Spatial and temporal analysis of the risks posed by polycyclic aromatic hydrocarbon, polychlorinated biphenyl and metal contaminants in sediments in UK estuaries and coastal waters

Marine Pollution Bulletin xxx (2015) xxx–xxx

Contents lists available at ScienceDirect

Marine Pollution Bulletin journal homepage: www.elsevier.com/locate/marpolbul

Baseline

Spatial and temporal analysis of the risks posed by polycyclic aromatic hydrocarbon, polychlorinated biphenyl and metal contaminants in sediments in UK estuaries and coastal waters E.E. Manuel Nicolaus a,⇑, Robin J. Law a, Serena R. Wright a, Brett P. Lyons b a b

Centre for Environment Fisheries and Aquaculture Science, Cefas Lowestoft Laboratory, Lowestoft, Suffolk NR33 0LB, UK Centre for Environment Fisheries and Aquaculture Science, Cefas Weymouth Laboratory, Weymouth, Dorset DT4 8UB, UK

a r t i c l e

i n f o

Article history: Available online xxxx Keywords: Contaminants Marine sediments Risk Characterisation Ratio Environmental Quality Standards (EAC, ERM, ERL)

a b s t r a c t The environmental risks of 22 contaminants, comprising 6 metals, 10 PAHs and 6 PCB congeners occurring in UK estuaries and coastal waters were assessed as single substances. Sediment samples were taken within 12 nautical miles of the English and Welsh coastlines between 1999 and 2011. The measured environmental concentrations were compared to quality standards including ERL, ERM and EAC, all of which have been established internationally. Out of a total of 38,031 individual samples analysed, 42.6% and 7.7% exceeded the ERL/EAC and ERM values, respectively. The highest Risk Characterisation Ratios (RCRs) for metals, PAHs and PCBs were observed for copper, fluorene and CB118 (2,30 ,4,40 ,5pentachlorobiphenyl). In general, the highest concentrations of PAHs and PCBs were observed in 2011 in the Lower Medway indicating a potential risk to the aquatic environment. This study suggests that re-suspension of contaminants banned over 20 years ago is still an ongoing issue. Ó 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http:// creativecommons.org/licenses/by/4.0/).

1. Introduction Estuaries are seen as one of the most productive marine ecosystems in the world and crucial to the life history and development of many aquatic groups (Chapman and Wang, 2001; Dauvin, 2008). These important ecosystems are also strongly susceptible to pollution from anthropogenic input via rivers, marine traffic and coastal construction. Organisms living in or near these environments are exposed to a range of chemicals, including polychlorinated biphenyls (PCBs), metals and polycyclic aromatic hydrocarbons (PAHs) that have the potential to affect sensitive species at both the individual and population level (Beyer et al., 2014). PCB contamination started in the 1940s, peaked in the 1970s and declined afterwards, due to prohibition of use in many countries. Nevertheless, concentrations of PCBs are still very high in many regions due to their hydrophobic nature and low solubility in water; properties which initially contributed to their widespread use (Sprovieri et al., 2007). PCBs may leach from residues within old electrical transformers and other dielectric fluids present in landfill, and once in the environment, can absorb to particulate matter and accumulate in sediments (Kang et al., 2000; Fox et al., 2001; Wiberg and Harris, 2002). As such sediments ⇑ Corresponding author. E-mail address: [email protected] (E.E. Manuel Nicolaus).

commonly form the final sink for PCBs, presenting a secondary form of contamination with bioavailability being increased through re-suspension after storms or dredging activities (Lee et al., 2001). Like PCBs, PAHs also bind to sediments due to their hydrophobicity and, in such matrices, they can persist for decades due to their low level of degradation in anaerobic environments (Sprovieri et al., 2007). PAHs normally reach the marine environment as a result of fossil fuel combustion, waste incineration and oil spills, posing a threat to benthic organisms due to their acutely toxic, mutagenic and carcinogenic properties (Law and Biscaya, 1994; Connell et al., 1997; Kannan et al., 2005). Metals are also released into the marine environment, as a result of both natural and anthropogenic inputs and are also strongly affiliated with particulate matter (Zhang et al., 2007). Sediment bound contamination has been shown to affect the water quality and resulting impacts have been documented in a range of marine invertebrate and vertebrate species (Besselink et al., 1997; Leung et al., 2005; Damiano et al., 2011). It is often difficult to pinpoint which combination is responsible for the observed impacts, as the contaminants may act in a number of possible additive, synergistic or antagonistic stressor effect combinations. The issues around environmental chemical mixture toxicity are currently poorly understood and is probably underestimated as a result (Beyer et al., 2014). A contaminant cocktail of individual chemicals, each of which is individually below a no observable effects

http://dx.doi.org/10.1016/j.marpolbul.2015.03.012 0025-326X/Ó 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

Please cite this article in press as: Manuel Nicolaus, E.E., et al. Spatial and temporal analysis of the risks posed by polycyclic aromatic hydrocarbon, polychlorinated biphenyl and metal contaminants in sediments in UK estuaries and coastal waters. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/ j.marpolbul.2015.03.012

2

E.E. Manuel Nicolaus et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx

concentration (NOEC), may contribute to a manifestation of significant effects through combined or joint toxicity (Brian et al., 2007; Kortenkamp, 2008). This can be influenced further by non-chemical factors dependent on the uptake, bioaccumulation and biomagnification of each contaminant and the characteristics of the organism being exposed (Beyer et al., 2014). Within the UK, the Clean Seas Environment Monitoring Programme (CSEMP) is one of the means by which our national and international commitments to monitoring in estuarine and marine waters are met. The major drivers for the current programme are the European Union (EU) Water Framework Directive (WFD) (European Commission, 2000), the EU Marine Strategy Framework Directive (MSFD) (European Commission, 2008a) and the Co-ordinated Environmental Monitoring Programme and Joint Assessment and Monitoring Programme of the Oslo and Paris convention (OSPAR). Under WFD, chemical status is assessed out to 12 nautical miles against seawater Environmental Quality Standards (EQSs) established by the EU. The list of chemical determinants to be studied was initially specified within the WFD and has since been extended as a result of the

Environmental Quality Standards Directive (EQSD) (European Commission, 2008b). A small number of EQSs have also been set for sediments and biota under WFD. The MSFD requires all European marine waters to meet Good Environmental Status (GES) by 2020, and one of the eleven descriptors (descriptor 8) by which this will be assessed relates to chemical contaminants and their effects (Law et al., 2010; Lyons et al., 2010). Within OSPAR, Environmental Assessment Criteria have been established for a range of contaminants in sediments and biota and for a range of biological effects responses in biota (OSPAR, 2009). In this paper, data for metals, PAHs and PCBs in coastal and estuarine sediments collected annually between 1999 and 2011 have been assessed. The guidelines provided by OSPAR and US EPA (2013) were incorporated in order to enable a simple assessment. A risk characterisation ratio (RCR) was introduced to facilitate the comparison of metals, PCBs and PAHs with one another, as the RCRs incorporated their Ecotoxicological Assessment Criteria (EACs), Effects Range Low (ERLs) and Effects Range Median (ERMs). Similar approaches have been proposed by Ghekiere et al. (2013) and van der Oost et al. (2003). Persuad

Table 1 CSEMP sediment inshore sampling stations. Region

Station name

Station

Latitude

Longitude

Anglia Anglia Anglia Anglia Anglia

Upper Medway (Burham) Lower Medway (Sun Pier) Blackwater (South of East Mersea) Thames Lower (Mucking) Thames (Woolwich)

1 2 3 4 5

51.3337 51.3884 51.7608 51.495 51.4972

0.476 0.52026 0.9971 0.4727 0.063

Cardigan Bay Cardigan Bay

Dovey (Ynys-hir) Mawddach (Bontddu)

6 7

52.549 52.7347

3.9672 3.9899

Eastern Eastern Eastern Eastern

Poole Harbour (Upper South Deep) Poole Harbour (Wytch) Solent (East Brambles Buoy) Southampton Water (Dockhead)

8 9 10 11

50.6864 50.6854 50.7871 50.8763

1.99 2.0297 1.22965 1.3803

Humber (Inside Spurn Head) Humber (Grimsby Road) Humber (Sunk Island) Wash (Off Boston) Wash (Cork Hole) Wash (Off Kings Lynn)

12 13 14 15 16 17

53.5909 53.5863 53.6264 52.942 52.8839 52.9151

0.0831 0.0434 0.1039 0.127 0.3921 0.3568

Cumbria Coast (St Bees Head) Dee (Mostyn Bank) Mersey Channel (C1 Buoy) Mersey (Seacombe Ferry) Mersey (Gladstone) Morecambe Bay Ribble (u/s 11-mile post) Ribble (u/s 8th Mile Post)

18 19 20 21 22 23 24 25

54.5 53.3372 53.527 53.4096 53.453 54.033 53.7267 53.7302

3.65 3.2753 3.161 3.0094 3.0242 3.1 3.0001 2.93665

Severn Severn Severn Severn

Milford Haven (Cosheston Point) Severn Lower (Bedwin) Severn Lower (Peterstone) Severn Middle (Purton)

