounds with dioxin-like effect that are bioavailable to aquatic organisms in the water bodies of the catchment. Importantly, only a small fraction of the EROD induction could be attributed to the PAHs and PCBs that were determined. This preliminary study demonstrates that the coupling of silicone rubber passive sampling techniques with in vitro bioassays is feasible and offers a cost effective early warning signal on water quality deterioration.
Chemosphere 07/2012; · 3.21 Impact Factor
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ABSTRACT: Short chain chlorinated paraffins (SCCPs) are a group of persistent organic pollutants (POPs) of increasing concern, but are to date not widely investigated in the environment, largely due to the challenges involved in their quantification. Here, SCCPs were quantified in marine sediments from the Firth of Clyde, Scotland, by gas chromatography with electron capture negative ionisation mass spectrometry (GC-ECNIMS) and through carbon skeleton analysis by gas chromatography with flame ionisation detection (GC-FID), and the analytical challenges encountered are discussed. Concentrations in the sediments ranged from 0.4 to 69 μg kg(-1) when determined by GC-ECNIMS, and from 5.6 to 379 μg kg(-1) when determined by GC-FID. For 8 out of 11 samples, analysis by GC-FID gave higher results than analysis by GC-ECNIMS. Unexpected aspects of the analysis, such as the presence of high concentrations of longer chain chlorinated paraffins in the samples, are also presented.
Chemosphere 03/2012; 88(3):292-9. · 3.21 Impact Factor
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ABSTRACT: The availability of polycyclic aromatic hydrocarbons (PAHs) from marine sediments to the ragworm (Nereis virens) was studied. Concentrations of PAHs in pore waters were determined using silicone rubber passive samplers. Calculated bioconcentration factors confirmed that partitioning of PAHs between the lipid phase of the polychaetes and pore water is a passive process. Low biota-sediment accumulation factors (BSAF) calculated using total sediment concentration suggested a fraction of the total PAH burden in the sediment may be strongly sorbed to organic carbon and not available to the polychaete. Organic carbon normalised concentrations of the potentially exchangeable fractions of contaminants and freely dissolved concentrations (measured using silicone rubber samplers) provide a better description of the observed bioaccumulation by the ragworms. These data indicate that the concept of availability should be included in environmental risk assessments based upon equilibrium partitioning models, and that silicone rubber samplers can provide the necessary information for these models.
Environmental pollution (Barking, Essex: 1987) 09/2011; 159(12):3351-6. · 3.43 Impact Factor
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ABSTRACT: Halogenated persistent organic pollutants [polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)] along with total lipid, were measured in the liver and muscle of three species of deep water fish (black scabbard, black dogfish (liver only) and roundnose grenadier) collected from the Rockall fishing area, to the west of Scotland, between 2006 and 2008. Both contaminant groups were detected in the muscle and liver, with concentrations of PCBs being higher than PBDEs. There were no significant differences in the PCB or PBDE concentrations between the three species, or different sampling locations in the Rockall fishing area. PCB concentrations (ΣICES (International Council for the Exploration of the Sea)7 PCBs) greater than 500 μg kg(-1) lipid weight were found in 26 of the 106 liver samples. PCB concentrations were compared to OSPAR assessment criteria, concentrations were above background but below Environmental Assessment Criteria. Estimated Toxic Equivalent (TEQ) concentrations, calculated using published models, in the fish muscle and liver indicated that consumption of deep water fish is unlikely to represent a risk to human health. The high squalene content in some of the black dogfish liver necessitated an additional clean-up step, involving gel permeation chromatography, when analyzing for PBDEs. Concentrations of PBDEs were low with many congeners being below detection limits, particularly in the muscle. There are currently no assessment criteria available for PBDEs. Furthermore, there is only very limited data on PBDEs in deep water fish. However, the concentrations observed in this study were similar to the concentrations recently reported in Mediterranean deep water fish.