26 27 28 29

51.7007 51.5611 51.4709 51.7281

4.9185 2.7725 3.0256 2.4755

Tyne Tyne Tyne Tyne Tyne Tyne Tyne Tyne Tyne Tyne Tyne Tyne Tyne

Northumberland Coast 1 Northumberland Coast 2 Tees (Billingham-Bamlett’s Bight) Tees mouth Tees (Seal Sands) Durham Coast (off Seaham) Tweed (Yarrow Slake) Tyne (Hebburn) Tyne (Ferry Crossing) Wear (Alexandra Bridge) Wear (Low Southwick) Wear (Sandy Point) 1 Wear (Sandy Point) 2

30 31 32 33 34 35 36 37 38 39 40 41 42

55.6124 55.6111 54.5916 54.6296 54.5947 54.8157 55.7703 54.985 54.9985 54.9134 54.9143 54.9168 54.9164

1.7592 1.7682 1.2522 1.163 1.1807 1.2779 2.0255 1.5263 1.4408 1.4057 1.4071 1.364 1.3642

Off Tamar (Jennycliffe Bay) Tamar (Warren Point) Tamar (Hamoaze)

43 44 45

50.3489 50.4228 50.3839

4.1309 4.2003 4.1971

Channel Channel Channel Channel

Humber Humber Humber Humber Humber Humber Irish Irish Irish Irish Irish Irish Irish Irish

Wash Wash Wash Wash Wash Wash

Sea Sea Sea Sea Sea Sea Sea Sea

Tees Tees Tees Tees Tees Tees Tees Tees Tees Tees Tees Tees Tees

Western Channel Western Channel Western Channel

Please cite this article in press as: Manuel Nicolaus, E.E., et al. Spatial and temporal analysis of the risks posed by polycyclic aromatic hydrocarbon, polychlorinated biphenyl and metal contaminants in sediments in UK estuaries and coastal waters. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/ j.marpolbul.2015.03.012

3

E.E. Manuel Nicolaus et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx

Table 2 Overview of sample analysis accuracy for PCBs, PAHs and Metals. Validation results include: Bias recovery (%), relative standard deviation (RSD %), Minimum Reported Value (MRV dry weight for sediment) and the Assured Quality Control (AQC) substance used. Group

Determinant

Test name

MRV

Units

Bias %

RSD %

AQC

PCB

2,4,40 -trichlorobiphenyl

PCB NMMP Sediment DW

0.1

lg/kg

2.92

5.4

2,20 ,5,50 -tetrachlorobiphenyl

PCB NMMP Sediment DW

0.1

lg/kg

4.85

5.02

2,20 ,4,5,50 -pentachlorobiphenyl

PCB NMMP Sediment DW

0.1

lg/kg

2.51

3.4

2,30 ,4,40 ,5-pentachlorobiphenyl

PCB NMMP Sediment DW

0.1

lg/kg

0.89

4.92

2,2 ,4,4 ,5,5 -hexachlorobiphenyl

PCB NMMP Sediment DW

0.1

lg/kg

1.9

4.52

2,20 ,3,4,40 ,5,50 heptachlorobiphenyl

PCB NMMP Sediment DW

0.1

lg/kg

2.14

6.3

Custom onto an Custom onto an Custom onto an Custom onto an Custom onto an Custom onto an

Mix from Thames Restek spiked in-house prepared clean soil Mix from Thames Restek spiked in-house prepared clean soil Mix from Thames Restek spiked in-house prepared clean soil Mix from Thames Restek spiked in-house prepared clean soil Mix from Thames Restek spiked in-house prepared clean soil Mix from Thames Restek spiked in-house prepared clean soil

Anthracene

PAH NMMP Suite PAH NMMP Suite PAH NMMP Suite PAH NMMP Suite PAH NMMP Suite PAH NMMP Suite PAH NMMP Suite PAH NMMP Suite PAH NMMP Suite PAH NMMP Suite

Sediment DW lg/kg Basic

20

lg/kg

1.34

5.44

Sediment DW lg/kg Basic

2

lg/kg

2.07

3.81

Sediment DW lg/kg Basic

10

lg/kg

1.38

6.52

Sediment DW lg/kg Basic

2

lg/kg

3.9

4.77

Sediment DW lg/kg Basic

2

lg/kg

1.2

3.69

Sediment DW lg/kg Basic

10

lg/kg

5.75

4.79

Sediment DW lg/kg Basic

10

lg/kg

0.34

9.15

Sediment DW lg/kg Basic

30

lg/kg

1.47

3.81

Sediment DW lg/kg Basic

10

lg/kg

0.41

4.26

Sediment DW lg/kg Basic

1

lg/kg

1.34

5.08

Custom onto an Custom onto an Custom onto an Custom onto an Custom onto an Custom onto an Custom onto an Custom onto an Custom onto an Custom onto an

Mix from Thames Restek spiked in-house prepared clean soil Mix from Thames Restek spiked in-house prepared clean soil Mix from Thames Restek spiked in-house prepared clean soil Mix from Thames Restek spiked in-house prepared clean soil Mix from Thames Restek spiked in-house prepared clean soil Mix from Thames Restek spiked in-house prepared clean soil Mix from Thames Restek spiked in-house prepared clean soil Mix from Thames Restek spiked in-house prepared clean soil Mix from Thames Restek spiked in-house prepared clean soil Mix from Thames Restek spiked in-house prepared clean soil

mg/ kg mg/ kg mg/ kg mg/ kg mg/ kg mg/ kg

3.62

2.94

RTC (Sigma Aldrich) CRM34

0.34

3.37

RTC (Sigma Aldrich) CRM34

0.48

3.6

RTC (Sigma Aldrich) CRM34

3.24

4.81

RTC (Sigma Aldrich) CRM34

0.36

4.68

RTC (Sigma Aldrich) CRM34

1.42

2.86

RTC (Sigma Aldrich) CRM36

0

PAH

0

0

Benz[a]anthracene Benzo[a]pyrene Benzo[ghi]perylene Chrysene (+ triphenylene)⁄ Fluorene Indeno[123-cd]pyrene Naphthalene Phenanthrene Pyrene Metal

Cadmium

Metals (Extended) ICPOES DW mg/kg

0.1

Chromium

Metals (Extended) ICPOES DW mg/kg

0.1

Copper

Metals (Extended) ICPOES DW mg/kg

0.1

Mercury

Mercury Sediment < 63 mg/kg

0.001

Lead

Metals (Extended) ICPOES DW mg/kg

1

Zinc

Metals (Extended) ICPOES DW mg/kg

0.5

NMMP- National Marine Monitoring Programme; ICPOES- Inductively Coupled Plasma optical emission spectroscopy; RTC- Resource Technology Corporation.

et al. (1992) also adopted an approach for metal contamination in sediments using the lowest effect level (LEL) and the severe effect level (SEL), which corresponds to ERL and ERM values, respectively as used by Long et al. (1995). Such an approach gives environmental managers a better understanding of the possible effects these elevated concentrations may have to aquatic organisms, as compared to merely seeing trends of measured contaminant concentrations that may not relate to any adverse outcome. As part of the CSEMP, the sediment samples were collected annually at up to 45 inshore sites around England and Wales by the UK Environment Agency (EA) (see Fig. 1 and Table 1). Using various EA research vessels, samples were collected using a 0.1 m2 Day grab, with up to five replicates being taken at each site within a 20 m radius of the nominal station position for estuarine sites. In the laboratory the samples were sieved and particle size analysis was conducted. A range of metals (Cd, Cr, Cu, Hg, Pb, Zn), PAHs (anthracene, benz[a]anthracene, benzo[ghi]perylene, chrysene/triphenylene, fluorene, indeno[1,2,3-cd]pyrene, naphthalene, phenanthrene, pyrene) and PCB congeners (CB28, CB52, CB101, CB118, CB153, CB180 – 6 of the ICES7

indicator CBs, Webster et al., 2013) were determined in the sediment samples. Brief summaries of the analytical methods employed follow. For metals, freeze-dried sediment samples were digested with nitric acid (Hg) or aqua regia (Cd, Cr, Cu, Pb and Zn). The digestion mixtures utilised microwave heating. The digests were filtered and made up to volume with de-ionised water. For Hg, acidic stannous chloride was used to generate mercury vapour which was detected and quantified using atomic fluorescence spectroscopy. For the other five trace metals, detection and quantification was by means of inductively-coupled/plasma mass spectrometry (ICP–MS) or inductively-coupled plasma/optical emission spectrometry (ICP– OES). For PCBs, freeze-dried sediment samples were extracted with 1:1 dichloromethane:acetone using accelerated solvent extraction (commonly known as ASE). Interfering compounds of high molecular weight were then removed using gel permeation chromatography (GPC). The resulting extract was further cleaned-up on a basic alumina column followed by an acid clean-up using concentrated sulphuric acid. The eluate was then reduced in volume and analysed using GC–MS in electron ionisation mode with

Please cite this article in press as: Manuel Nicolaus, E.E., et al. Spatial and temporal analysis of the risks posed by polycyclic aromatic hydrocarbon, polychlorinated biphenyl and metal contaminants in sediments in UK estuaries and coastal waters. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/ j.marpolbul.2015.03.012

4

E.E. Manuel Nicolaus et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx

Table 3 EAC, ERL and ERM values provided by the OSPAR Commission (2009) and US EPA (2013) which were used to calculate RCR for EAC, ERL and ERM. Concentrations are expressed on a dry weight basis. Group

Contaminant

Contaminant symbol

EAC (lg/kg)

ERL (lg/kg)

ERM (lg/kg)

PCB

2,4,40 trichlorobiphenyl 2,20 ,5,50 tetrachlorobiphenyl 2,20 ,4,5,50 pentachlorobiphenyl 2,30 ,4,40 ,5pentachlorobiphenyl 2,20 ,4,40 ,5,50 hexachlorobiphenyl 2,20 ,3,4,40 ,5,50 heptachlorobiphenyl

CB28

1.7

NA

NA

CB52

2.7

NA

NA

CB101

3

NA

NA

CB118

0.6

NA

NA

CB153

40

NA

NA

CB180

12

NA

NA

Anthracene Benz[a]anthracene Benzo[a]pyrene Benzo[ghi]perylene Chrysene (+ triphenylene)a Fluorene Indeno[123cd]pyrene Naphthalene Phenanthrene Pyrene

ANT BAA BAP BGHIP CHRTR

NA NA NA NA NA

85 261 430 85 384

1100 1600 1600 NA 2800

FLU ICDP

NA NA

19 240

540 NA

NAP PA PYR

NA NA NA

160 240 665

2100 1500 2600

Cadmium Chromium Copper Mercury Lead Zinc

Cd Cr Cu Hg Pb Zn

NA NA NA NA NA NA

1200 81,000 34,000 150 47,000 150,000

9600 370,000 270,000 710 220,000 410,000

PAH

Metal

a Chrysene and triphenylene are not resolved on the GC columns commonly used for PAH analysis; EAC- Ecotoxicological Assessment Criteria; ERL- Effects Range Low; ERM- Effects Range Median.

selected ion monitoring. For PAHs, a similar procedure was followed, except that the clean-up employed was GPC followed by a further silica column clean-up. In both cases (PAHs and PCBs), known amounts of labelled surrogate standards were added at the start of the procedure for quantification purposes. In all cases, certified reference materials were analysed withinbatch in order to monitor method performance day-to-day. The results obtained for these samples were assessed against preset criteria which allowed the acceptance or rejection of the batch data to be decided. Rejected batches were re-analysed. In addition to the in-house AQC, the laboratory participated in external laboratory proficiency schemes, including QUASIMEME (Quality Assurance of Information for Marine Environmental Monitoring in Europe). Also, the analyses of the trace metals and PCBs are accredited by the United Kingdom Accreditation Service (UKAS). A summary of the accuracy of the analytical methods can be found in Table 2. More information on sample collection, analysis and quality assurance can be found in the CSEMP Green book (Cefas, 2012) and associated appendices. In order to conduct an assessment of the likely effects which might occur in the environment as a result of the contaminant concentrations observed, the Measured Environmental Concentration (MEC) for each contaminant and site was calculated. These were then compared to derived assessment criteria. For the PCB congeners, EACs derived by OSPAR were used (OSPAR, 2009). In the absence of EACs for metals and PAHs, ERL and ERM values were used in their assessments. The ERL and ERM represent sediment quality guidelines (SQGs) derived from a large database of sediment toxicity and benthic community information (Long et al.,

1998). The ERL and ERM represent, respectively, the 10th and 50th percentiles of the effects dataset. In broad terms, the ERL indicates a concentration above which effects are possible and the ERM a concentration above which effects are likely to occur. To establish a comparison across the three contaminant groups, RCRs were calculated in which the measured environment concentrations were divided by the ERL or the EAC. EACs represent the concentration below which no chronic effects are expected to occur in marine species, including the most sensitive species. Values of RCR above 1 therefore indicate that environmental effects are likely to result due to that specific contaminant. Finally, a comparison was made of RCRs calculated using ERL and ERM values. Prior to calculation of the RCRs, concentrations of metals were normalised to 5% aluminium concentration and of PAHs to 2.5% organic carbon content. If the concentration of a normaliser was not available for a sample then the raw concentration data were used. The relationship between total metal contaminants and Al, and total PAH concentration and TOC was identified using a linear mixed model, with region and year set as random factors (lme4 package, R). Models were compared and selected based on values of Akaike’s information criterion (AIC) (Sakamoto et al., 1986). There was a significant positive effect of Al on metal contaminants (Fig. S1a) and TOC on PAH (Fig. S1b) (p < 0.0001). For PCBs, RCREAC = MEC . For metals and PAHs, RCRERM = MEC and EAC ERM where MEC is the (usually normalised) measured RCRERL = MEC ERL environmental concentration for a station and year of sampling. The EAC, ERM and ERL values used are given in Table 3 and were derived from the OSPAR Background document on CEMP assessment criteria prepared in advance of the 2010 Quality Status Report and from the US EPA (OSPAR, 2009; US EPA, 2013). Temporal and spatial assessments were carried out on the three main contaminant groups (metals, PAHs and PCBs) separately, and together, using the RCRs. Taking all stations and years into consideration it can be seen that each group had a mean value above 1, ranging from 1.29 for PCBs (RCREAC) and 1.83 for metals (RCRERL) to 10.58 for PAHs (RCRERL; Table S1). Assessing the data on a year to year basis it was observed that, on average, all metals and PAHs had a RCRERL value above 1 while, for PCBs, RCREAC values were above 1 in 8 out of 13 sampling years, when assessments from all stations were taken into consideration (Table S2). The data indicate a stable trend with slight fluctuations until 2007 and an increase to 2011 (Fig. S2). The high level of the RCRERL for PAHs in 2011 is due to a very strong rise in concentrations at stations 2 (Lower Medway -Sun Pier; Fig. S3) and 5 (Thames – Woolwich; Fig. S4). An increase in concentrations of metals was also observed in the Tyne-Tees area at stations 35 and 38 (Durham Coast off Seaham and Tyne Ferry Crossing, respectively; Fig. S5). Carrying out a more detailed spatial assessment it can be seen that levels vary around the English and Welsh coastline for the different contaminant groups (Fig. 2), while the Anglia and Severn regions indicate significant contamination by all three groups of contaminants (Table S3). The Eastern Channel, Cardigan Bay, Humber, Tyne Tees, Western Channel and Irish Sea are more affected by metals and PAHs, and high PCB concentrations can also be seen at station 21 (Mersey -Seacombe Ferry). Using these data to highlight which contaminant group has affected a particular area/site in a specific year it can be further examined to determine the individual metal, PAH and/or PCB contributing to the elevated RCR values. Table 4 gives an indication of the maximum MEC at a specific site in a specific year and the % of RCRs observed for a specific contaminant. The data clearly indicate that the highest PAH and PCB concentrations were observed between 2009 and 2011, while MEC for metals were spread over a wider temporal period depending on a specific contaminant. The highest RCRERL was observed for the PAH fluorene (FLU), which was almost

Please cite this article in press as: Manuel Nicolaus, E.E., et al. Spatial and temporal analysis of the risks posed by polycyclic aromatic hydrocarbon, polychlorinated biphenyl and metal contaminants in sediments in UK estuaries and coastal waters. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/ j.marpolbul.2015.03.012

E.E. Manuel Nicolaus et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx

5

CSEMP Sediment Sampling Fig. 1. CSEMP sediment sampling stations around the English and Welsh Coastline.