Chemosphere 03/2011; 83(6):839-50. · 3.21 Impact Factor
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ABSTRACT: Concentrations of persistent organic pollutants (POPs), including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were determined in sediment and biota (fish liver) from around Scotland. The concentrations were investigated using assessment criteria developed by OSPAR and ICES. Organic contaminant concentrations, PAHs, PCBs and PBDEs in sediment, and PCBs and PBDEs in fish liver, were significantly higher in the Clyde compared to all other sea areas. This is mainly due to historic industrial inputs. Highest PCB and PAH concentrations were found in the strata furthest up the Clyde estuary, with concentrations of POPs in these strata being at levels such that there is an unacceptable risk of chronic effects occurring in marine species. Furthermore, for PAHs in Clyde sediment there was a significant negative gradient going from north to south towards the open sea. PAH and PCB concentrations in sediment and biota in all other Scottish sea areas (except for PCBs in sediment from East Scotland) were unlikely to give rise to pollution effects, being below relevant assessment criteria. Although no assessment criteria are available for PBDEs, the concentrations observed in Scottish sediments were low with all congeners below the limit of detection (LoD; 0.03 µg kg(-1) dry weight) in 140 out of a total of 307 samples analysed. Where PBDEs were detected, the dominant congeners were BDE47 and BDE99. PBDEs were detected in fish livers, although concentrations were less than 150 µg kg(-1) lipid weight in all sea areas except the Clyde where concentrations ranged between 8.9 and 2202 µg kg(-1) lipid weight. Few trends were detected in contaminant concentrations in biota or sediment at any Scottish site with more than five years data. Downward trends were detected in PAHs in sediment from the Clyde, Irish Sea and Minches and Malin Sea and PCBs in fish liver from the Moray Firth. Rules were developed for the aggregation of the contaminant data across a sea area. An overall assessment for each sea area was then assigned, looking at the frequency of sites or strata within each sea area that were above or below the relevant assessment criteria. Overall the status of the various sea areas, with respect to the assessed POPs, can be considered to be acceptable in that they were below concentrations likely to result in chronic effects for all sea areas except the Clyde.
Journal of Environmental Monitoring 03/2011; 13(5):1288-307. · 1.99 Impact Factor
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ABSTRACT: Efficient oil spill management in the marine environment requires the ability to predict the rate of loss of individual priority hydrocarbon compounds from marine organisms. Rate of elimination of polycyclic aromatic hydrocarbons (PAHs) from mussels decreases with increase in molecular weight and degree of alkylation.
Journal of Environmental Monitoring 07/2009; 11(6):1284-91. · 1.99 Impact Factor
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ABSTRACT: Halogenated persistent organic pollutants (chlorobiphenyls (CBs), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD) and tetrabromobisphenol-A (TBBP-A)) and total lipid content were measured in the liver and muscle of three species of deep water fish (black scabbard, roundnose grenadier and black dogfish) collected from the Rockall Trough, to the west of Scotland, in 2006. CB concentrations (SigmaICES (International Council for the Exploration of the Seas)7 CBs) >500 microg kg(-1) lipid weight) were found in 9 of the 31 deep water fish liver samples. Non-ortho CBs were measured in samples with the highest ortho CB concentrations. Non-ortho CBs (CB81, 77, 126 and 169) were not detected in any of the fish muscle samples. In liver, CB81 was not detected in any of the samples while CB169 was detected in all but one sample. The total 'dioxin-like' CB concentration was calculated based on the 5 mono-ortho and 4 non-ortho CBs measured. The non-ortho CB concentration made a very small contribution to the total 'dioxin-like' CB concentrations (<1%). Concentrations for the individual ICES7 CBs in fish liver were above OSPAR Background Assessment Concentrations (BACs) in all three species, except for CB28 and 101 in black dogfish. Toxic Equivalent (TEQs) concentrations calculated for the five mono-ortho and four non-ortho CBs measured, and estimated TEQs calculated using published models in the fish muscle indicated that consumption of deep water fish muscle is unlikely to represent a risk to human health. However, dioxins and furans were not measured and the contribution to the calculated TEQs from these compounds was not taken into account. Calculated and estimated TEQs for some roundnose grenadier liver samples exceeded the 25 pg g(-1) wet weight limit for fish liver and, therefore, there may be a health risk if consumed. PBDEs were detected in both the liver and muscle of the deep water fish, whilst HBCD and TBBP-A were not detected in any of the deep water fish.
Journal of Environmental Monitoring 02/2009; 11(2):406-17. · 1.99 Impact Factor
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03/2008; , ISBN: 9780470061572
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ABSTRACT: Silicone rubber sheeting can be used as a passive sampling device for hydrophobic organic contaminants in the environment to determine the available concentrations in water and sediments. Reliable sampler-water partition coefficients are required to determine the sampling rates and the dissolved contaminant concentrations in water and in sediment pore water. Log partition coefficients (logK(sr,w)) for silicone rubber-water have been estimated for 32 polycyclic aromatic hydrocarbons (PAHs), 2 deuterated PAH analogues and 32 chlorobiphenyls (CBs) using the cosolvent method, with methanol as cosolvent. Strong linear relationships were found with literature values for the corresponding log octanol-water partition coefficients (logK(ow)) for both CBs and PAHs, confirming that partitioning into the silicone rubber is strongly determined by the hydrophobicity of the compounds, which suggests logK(ow) is a good predictor of logK(sr,w) and that absorption is the main mechanism for accumulation of analytes into the silicone rubber polymer.