25,000 times higher than the ERL at station 2 (Lower Medway -Sun Pier; Table 4). As not all sites were sampled until 2011 Table 5 gives an overview of all sites and their last associated sampling year with their associated highest RCRERL and MEC measured at this station. The table also highlights all other contaminants that exceeded the RCRERL of one. Only two sites (Morecambe Bay and Northumberland Coast 1, station 23 and 30, respectively) did not exceed the assessment criteria thresholds, while all other sites had exceedances from a variety of contaminants. Taking all years into consideration, contaminant levels were also assessed against the ERM values which indicate a higher degree of risk to exposed organisms. It was observed that metals were below RCRERM threshold levels at all stations, apart from station 5 (Thames -Woolwich), which had an RCRERM of 1.41 (Table S4). For PAHs, it was observed that five sites showed RCRERM greater than one which indicates a high likelihood of effects to the marine organisms living in these areas, which include Anglia (station. 2), Irish Sea (station. 21) and the Tyne Tees region (station. 32, 34 and 37; Table S4). There are no ERMs available for individual PCB congeners. As not all sites were sampled until 2011 Table 6 gives an overview of all sites and their last associated sampling year with their associated highest RCRERM and MEC measured at this station. The table also highlights all other contaminants that still exceeded the RCRERM of one. Only 19 sites did not exceed the ERM assessment criteria thresholds, while all other sites had exceedances from a variety of contaminants. The overall temporal assessment that could be made after analysing the slopes of the time trends of 22 different contaminants for each station showed that there is very high variability between stations and contaminant concentrations (Table 7). All PAHs, apart from ICDP, indicated a significant reduction at station 4 (Thames

Lower -Mucking) while, at all other stations concentrations varied very greatly depending on the parameter considered. Comparing station 4 and 5 with one another suggested that contamination further up the Thames is an ongoing problem while, further down the Thames, a reduction in contamination was observed. There is a long history of electricity generation on the Thames using coal and oil fired power stations at a number of locations (Wheeler, 1969; Turnpenny and Coughlan, 1992) and, of course, a large population, traffic, and a diversity of other industries. Overall, it can be said that the inshore English and Welsh coastline still shows an above ERL/EAC level of contamination for most analysed contaminants in this study. Taking all 22 contaminants into consideration, it was observed that 18 had on average an RCR value above 1 with CB118, fluorene and Hg being the highest for PCBs, PAHs and metals, respectively (Table S1). The observed maximum values were mainly concentrated in the Thames estuary (PAHs and PCBs), while metal concentrations were more widely spread within different estuaries (Table 4). Although some sites showed declines over 13 years of monitoring, many contaminants were still above the ERL and ERM limit during the final (2011) sampling year (Tables 5, 6 and 8). At all sites monitored in 2011, RCR values for metals against ERLs were still above one, while 12 out of 15 values for PAH concentrations were also above one. PCBs were below one at all sites apart from the two sampled Anglia sites in the upper Thames and Lower Medway (station 5 and 2, respectively; Table 8). Looking at the RCR values against ERMs for metals and PAHs, overall 14 out of the 15 sites showed values above one for specific contaminants (Table 6). Hg was above one at 12 out of the 15 sites. This study indicates that there are still a number of environmental quality standard exceedances in estuarine and coastal sites

Please cite this article in press as: Manuel Nicolaus, E.E., et al. Spatial and temporal analysis of the risks posed by polycyclic aromatic hydrocarbon, polychlorinated biphenyl and metal contaminants in sediments in UK estuaries and coastal waters. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/ j.marpolbul.2015.03.012

6

E.E. Manuel Nicolaus et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx

Fig. 2. Spatial assessment of metals, PAHs and PCBs using RCRERL/EAC as assessment criteria. The map shows that metals and PAHs are still very high around England and Wales while PCBs are rather low in comparison. RCR- Risk Characterisation Ratio; EAC- Ecotoxicological Assessment Criteria; ELR- Effects Range Low.

Table 4 Maximum Measured Environmental Concentration (MEC) values recorded and their associated RCR collected at a specific year at a specific site followed by the overall occurrence (%) of RCRs taking all collected samples into consideration since 1999. Group

Contaminant

MEC max (lg kg1)

RCR

RCRERM

Station

Sample year

% RCR

% RCRERM

N

PCB

CB28 CB52 CB101 CB118 CB153 CB180

182 308 258 131 189 159

107.1 114.1 86 218.3 4.7 13.3

NA NA NA NA NA NA

5 2 2 2 2 2

2010 2011 2011 2011 2011 2011

20.84 15.5 6.18 47.84 1.54 3.07

NA NA NA NA NA NA

1636 1736 1763 1758 1758 1496

PAH

ANT BAA BAP BGHIP CHRTRa FLU ICDP NAP PA PYR

106,636 322,531 299,383 147,068 58,810 473,765 90,432 61,420 313,272 402,778

1255 1236 696.2 1730 153.2 24,935 376.8 383.9 1305 605.7

96.6 201.6 187.11 NA 21 877.3 NA 29.3 208.9 154.9

2 2 2 2 2 2 2 2 2 2

2011 2011 2011 2011 1999 2011 2011 2011 2011 2011

48.52 42.41 32.26 70.52 33.83 93.74 47.28 57.04 54.68 28.8

1.96 3.34 5.66 NA 1.88 39.12 NA 3.39 8.14 4.51

1785 1825 1714 1584 1274 1756 1802 1299 1794 1750

Metal

Cd Cr Cu Hg Pb Zn

11,614 3,196,000 1,957,500 7651 1,187,500 2,585,938

9.7 39.5 57.6 51 25.3 17.2

12.1 8.6 7.3 10.8 5.4 6.3

1 19 44 38 39 44

2011 2007 2005 2007 2001 2005

10.84 54.29 71.68 68.01 72.63 56.16

0.11 2.01 2.06 15.67 11.14 8.81

1892 1888 1889 1863 1885 1884

MEC = Measured Environmental Concentration; EAC = Ecotoxicological Assessment Criteria; ERL = Effects Range Low; ERM = Effects Range Median; RCR = Risk Characterisation Ratio for EAC and ERL. a CHRTR was not determined in 2011.

Please cite this article in press as: Manuel Nicolaus, E.E., et al. Spatial and temporal analysis of the risks posed by polycyclic aromatic hydrocarbon, polychlorinated biphenyl and metal contaminants in sediments in UK estuaries and coastal waters. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/ j.marpolbul.2015.03.012

E.E. Manuel Nicolaus et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx

7

Table 5 Spatial contaminant assessment using risk characterisation ratio (RCR) as criteria level highlighting the high exposure levels of all sampled sites in their last sample year. Station

Contaminant

RCREAC/ERL max measured at last year sampled

MEC

Last year sampled

% of samples above RCREAC/ERL in this year

N

All Contaminants with RCREAC/ERL > 1 at last year sampled

1

FLU

67.9

1290

2008

80.95

105

2

FLU

24935.0

473,765

2011

87.62

105

3 4 5

FLU Hg FLU

7.2 1.5 184.6

137 225 3507

2008 2008 2011

12.38 50 100

105 2 104

6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Cr FLU Hg FLU FLU FLU FLU FLU FLU Cu FLU Cr FLU Hg FLU

6.2 15.7 18.6 5.7 9.9 82.1 14.5 23.2 13.5 11.2 16.6 1.3 20.6 41.7 59.5

502,000 287 2793 108 187 1560 276 442 257 380,597 316 104,569 391 6250 1131

2007 2007 2011 2008 1999 2008 2008 2008 2011 2011 2001 2007 2011 2011 2011

20.91 25.45 19.05 20.2 7.62 21.94 30.63 43.24 24.76 19.05 11.44 9.52 36.19 31.43 56.19

110 110 105 99 105 105 111 111 105 105 101 21 105 105 105

21 22

Hg FLU

5.7 26.8

851 509

2004 2008

60 66.67

55 21

23 24 25 26

Pb FLU Cr FLU

0.9 15.7 2.1 1674.6

42,567 298 173,423 31,818

2006 2008 2009 2011

0 20 4.76 60

80 105 105 105

27

FLU

42.5

807

2008

51.43

105

28

FLU

96.8

1840

2008

68.57

105

29 30 31 32

Pb Cr FLU FLU

9.3 0.8 19.2 82.5

436,111 64,798 365 1567

2007 2004 2008 2011

34.55 0 17.14 76.19

110 55 105 105

33

FLU

41.5

789

2008

52.38

105

34

FLU

129.0

2450

2008

74.29

105

35

FLU

108.7

2064

2011

52.38

105

36 37

FLU FLU

8.3 126.3

157 2380

2008 2008

15.55 80.19

90 106

38 39 40

FLU Pb FLU

28.7 6.8 96.3

544 320,175 1830

2011 2004 2008

57.12 76.36 65.71

105 55 105

41 42 43

PA Hg FLU

5.8 11.8 77.8

1380 1773 1479

2004 2011 2011

58.18 41.67 62.86

55 60 105

44 45

FLU FLU

32.3 47.6

614 905

2011 2008

50.48 62.86

105 105

Cr, Cu, Hg, Pb, Zn, ANT, BAA, BAP, BGHIP, FLU, ICDP, NAP, PA, PYR, CB28, CB52, CB118 Cr, Cu, Hg, Pb, Zn, ANT, BAA, BAP, BGHIP, FLU, ICDP, NAP, PA, PYR, CB28, CB52, CB101, CB118, CB153, CB180 Cr, Cu, FLU Hg Cd, Cr, Cu, Hg, Pb, Zn, ANT, BAA, BAP, BGHIP, FLU, ICDP, NAP, PA, PYR, CB28, CB52, CB101, CB118, CB153, CB180 Cr, Cu, Pb, Zn, FLU, NAP, CB118 Cr, Cu, Hg, Pb, Zn, BGHIP, FLU, NAP, CB118 Cr, Cu, Hg, FLU Cr, Cu, Hg, Flu, NAP Cu, Hg, Pb, FLU Cr, Cu, Hg, ANT, BAA, BAP, BGHIP, FLU, ICDP, NAP, PA, PYR Cr, Cu, Pb, BGHIP, FLU, NAP, PA Cr, Cu, Hg, Pb, Zn, ANT, BGHIP, FLU, ICDP, NAP, PA Cr, Cu, Hg, Pb, Zn, BGHIP, FLU, NAP, PA Cr, Cu, Pb, Zn, FLU Hg, Pb, ANT, BGHIP, FLU, PA, CB28, CB52, CB101, CB118 Cr, Pb Cr, Cu, Pb, Zn, BGHIP, FLU, ICDP, NAP, PA Cr, Cu, Hg, Pb, Zn, BAA, BAP, BGHIP, FLU, ICDP, NAP Cr, Cu, Hg, Pb, Zn, ANT, BAA, BAP, BGHIP, FLU, ICDP, NAP, PA, PYR, CB28, CB118 Cr, Cu, Hg, Pb, Zn, ANT, BAA, ICDP, PA Cr, Cu, Hg, Pb, Zn, ANT, BAA, BGHIP, FLU, ICDP, NAP, PA, CB28, CB118 None Cd, Cr, Cu, Hg, Zn, BGHIP, FLU Cr, Cu Cr, Cu, Hg, Pb, Zn, ANT, BAA, BAP, BGHIP, FLU, ICDP, NAP, PA, PYR, CB118 Cu, ANT, BAA, BGHIP, FLU, FLU, ICDP, NAP, PA, CB28, CB52, CB101, CB118, CB180 Cu, Hg, Pb, Zn, ANT, BAA, BAP, BGHIP, FLU, ICDP, NAP, PA, PYR, CB28, CB52, CB101, CB118 Cd, Cr, Cu, Hg, Pb, Zn, FLU, CB118 None Cr, Cu, Pb, BGHIP, FLU, NAP, PA Cd, Cr, Cu, Hg, Pb, Zn, ANT, BAA, BAP, BGHIP, FLU, ICDP, NAP, PA, PYR, CB28, CB118 Cr, Cu, Hg, Pb, Zn, ANT, BAA, BAP, BGHIP, FLU, ICDP, NAP, PA, PYR, CB52 Cr, Cu, Hg, Pb, Zn, ANT, BAA, BAP, BGHIP, FLU, ICDP, NAP, PA, PYR, CB52, CB118 Cr, Cu, Hg, Pb, Zn, ANT, BAA, BAP, BGHIP, FLU, ICDP, NAP, PA, PYR Cr, Cu, FLU Cd, Cr, Cu, Hg, Pb, Zn, ANT, BAA, BAP, BGHIP, FLU, ICDP, NAP, PA, PYR, CB28, CB101, CB118 Cr, Cu, Hg, Pb, Zn, ANT, BAA, BGHIP, FLU, NAP, PA, CB118 Cu, Hg, Pb, Zn, ANT, BAA, CHRTR, ICDP, PA Cd, Cr, Cu, Hg, Pb, Zn, ANT, BAA, BAP, BGHIP, FLU, ICDP, NAP, PA, PYR, CB52, CB118 Cu, Hg, Pb, Zn, ANT, BAA, CHRTR, ICDP, PA Cr, Cu, Hg, Pb, Zn Cr, Cu, Hg, Pb, ANT, BAA, BAP, BGHIP, FLU, ICDP, NAP, PA, PYR, CB118 Cr, Cu, Hg, Pb, ZN, ANT, BAA, BAP, BGHIP, FLU, PA, CB118 Cr, Cu, Hg, Pb, Zn, ANT, BAA, BAP, BGHIP, FLU, ICDP, NAP, PA, PYR

MEC = Measured Environmental Concentration; EAC = Ecotoxicological Assessment Criteria; ERL = Effects Range Low; RCR = Risk Characterisation Ratio for EAC and ERL.

around England and Wales. The highest level of contamination for PCBs and PAHs was observed in 2011, by which time much environmental protection procedures for contaminants such as PCBs, have been in place for a number of years. This indicates that re-mobilisation of legacy contaminants may still impact biota living in environments chronically polluted with historic contaminants, thus leaving a limited number of mitigation measures available to policy makers. Previous work in a number of sentinel species has indicated that organisms inhabiting UK estuaries are

exposed to levels of genotoxic contaminants capable of eliciting observable biological effects (Lyons et al., 1999, 2004; Brooks et al., 2009). These studies indicated that both fish and shellfish populations were exposed to complex mixtures of genotoxic and possibly carcinogenic contaminants in a number of coastal sites including Southampton, Thames, Mersey and Tyne estuaries. Comparing the concentrations of PAHs and PCBs in sediments at the time of these studies (2002–2006) to the most recent data presented from 2011 indicates that no significant trend has been

Please cite this article in press as: Manuel Nicolaus, E.E., et al. Spatial and temporal analysis of the risks posed by polycyclic aromatic hydrocarbon, polychlorinated biphenyl and metal contaminants in sediments in UK estuaries and coastal waters. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/ j.marpolbul.2015.03.012

8

E.E. Manuel Nicolaus et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx

Table 6 Spatial contaminant assessment using risk characterisation ratio (RCRERM) as criteria level highlighting the high exposure levels of all sampled sites in their last sample year. Station

Contaminant

RCRERM max measured at last year sampled

MEC

Last year sampled

% of samples above RCRERM in this year

N

All Contaminants with RCRERM > 1 at last year sampled

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

FLU FLU FLU Hg Hg Cr FLU Hg FLU FLU FLU FLU FLU FLU Cu FLU Cr FLU Hg FLU Hg FLU Pb FLU Cr FLU FLU FLU Zn Cr FLU Pb Pa FLU FLU FLU FLU Hg Pb FLU PA Hg FLU Hg FLU

2.4 877.3 0.3 0.3 7.7 1.4 0.5 3.9 0.2 0.3 2.9 0.5 0.8 0.5 1.4 0.6 0.3 0.7 8.8 2.1 1.2 0.9 0.2 0.6 0.5 58.9 1.5 3.4 2.8 0.2 0.7 3.2 1.5 4.5 3.8 0.3 4.4 2.7 1.5 3.4 0.9 2.5 2.7 3.0 1.7

1290 473,765 137 225 5428 502,000 287 2793 108 187 1560 276 442 257 380,597 316 104,569 391 6250 1131 851 509 42,568 298 173,423 31,818 807 1840 1,133,333 64,798 365 706,522 2300 2450 2064 157 2380 1887 320,175 1830 1380 1773 1479 2146 905

2008 2011 2008 2008 2011 2007 2007 2011 2008 1999 2008 2008 2008 2011 2011 2001 2007 2011 2011 2011 2004 2008 2006 2008 2009 2011 2008 2008 2007 2004 2008 2011 2008 2008 2011 2008 2008 2011 2004 2008 2004 2011 2011 2011 2008

16.92 50.77 0.00 0.00 51.56 8.57 0.00 7.69 0.00 0.00 1.54 0.00 0.00 0.00 3.08 0.00 0.00 0.00 7.69 6.15 8.00 0.00 0.00 0.00 0.00 41.54 7.69 7.69 15.71 0.00 0.00 29.23 20.00 30.77 15.38 0.00 27.27 9.23 10.00 15.38 0.00 26.67 9.23 15.38 12.31

65 65 65 2 64 70 70 65 65 70 65 65 65 65 65 66 13 64 65 65 50 13 70 65 65 65 65 65 70 50 65 65 65 65 65 58 66 65 50 65 50 30 65 65 65

Cu, FLU, PA Hg, ANT, BAA, BAP,FLU, NAP, PA, PYR None None Cd, Hg, Pb, Zn, BAA, BAP, FLU, PYR Cr, Zn None Hg None None FLU None None None Cr, Cu None None None Hg FLU, Hg Hg None None None None Hg, ANT, BAA, BAP, FLU, NAP, PA, PYR FLU FLU Hg, Pb, Zn None None Hg, Pb, Zn, FLU FLU, NAP, PA Hg, BAP, FLU, NAP, PA, PYR Cr, Cu, Hg, FLU, PA None Pb, Zn, FLU, PA Hg, FLU Pb Pb, FLU, PA None Hg, Pb Hg, FLU Cu, Hg, FLU Hg, FLU

MEC = Measured Environmental Concentration; ERM = Effects Range Median; RCR = Risk Characterisation Ratio for ERM.

observed, therefore, implying that resident organisms could still be under threat of contamination effects in these areas. While carnivorous fish are more likely impacted through bioaccumulation of hazardous contaminants, filter, suspension and deposit feeders are directly impacted by increased contaminant levels in sediments (Bryan and Langston, 1992). Leung et al. (2005) identified that only 1.4 lg kg1 of Cd is necessary to affect 5% of sensitive benthic taxonomic groups like mollusca, polycheata, echinodermata, crustacea and platyhelminthes, while over 90% were affected at 1000 lg kg1, which is below the ERL for Cd. Approximately 10% of the samples assessed in this current study exceeded the ERL for Cd, suggesting that sensitive species could be adversely affected. Similar work undertaken on the effects of Cu on benthic organisms from Norwegian fiords demonstrated that a concentration of 200,000 lg kg1 (just below the ERM for Cu) reduced the biodiversity by 40% (Rygg, 1985). Rygg (1985) went on to further suggest that for every 10-fold increase in copper concentration a 50% reduction in species richness could occur. Such finding would suggest that at the most impacted UK locations biodiversity could be adversely impacted (>2% of all UK samples had an RCRERM >1 for copper only in this study). Long et al.