Journal of Environmental Monitoring 11/2007; 9(10):1116-21. · 1.99 Impact Factor
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ABSTRACT: A composite random sampling design was used to estimate the concentrations of hydrocarbons in sediments from two near-shore areas of Scotland (Firth of Clyde and Firth of Forth). The aim of this work was to estimate a mean value for each parameter in these areas, and to determine whether this can be done with more thorough coverage (better representation), better precision and less variance at lower analytical cost through a composite random sampling scheme rather than a simple random sampling scheme, and thereby contribute to the re-design of the UK National Marine Monitoring Programme (NMMP), re-named the UK Clean Seas Environmental Monitoring Programme (CSEMP) in 2006. Samples were collected using a simple random sampling design during 2005. All sediment samples were analysed for their particle size distribution and total organic carbon (TOC). All sediments were analysed for polycyclic aromatic hydrocarbons (PAHs) and n-alkanes. The concentrations of PAHs and n-alkanes in the study areas are described, and sources of PAHs were investigated through the PAH distributions and n-alkane profiles. Individual sediment samples from each area were combined to give a series of composite sub-samples, each comprised of 5 individual sediment samples. These composite samples were re-analysed for the same parameters as the individual samples. Mean total PAH (2- to 6-ring parent and branched) concentrations, based on the individual original sediment samples collected through simple random sampling, were 1858 microg kg(-1) dry weight (SE = 196 microg kg(-1) dry weight, n = 25) and 532.4 microg kg(-1) dry weight (SE = 59 microg kg(-1) dry weight, n = 25) in the Clyde and Forth, respectively. Mean total PAH concentrations of the composite samples were 1745 microg kg(-1) dry weight (SE = 121.0 microg kg(-1) dry weight, n = 5) in the Clyde and 511.6 microg kg(-1) dry weight (SE = 37.4 microg kg(-1) dry weight, n = 5) in the Forth. No significant differences were found between the mean PAH concentrations from the two sampling designs. This study demonstrated that the composite random sampling design gave a mean value with less variance than the simple random sampling design, at significantly reduced analytical effort (and cost).
Journal of Environmental Monitoring 08/2007; 9(7):730-9. · 1.99 Impact Factor
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ABSTRACT: Concentrations of organic contaminants were determined in sediment and fish collected annually at six sites around Scotland between 1999 and 2005, as part of the UK National Marine Monitoring Programme. Polycyclic aromatic hydrocarbons (PAHs) and chlorobiphenyls (CBs) were measured in sediment, while CBs and ethoxyresorufin-O-deethylase (EROD) activities were measured in the fish. Highest PAH concentrations in sediment were found at sites where higher coastal influences would be expected (e.g., Clyde and Solway) and four of the six sites gave PAH concentrations above OSPAR background assessment concentrations (BACs). A significant downward trend in the median total PAH concentrations, normalised to total organic carbon (TOC), was found at one of the six sites (Minches). The PAH profiles at all sites were consistent over the 6 year period, indicating that the sites are relatively stable and PAH sources are not changing. There was an indication of a greater petrogenic input on the west coast, with sediment from the Clyde, Solway and Minches having a greater proportion of 2- and 3-ring PAHs and a lower proportion of 5-ring PAHs. CB concentrations at all sites were low compared with UK estuarine sites and similar to sediment from more remote areas: however, BACs were exceeded. No significant trends were detected in either the sediment CB concentrations or patterns at any of the six sites. CB concentrations were significantly higher in fish liver collected from the Clyde. Concentrations at the other five sites were low, with the majority of samples having concentrations for the ICES7 CBs of <500 microg kg(-1) lipid weight. However, individual CB concentrations were still above the BACs. Hepatic EROD activities were measured in male plaice from 2002-2005 and were generally low (<10 pmol min(-1) mg protein(-1)). No temporal trends were detected in either CB concentrations or the EROD activity.
Journal of Environmental Monitoring 06/2007; 9(6):616-29. · 1.99 Impact Factor
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Polycyclic Aromatic Compounds 08/2006; 26(4):283-298. · 1.02 Impact Factor
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ABSTRACT: A method was developed for the determination of the major storage lipids, wax ester and triglycerides, in the copepod Calanus finmarchicus. A variation of the Folch method was used to extract the lipid. The method was scaled down to enable the extraction of either pooled (-1 mg) or individual (approximately 200 microg) copepods. The major lipid classes were identified using TLC and quantified using HPLC coupled with evaporative light scattering detection. Analysis of laboratory reference materials indicated that this method underestimated the minor triglyceride component, but gave a good estimate of the major wax ester component. The fatty acid and fatty alcohol composition of the C. finmarchicus were determined following trans-esterification of the lipid extract in methanol. Fatty acids and fatty alcohols were initially identified by comparison with authentic standard and by mass spectroscopy. Using GC with flame ionisation detection the normalised area percentage of the fatty alcohols and fatty acid methyl esters was determined simultaneously in one run for either pooled or individual copepod samples. These methods were applied to C. finmarchicus collected from the Irminger Sea, North Atlantic in 2001 and 2002.