(2006) also observed a benthic invertebrate species richness decline from 91 to 6 species after comparing habitats having an ERM of <0.03 compared to >0.2 to 2. The ERMs from maximum MECs observed in this study were on average all above 5 (Table 4) indicating a strong decrease to sensitive benthic invertebrates affecting biodiversity of UK estuarine habitats especially at stations in the lower Thames (2), Mersey (21), and Tees (32–34). Looking at specific sites in more detail (Table 6), it can be seen that all 45 sites observed at least one determinant above 0.2 in their last sample year, indicating a decrease in benthic invertebrate richness. Further assessments on the biodiversity of UK estuaries effected by high levels of contaminants need to be carried out to see if similar biodiversity reductions as mentioned by Long et al. (2006) and Rygg (1985) would also apply to UK estuaries. This baseline study gave a good indication of the current contaminant levels in UK inshore areas highlighting that re-suspension of contaminants are still a threat to the marine environment. Future risk based studies within strongly polluted estuaries would provide us with a better knowledge of where the hot spots are within an estuary. Therefore, the authors would suggest to carry out smaller more intensive surveys within estuaries such as the Thames,

Please cite this article in press as: Manuel Nicolaus, E.E., et al. Spatial and temporal analysis of the risks posed by polycyclic aromatic hydrocarbon, polychlorinated biphenyl and metal contaminants in sediments in UK estuaries and coastal waters. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/ j.marpolbul.2015.03.012

PCB

Region Anglia Anglia Anglia Anglia Anglia Cardigan Bay Cardigan Bay Eastern Channel Eastern Channel Eastern Channel Eastern Channel Humber Wash Humber Wash Humber Wash Humber Wash Humber Wash Humber Wash Irish Sea Irish Sea Irish Sea Irish Sea Irish Sea

PAH

Metal

Station

CB28

CB52

CB101

CB118

CB153

CB180

ANT

BAA

BAP

BGHIP

CHRTR

FLU

ICDP

NAP

PA

PYR

Cd

Cr

Cu

Hg

Pb

Zn

Mean

1 2 3 4 5

-0.56 0.70 -0.27 -0.47 0.56

-0.47 0.64 0.32 -0.59 0.57

-0.56 0.59 0.63 -0.36 0.56

-0.37 0.59 0.38 -0.41 0.45

-0.41 0.49 -0.11 0.33 0.44

-0.38 0.43 0.26 -0.30 0.49

0.85 0.53 -0.63 -0.93 0.50

0.15 0.57 -0.25 -0.87 0.42

-0.27 0.57 -0.61 -0.88 0.41

0.33 0.61 -0.48 -0.82 0.20

-0.06 -0.36 0.32 -0.86 0.22

-0.16 0.53 -0.20 -0.94 0.17

0.70 0.73 -0.41 -0.57 -0.01

0.03 0.58 -0.39 -0.96 0.21

0.36 0.59 -0.21 -0.89 0.49

-0.11 0.54 -0.23 -0.94 0.18

-0.25 0.15 0.90 -0.03 0.75

0.69 0.52 0.79 0.52 0.59

0.57 0.56 0.70 -0.29 0.53

0.38 0.28 0.05 -0.44 0.54

0.51 0.25 0.14 0.59 0.49

0.48 0.22 -0.18 0.04 0.63

0.12 0.45 0.02 -0.45 0.41

6 7

-0.12 -0.36

0.57 0.09

0.44 0.45

0.50 0.29

0.59 0.28

0.51 -0.06

-0.66 -0.34

-0.74 -0.36

-0.75 -0.35

-0.61 -0.45

-0.73 -0.43

-0.75 -0.36

-0.67 -0.40

-0.61 -0.85

-0.69 -0.74

-0.78 -0.36

0.35 0.37

0.52 0.53

-0.08 0.17

0.59 0.28

0.57 0.59

0.44 0.44

-0.13 -0.07

8 9

-0.44 -0.44

-0.64 -0.63

-0.44 -0.51

-0.52 -0.49

-0.64 -0.58

-0.45 -0.42

-0.45 -0.37

0.01 -0.50

0.05 -0.27

-0.34 -0.21

-0.67 -0.48

-0.31 -0.30

-0.33 0.40

0.46 -0.52

-0.03 -0.72

-0.13 -0.23

-0.05 -0.24

0.47 0.11

0.60 -0.65

-0.10 -0.15

-0.17 -0.61

-0.13 -0.34

10 11

* -0.23

* -0.58

* -0.25

* -0.50

* -0.33

* -0.11

* 0.00

* -0.17

* -0.40

* -0.32

* -0.79

* -0.23

* -0.61

* 0.03

* -0.11

* -0.28

* 0.16

0.36 0.10 * 0.35

* 0.28

* -0.61

* 0.44

* 0.49

* -0.15

12 13 14 15 16 17

-0.14 -0.29 -0.29 -0.46 * *

-0.04 -0.46 0.00 -0.45 0.84 *

-0.32 -0.28 -0.08 -0.43 0.74 *

-0.10 -0.54 -0.18 -0.51 0.70 *

-0.24 -0.34 0.01 -0.52 0.87 *

-0.63 -0.57 -0.55 0.01 * *

-0.68 -0.47 -0.48 -0.62 -0.60 *

-0.62 -0.78 -0.38 -0.58 -0.90 *

-0.77 -0.70 -0.65 -0.64 * *

-0.53 -0.79 -0.38 -0.60 -0.96 *

0.03 -0.75 -0.17 -0.70 -0.92 *

-0.70 -0.87 -0.42 -0.61 -0.97 *

-0.55 -0.62 -0.40 -0.58 -0.90 *

-0.41 -0.55 0.04 -0.63 * *

-0.49 -0.42 -0.36 -0.58 -0.90 *

-0.66 -0.80 -0.40 -0.60 -0.98 *

0.45 0.49 -0.31 0.20 * 0.13

0.69 0.31 0.41 0.68 * 0.94

0.69 0.24 0.27 0.82 * 0.98

-0.89 -0.74 0.39 0.25 * 0.33

-0.50 -0.52 -0.58 0.10 * -0.01

-0.67 -0.17 -0.48 0.20 * 0.99

-0.34 -0.44 -0.24 -0.27 -0.44 0.56

18 19 20 21 22 23

-0.56 0.26 -0.46 -0.32 * -0.34

-0.35 0.01 -0.46 -0.48 * *

-0.50 0.01 -0.54 -0.49 * *

-0.46 0.00 -0.51 -0.33 * -0.29

-0.49 0.00 -0.49 -0.22 * *

-0.83 -0.27 -0.29 * * -0.76

-0.52 -0.27 -0.20 -0.79 0.78 0.94

-0.51 0.43 -0.22 -0.71 0.99 -0.18

-0.58 0.39 -0.34 * 0.95 -0.63

-0.73 0.06 0.06 * 0.83 -0.97

-0.87 0.25 -0.93 * * -0.44

-0.61 0.12 -0.27 * 0.99 -0.70

-0.52 0.30 -0.35 -0.81 0.19 -0.53

-0.08 0.57 0.05 * 0.62 0.36

0.12 0.14 -0.12 -0.98 0.99 -0.01

-0.61 0.30 -0.29 * 0.99 -0.73

-0.07 -0.30 -0.44 -0.88 0.70 -0.15

0.65 0.24 0.53 -0.80 0.35 0.33

-0.65 0.55 -0.58 -0.74 -0.40 -0.96

0.47 0.28 -0.50 -0.87 -0.70 0.14

0.44 0.24 -0.47 -0.87 -0.65 -0.15

-0.28 0.16 -0.28 -0.65 0.51 -0.29

0.35

0.17

-0.89

-0.77

-0.56

*

*

*

*

*

24

-0.16

-0.16

-0.16

-0.21

-0.14

-0.63

-0.76

-0.71

-0.84

-0.81

-0.88

-0.85

-0.69

-0.78

-0.77

-0.84

-0.38

Irish Sea Irish Sea Severn

25

*

*

*

*

*

*

*

*

*

*

*

*

*

*

*

*

*

0.79 0.11 0.22 0.08 0.99 0.42 0.52 *

26

-0.80

-0.29

-0.47

-0.60

-0.47

-0.34

0.53

0.53

0.52

0.50

-0.08

0.54

0.52

0.39

0.58

0.53

0.36

0.19

0.57

0.44

-0.06

-0.09

0.20

Severn Severn Severn

27 28 29

-0.74 -0.29 -0.06

-0.28 0.25 -0.01

-0.17 0.41 -0.01

-0.39 0.19 0.01

-0.13 0.30 0.03

-0.30 0.17 0.03

0.24 0.63 -0.23

0.40 0.44 -0.17

0.42 0.48 -0.14

0.38 0.57 -0.32

-0.58 -0.01 -0.33

0.06 0.44 -0.41

0.49 0.61 -0.20

-0.49 -0.59 0.30

-0.17 0.17 -0.46

0.06 0.45 -0.44

-0.71 -0.23 0.65

0.22 0.14 0.78

-0.29 -0.24 0.32

-0.22 0.10 0.69

0.28 0.45 0.50

0.13 0.32 0.55

-0.04 0.24 0.06

-0.59

-0.04

-0.80

-0.75

0.18

0.72 0.66 0.64 0.31 0.71 0.90 0.54 0.61 -0.20

0.17 0.27 0.27 0.19 0.61 0.19 0.16 0.48 0.07

0.29 0.19 0.36 0.23 0.25 0.14 0.44 0.11 -0.42

0.21 0.39 0.43 0.21 0.33 0.35 0.34 0.08 -0.33

-0.02 0.08 0.11 0.05 0.38 -0.08 0.38 0.20 -0.28

-0.35

-0.30

-0.91

-0.93

-0.31

0.80 0.63

-0.05 0.61

-0.09 -0.24

0.06 -0.20

0.03 -0.06 0.15 -0.08 0.51

Irish Sea

Tyne Tees Tyne Tees Tyne Tees Tyne Tees Tyne Tees Tyne Tees Tyne Tees Tyne Tees Tyne Tees Tyne Tees Tyne Tees Tyne Tees Tyne Tees Western Channel Western Channel Western Channel

30

0.00

0.74

0.79

0.77

0.84

*

0.20

0.28

0.06

0.76

0.26

0.84

0.22

*

0.31

0.83

-0.74

31 32 33 34 35 36 37 38 39

-0.39 0.02 -0.41 0.59 -0.31 -0.02 0.35 0.21 0.39

-0.88 -0.01 0.33 -0.30 0.43 0.25 0.58 0.25 0.48

-0.26 0.24 -0.62 -0.12 -0.24 -0.37 0.51 0.29 -0.10

-0.20 -0.18 0.10 -0.14 -0.01 -0.37 0.62 0.03 0.26

-0.51 0.17 0.11 -0.15 -0.04 -0.79 0.27 0.02 -0.04

-0.14 -0.05 -0.38 0.64 0.51 -0.77 0.26 -0.28 *

0.52 -0.20 0.13 -0.10 0.58 -0.32 0.63 0.36 -0.25

-0.07 -0.19 0.12 -0.10 0.40 -0.35 0.49 0.29 -0.30

-0.06 -0.22 0.00 -0.10 0.58 -0.30 0.50 0.19 -0.56

-0.24 -0.21 0.03 -0.50 0.44 -0.24 0.74 0.15 -0.46

-0.64 0.11 -0.15 -0.05 0.22 -0.23 -0.02 0.56 -0.44

-0.16 -0.21 -0.14 -0.10 0.54 -0.34 -0.12 0.06 -0.54

-0.24 0.18 0.28 -0.10 0.50 -0.25 0.79 0.21 -0.40

0.62 0.27 0.08 0.40 0.11 0.25 0.77 0.15 *

0.26 -0.09 0.18 0.08 0.44 -0.29 -0.09 0.18 0.01

-0.07 -0.19 -0.09 -0.10 0.57 -0.35 0.01 0.13 -0.54

-0.66 0.26 0.48 0.21 0.35 0.80 0.31 -0.08 -0.65

40

-0.83

-0.60

-0.77

-0.82

-0.73

-0.88

0.25

0.48

0.27

-0.16

-0.54

0.16

-0.26

0.65

0.27

0.25

-0.92

41 42

0.38 -0.71

0.63 -0.39

0.23 -0.40

0.14 -0.49

-0.55 -0.24

* -0.25

0.51 -0.11

0.26 -0.27

-0.33 -0.31

-0.80 -0.20

0.08 0.96

-0.13 -0.30

-0.24 -0.44

* 0.30

0.52 0.18

-0.10 -0.19

0.13 -0.59

0.04 0.13 0.46 0.41 0.25 0.73 0.72 0.51 0.38 0.21 0.97 0.04 0.43

43 44 45

-0.50 -0.66 -0.67

-0.15 -0.58 0.10

-0.32 -0.57 0.30

-0.31 -0.39 0.28

-0.52 -0.70 0.27

-0.60 -0.57 0.22

0.70 0.31 0.79

0.70 0.42 0.71

0.64 0.24 0.70

0.46 -0.43 0.59

0.12 -0.19 -0.14

0.61 0.28 0.72

0.51 -0.38 0.72

0.30 -0.72 -0.61

0.52 -0.09 0.75

0.60 0.12 0.72

-0.36 0.03 0.68

0.37 0.21 0.65

-0.06 0.25 0.64

-0.11 0.46 0.83

-0.06 0.12 0.75

-0.21 0.10 0.60

Mean

-0.22

-0.04

-0.08

-0.10

-0.11

-0.20

0.00

-0.04

-0.09

-0.14

-0.26

-0.14

-0.10

-0.02

-0.05

-0.12

0.02

0.34

0.34

0.06

0.03

0.02

E.E. Manuel Nicolaus et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx

Bold indicates a significant up or downward trend at the 95% confidence interval (P 6 0.05). Grey highlighted stations were sampled up to 2011.

9

Please cite this article in press as: Manuel Nicolaus, E.E., et al. Spatial and temporal analysis of the risks posed by polycyclic aromatic hydrocarbon, polychlorinated biphenyl and metal contaminants in sediments in UK estuaries and coastal waters. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/ j.marpolbul.2015.03.012

Table 7 Trend (slope) values of the 22 collected contaminants at a specific sampling site over the sampling period of up to 13 years.

10

E.E. Manuel Nicolaus et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx

Table 8 RCR values of contaminant groups of all sampled sites in 2011. Region

Station

RCRERL Metals

SE Metals

N

RCRERL PAHs

SE PAHs

N

RCREAC PCBs

SE PCBs

N

Anglia Anglia

2 5

2.02 10.00

0.26 1.69

30 30

1206 24.80

623.25 7.89

45 44

18.30 36.00

8.28 6.27

30 30

Eastern Channel Humber Wash

8 14

3.77 2.34

1.12 0.53

30 60

0.74 1.17

0.21 0.24

45 90

0.05 0.07

0.01 0.01

30 60

Humber Wash

15

2.16

0.48

30

0.61

0.16

45

0.05

0.01

30

Irish Sea Irish Sea Irish Sea

18 19 20

1.36 4.12 1.96

0.22 1.45 0.29

30 30 30

2.88 2.24 5.51

0.76 0.69 1.95

45 45 45

0.08 0.22 0.28

0.02 0.05 0.08

30 30 30

Severn

26

3.16

0.70

30

99.20

43.01

45

0.45

0.15

30

Tyne Tyne Tyne Tyne

32 35 38 42

6.38 3.94 3.03 3.78

0.93 0.75 0.63 0.68

30 30 30 30

10.90 7.57 4.19 NA

3.10 2.77 1.15 NA

45 45 45 NA

0.55 0.08 0.45 0.13

0.09 0.03 0.10 0.03

30 30 30 30

43 44

1.37 4.78

0.23 0.88

30 30

9.97 3.87

2.96 1.21

45 45

0.28 0.39

0.09 0.12

30 30

Tees Tees Tees Tees

Western Channel Western Channel

RCR values are mean values taking all samples for a specific contaminant group into consideration; MEC = Measured Environmental Concentration; EAC = Ecotoxicological Assessment Criteria; ERL = Effects Range Low; RCR = Risk Characterisation Ratio for EAC and ERL; SE Standard Error around the mean .

Medway, Mersey and Tyne Tees, where concentrations are still very high and potentially causing harm to the marine environment. Acknowledgements The authors would like to thank the Environment Agency for providing the sediment contaminant data, and the quality control and assurance information to the British Oceanographic Data Centre who make the information publically available. We would also like to thank the Department for Environment, Food and Rural Affairs for funding this study under the contract code SLA22. Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.marpolbul.2015. 03.012.