Journal of Separation Science 07/2006; 29(9):1205-16. · 2.73 Impact Factor
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ABSTRACT: The distribution and composition of hydrocarbons in sediment from the Fladen Ground oilfield in the northern North Sea have been investigated. The total PAH concentrations (2- to 6-ring parent and alkylated PAHs, including the 16 US EPA PAHs) in sediments were relatively low (<100 microg kg(-1) dry weight). The PAH, the Forties crude and diesel oil equivalent concentrations were generally higher in sediment of fine grain size and higher organic carbon concentration. PAH distributions and concentration ratios indicated a predominantly pyrolytic input, being dominated by the heavier, more persistent, 5- and 6-ring compounds, and with a high proportion of parent PAHs. The n-alkane profiles of a number of the sediments contained small, high boiling point, UCMs, indicative of weathered oil arising from a limited petrogenic input. The geochemical biomarker profiles of the sediments that contained UCMs showed a small bisnorhopane peak and a high proportion of norhopane relative to hopane, indicating that there was contamination from both Middle Eastern and North Sea oils. Therefore contamination was not directly as a result of oil exploration activity in the area. The most likely source of petrogenic contamination was from general shipping activity.
Journal of Environmental Monitoring 02/2006; 8(2):307-16. · 1.99 Impact Factor
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ABSTRACT: To assess contaminant concentrations in the Firth of Clyde in relation to the former sewage sludge dump site at Garroch Head, and investigate any temporal changes, fish have been sampled annually since 1992 and sediment since 1999. In addition, a further four locations in the Clyde (Holy Loch, Hunterston, Skelmorlie and Irvine Bay) have been sampled for fish and sediment since 1999. Chlorobiphenyls (CBs) were measured in fish samples and polycyclic aromatic hydrocarbons (PAHs) and CBs in sediment. Since sampling was initiated the concentration for the summation operatorICES7 CBs in fish liver has been consistently >500 microg kg(-1) lipid weight at Garroch Head and the other Clyde sites and lower at the reference sites (Pladda, Colonsay, Broad Bay). Although the lowest CB concentrations of the eleven year period in plaice liver from Garroch Head were found in 2002, CB concentrations were found not to have decreased significantly since sewage sludge dumping ceased in 1998. However, a change in CB profile was observed with fish liver collected between 1992 and 1998 from Garroch Head showing a lower proportion of the less chlorinated CBs compared to the 1999-2002 liver samples. Highest CB and PAH concentrations in sediment were found at Garroch Head and Holy Loch with concentrations at these sites being significantly higher than at all other sites.
Journal of Environmental Monitoring 12/2005; 7(12):1378-87. · 1.99 Impact Factor
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ABSTRACT: Sediments were collected from the 110 mile hole and along a transect from 58 degrees 58.32' N 1 degree 10.38' W to the UK National Marine Monitoring (NMMP) site in the inner Moray Firth, for determination of hydrocarbon concentration and composition. Total PAH concentrations (2- to 6-ring PAHs, parent and branched) were highest at NMMP site 95 and at the associated end of the transect in the inner Moray Firth. PAHs in this area were of predominately pyrolytic origin and could be attributed to urban and industrial activities. The majority of sediments collected in the middle section of the transect had low total PAH concentrations (< 100 ng g(-1) dry weight). The high proportion of naphthalenes and alkylated PAHs in this area suggested a predominately petrogenic input. The GC-FID aliphatic hydrocarbon profiles showed that the majority of sediments, including those in the inner Firth, had a limited petrogenic input. This was supported by the geochemical biomarker profiles, which contained triterpanes typical of Middle Eastern crude oil. Principal component analysis was used to investigate spatial trends in the PAH distributions and demonstrated that there were differences between areas. The NMMP site 95 and transect start and middle sediments were well separated. PCA further confirmed that sediments from the NMMP site 95, the 110 mile hole and the inner Moray Firth (south west) end of the transect contained PAHs from predominately pyrolytic sources, whereas sediments from the north east end (start) and the middle of the transect were typified by a greater petrogenic component.
Journal of Environmental Monitoring 06/2003; 5(3):395-403. · 1.99 Impact Factor