References Besselink, H.T., Denison, M.S., Hahn, M.E., Vethaak, A.D., Koeman, J.H., Brouwer, A., 1997. High induction of cytochrome P4501A activity without changes in retinoid and thyroid hormone levels in flounder (Platichthys flesus) exposed to 2,3,7,8-tetraachlorodibenzo-p-dioxin. Environ. Toxicol. Chem. 16, 816–823. Beyer, J., Peterson, K., Song, Y., Ruus, A., Grung, M., Bakke, T., Tollefsen, K.E., 2014. Environmental risk assessment of combined effects in aquatic ecotoxicology: a discussion paper. Mar. Environ. Res. 96, 81–91. Brian, J.V., Harris, C.A., Scholze, M., Kortenkamp, A., Booy, P., Lamoree, M., Pojana, G., Jonkers, N., Marcomini, A., Sumpter, J.P., 2007. Evidence of estrogenic mixture effects on the reproductive performance of fish. Environ. Sci. Technol. 41, 337–344. Brooks, S., Lyons, B.P., Bignell, J.P., Thain, J.E., 2009. Biomarker responses in mussels, an integrated approach to biological effects measurements. J. Toxicol. Environ. Health. A 72, 196–208. Bryan, G.W., Langston, W.J., 1992. Bioavailability, accumulation and effects of heavy metals in sediments with special reference to United Kingdom estuaries: a review. Environ. Pollut. 76, 89–131. Cefas, 2012. CSEMP Green Book. (accessed 19.02.15). Chapman, P.M., Wang, F., 2001. Assessing sediment contamination in estuaries. Environ. Toxicol. Chem. 20, 3–22. Connell, D.W., Hawker, D.W., Warne, M.J., Vowles, P.P., 1997. Polycyclic aromatic hydrocarbons (PAHs). In: McCombs, K., Starkweather, A.W. (Eds.), Introduction Into Environmental Chemistry. CRC Press LLC, Boca Raton, FL, pp. 205–217. Damiano, S., Papetti, P., Menesatti, P., 2011. Accumulation of heavy metals to assess the health status of swordfish in a comparative analysis of Mediterranean and Atlantic areas. Mar. Pollut. Bull. 62, 1920–1925. Dauvin, J.-C., 2008. Effects of heavy metal contamination on the macrobenthic fauna in estuaries: the case of the Seine estuary. Mar. Pollut. Bull. 57, 160–169. European Commission, 2000. Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000 establishing a framework for Community action in the field of water policy.

European Commission, 2008a. Directive 2008/56/EC of the European Parliament and of the Council of 17 June 2008 establishing a framework for Community action in the field of marine environmental policy. European Commission, 2008b. Directive 2008/105/EC of the European Parliament and of the Council on environmental quality standards in the field of water policy, amending and subsequently repealing Council Directives 82/176/EEC, 83/513/EEC, 84/156/EEC, 84/491/EEC, 86/280/EEC and amending Directive 2000/60/EC of the European Parliament and of the Council. Fox, W.M., Connor, L., Copplestone, D., Johnson, M.S., Leah, R.T., 2001. The organochlorine contamination history of the Mersey estuary, UK, revealed by analysis of sediment cores from salt marshes. Mar. Environ. Res. 51, 213–227. Ghekiere, A., Verdonck, F., Claessens, M., Monteyne, E., Roose, P., Wille, K., Goffin, A., Rappe, K., Janssen, C.R., 2013. Monitoring micropullutants in marine waters, can quality standards be met? Mar. Pollut. Bull. 69, 243–250. Kang, Y., Sheng, G., Fu, J., Mai, B., Zhang, G., Lin, Z., Min, Y., 2000. Polychlorinated biphenyls in surface sediments from Pearl River Delta and Macau. Mar. Pollut. Bull. 40, 794–797. Kannan, K., Johnson, B.-R., Yohn, S.S., Giesy, J.P., Long, D.T., 2005. Spatial and temporal distribution of polycyclic aromatic hydrocarbons in sediments from inland lakes in Michigan. Environ. Sci. Technol. 39, 4700–4706. Kortenkamp, A., 2008. Low dose mixture effects of endocrine disrupters: implications for risk assessment and epidemiology. Int. J. Androl. 31, 233–240. Law, R.J., Biscaya, J.L., 1994. Polycyclic aromatic hydrocarbons (PAH)—problems and progress in sampling, analysis and interpretation. Mar. Pollut. Bull. 29, 235–241. Law, R., Hanke, G., Angelidis, M., Batty, J., Bignert, A., Dacks, J., Daries, I., Denga, Y., Duffek, A., Herut, B., Hylland, K., Lepom, P., Leonards, P., Mehtonen, J., Piha, H., Roose, P., Tronegynski, J., Velikova, V., Vethaak, D., 2010. Marine Strategy Framework Directive Task Group 8 report: Contaminants and pollution effects. H. Piha (editor). JRC Scientific and Technical Report, European Union and ICES, IBAN 978–92-79-15648-9. pp.171. Lee, K.T., Tanabe, S., Koh, C.H., 2001. Distribution of organochlorine pesticides in sediments from Kyeonggi Bay and nearby areas. Korea. Environ. Pollut. 114, 207–213. Leung, K.M.Y., Bjørgesæter, A., Gray, J.S., Li, W.K., Lui, G.C.S., Wang, Y., Lam, P.K.S., 2005. Deriving sediment quality guidelines from field-based species sensitivity distributions. Environ. Sci. Technol. 39, 5148–5156. Long, E.R., Macdonald, D.D., Smith, S.L., Calder, F.D., 1995. Incidence of adverse biological effects within ranges of chemical concentrations in marine estuarine sediments. Environ. Manage. 19, 81–97. Long, E.R., Field, L.J., MacDonald, D.D., 1998. Predicting toxicity in marine sediments with numerical sediment quality guidelines. Environ. Toxicol. Chem. 17, 714– 727. Long, E.R., Ingersoll, C.G., MacDonald, D.D., 2006. Calculation and uses of mean sediment quality guideline quotients: a critical review. Environ. Sci. Technol. 40, 1726–1736. Lyons, B.P., Kirby, M.F., Stewart, C., 1999. The detection of biomarkers of genotoxin exposure in the European flounder (Platichthys flesus) collected from the Tyne Estuary. Mutat. Res. Toxicol. Environ. Mutagen. 446, 111–119. Lyons, B.P., Stentiford, G.D., Green, M., Bignell, J., Bateman, K., Feist, S.W., Goodsir, F., Reynolds, W.J., Thain, J.E., 2004. DNA adduct analysis and histopathological biomarkers in European flounder (Platichthys flesus) sampled from UK estuaries. Mutat. Res. 552, 177–186. Lyons, B.P., Thain, J.E., Stentiford, G.D., Hylland, K., Davies, I.M., Vethaak, A.D., 2010. Using biological effects tools to define good environmental status under the European Union Marine Strategy Framework Directive. Mar. Pollut. Bull. 60, 1647–1651. OSPAR, 2009. Background document on CEMP assessment criteria for QSR 2010. Publication Number: 461/2009. pp. 23.

Please cite this article in press as: Manuel Nicolaus, E.E., et al. Spatial and temporal analysis of the risks posed by polycyclic aromatic hydrocarbon, polychlorinated biphenyl and metal contaminants in sediments in UK estuaries and coastal waters. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/ j.marpolbul.2015.03.012

E.E. Manuel Nicolaus et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx Persuad, D., Jaagumagi, R., Hayton, A., 1992. Guidelines for the Protection and Management of Aquatic Sediment Quality in Ontario. Ontario Ministry of the Environment, Queen’s Printer for Ontario. Rygg, B., 1985. Effect of sediment copper on benthic fauna. Mar. Ecol. Prog. Ser. 25, 83–89. Sakamoto, Y., Ishiguro, M., Kitagawa, G., 1986. Akaike Information Criterion Statistics. Mathematics and Its Application. KTK Scientific Publishers. Sprovieri, M., Feo, M.L., Prevedello, L., Manta, D.S., Sammartino, S., Tamburrino, S., Marsella, E., 2007. Heavy metals, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in surface sediments of the Naples harbour (southern Italy). Chemosphere 67, 998–1009. Turnpenny, A.W.H., Coughlan, J., 1992. Power generation on the British coast: thirty years of marine biological research. Hydroécologie Appliquée 4, 1–11. US EPA, 2013. (accessed 02. 09.13).

11

Van der Oost, R., Beyer, J., Vermeulen, N.P.E., 2003. Fish bioaccumulation and biomarkers in environmental risk assessment: a review. Environ. Toxicol. Pharmacol. 13, 57–149. Webster, L., Roose, P., Bersuder, B., Kotterman, M., Haarich, M., Vorkamp, K., 2013. Determination of polychlorinated biphenyls (PCBs) in sediment and biota. ICES Tech. Mar. Environ. Sci. (53), 18 Wheeler, A., 1969. Fish-life and pollution in the lower Thames: a review and preliminary report. Biol. Conserv. 2, 25–30. Wiberg, P.L., Harris, C.K., 2002. Desorption of p, p’-DDE from sediment during resuspension events on the Palos Verdes shelf, California: a modelling approach. Cont. Shelf Res. 22, 1005–1023. Zhang, L.P., Xin, Y., Huan, F., Jing, Y.H., Ouyang, T., Yu, X.T., 2007. Heavy metal contamination in western Xiamen Bay sediments and its vicinity. China. Mar. Pollut. Bull. 54, 974–982.

Please cite this article in press as: Manuel Nicolaus, E.E., et al. Spatial and temporal analysis of the risks posed by polycyclic aromatic hydrocarbon, polychlorinated biphenyl and metal contaminants in sediments in UK estuaries and coastal waters. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/ j.marpolbul.2015.03.012