Table ESI-1 Sediment PAHs concentrations (µg/kg, except THC mg/kg) in Milford Haven, October 1993 (MHWESG survey; Levell 30 )

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1 Electronic Supplementary Material (ESI) for Environmental Science: Processes & Impacts. This journal is The Royal Society of Chemistry 2014 Table ESI-1 Sediment PAHs concentrations (µg/kg, except THC mg/kg) in Milford Haven, October 1993 (MHWESG survey; Levell 30 ) Site Location Latitude, Longitude % < 63 µm Naphthalene C1-N C2-N C3-N Phenanthrene Anthracene C1-P Fluoranthene Pyrene 1 Black Hill N o, W o < < Hook Bight N o, W o < < Underwood Quay N o, W o 3.47 < < 24 < < Picton Point N o, W o < < 5 < < off Rigan Pill N o, W o < 26 < < < Crafty Wood Fort N o, W o < < 5 < off Landshipping Quay N o, W o < 18 < < < Knap Wood N o, W o < < 17 < off Llangwm Pill N o, W o < 5 < < Garron Pill N o, W o 27.7 < < 26 < < Jenkins Point N o, W o < 45 < 165 < downstream Lawrenny N o,w o < < 11 < < Cosheston Point N o, W o < < 48 < Cosheston Pill N o, W o < 180 < < Neyland Bridge N o, W o < < 150 < < off Hobbs Point N o, W o < < off Llanstadwell N o, W o < 15 < < off Hazelbeach N o, W o < < 19 < < off Llanreath N o, W o < < Pembroke River N o, W o < 52 < off Pennar N o, W o < < < Mid-channel off Gulf N o, W o < < < off Mine Depot jetty N o, W o < < < off Texaco jetty N o, W5.027 o < 60 < 60 < off Hakin Point N o, W o < 51 < 51 < < Texaco to Elf jetties N o, W o <

2 Site Location Latitude, Longitude % < 63 Naphthalene C1-N C2-N C3-N Phenan- Anthra- C1-P Fluoran- Pyrene µm threne cene thene 78 off Angle point N o, W o < 40 < < Angle Bay N o, W o < 32 < < Mid-channel Angle Pen. N o, W.0865 o < 48 < 48 < 20 < off West Pill N o, W o < 25 < 25 < 15 < Dale Roads N o, W o < 22 < 22 < 14 < Dale Pt. to Thorn Pt. N o, W o < 28 < 28 < 21 < < < Castlebeach Bay N o, W o < < off St. Ann's Head N o, W o < 6 < 6 < 5 < < 5 < 7 < 6 Table ESI-1 Continued Site Location B[a]A Chrysene "2,3BA" B[b]F B[jk]F B[e]P B[a]P Perylene I[123-cd]P B[ghi]P PAH THC 1 Black Hill < < < Hook Bight < < Underwood Quay < 25 < 24 < < 7 < 10 < Picton Point < < off Rigan Pill < < Crafty Wood Fort 36.2 < 36 < 65 < < 43 < 290 < off Landshipping Quay < < < 14 < Knap Wood < < 48 < off Llangwm Pill < < < 17 < 10 < 44 < Garron Pill < < < 415 < < Jenkins Point < 105 < < downstream of Lawrenny < < 54 < Cosheston Point < < 93 < Cosheston Pill < < Neyland Bridge < 320 < < off Hobbs Point < <

3 Site Location B[a]A Chrysene "2,3BA" B[b]F B[jk]F B[e]P B[a]P Perylene I[123-cd]P B[ghi]P PAH THC 48 off Llanstadwell < < 46 < off Hazelbeach < < off Llanreath < Pembroke River < < 170 < off Pennar < < < Mid-channel to Pwllcrochan < 340 < < 160 < off Mine Depot jetty < < 46 < off Texaco jetty < < 140 < off Hakin Point < 108 < 310 < 107 < < 163 < Texaco to Elf jetties < < 427 < off Angle point < 34 < 25 < 12 < < 7.1 < 10.6 < Angle Bay < 59 < 43 < 20 < < 10 < Mid-channel Angle Pen < 200 < < 26 < 55 < off West Pill < 105 < < 12 < Dale Roads < 54 < 47 < < Dale Pt. to Thorn Pt < 69 < 49 < < Castlebeach Bay < 80 < 55 < < 12 < off St. Ann's Head < 5 < 5 < 8 < 5 < 5 < 5 < 5 < 5 < 5 < [Source: Milford Haven Waterway Environmental Surveillance Group (MHWESG) 1993 survey; Levell 30 ]

4 Table ESI-2 Sediment PAHs concentrations (µg/kg, except THC mg/kg) in Milford Haven, 14 October - 8 November 1996 (SEEEC survey; Levell 30 ) Site Location % < 63 Naphth- C1-N C2-N C3-N Phenan- Anthra- C1-P Fluoran- Pyrene B[a]A µm alene threne cene thene 1 Black Hill Hook Bight Underwood Quay < Picton Point 5.51 < < off Rigan Pill < Crafty Wood Fort 22.3 < off Landshipping Quay Knap Wood < 5 < < off Llangwm Pill < 5 < 5 < 5 < < 5 < Beggars Reach < 5 < Garron Pill < Jenkins Point Black Mixen Pool downstream of Lawrenny < 8.5 < 5 < 5 < < 5 < 5 < < 5 35 Cosheston Point < < Cosheston Pill Neyland Bridge < < off Hobbs Point < off Llanstadwell < off Hazel Beach < off Llanreath < Pembroke River < < < off Pennar < < Mid-channel to Pwllcrochan 6.72 < off mine depot jetty 39.9 < < off Texaco jetty < <

5 Site Location % < 63 µm Naphthalene C1-N C2-N C3-N Phenanthrene Anthracene C1-P Fluoranthene Pyrene B[a]A 72 off Hakin Point 66.3 < between Texaco & Elf jetties < off Angle point < < Angle Bay < < Mid-channel Angle Peninsula 54.1 < < off West Pill < Dale Roads < < between Dale Point & Thorn Pt < < Castle Beach Bay < < 5 < off St. Ann's Head 0.48 < 5 < 5 < 5 < 5 < 5 < 5 < 5 < 5 < 5 < 5 Table ESI-2 Continued Site Location Chrysene "2,3BA" B[b]F B[jk]F B[e]P B[a]P Perylene I[123-cd]P B[ghi]P PAH THC 1 Black Hill 647 < 675 < < 650 < Hook Bight 1122 < Underwood Quay 393 < < Picton Point 40.8 < < off Rigan Pill 89.1 < < Crafty Wood Fort 65.3 < 92 < < off Landshipping Quay 251 < < 200 < 222 < Knap Wood < 5 < 25 < 9 < 5 < 6 < 5 < 5 < 5 < off Llangwm Pill 11 < 25 < < Beggars Reach 29.5 < 42 < Garron Pill 54.3 < Jenkins Point < Black Mixen Pool < downstream of Lawrenny < 5 - < 12 < 5 < < 8 < 5 <

6 Site Location Chrysene "2,3BA" B[b]F B[jk]F B[e]P B[a]P Perylene I[123-cd]P B[ghi]P PAH THC 35 Cosheston Point < Cosheston Pill < Neyland Bridge < < off Hobbs Point < off Llanstadwell < off Hazel Beach 64.5 < < off Llanreath 142 < Pembroke River < 5 < < off Pennar 179 < Mid-channel to Pwllcrochan 59.8 < off mine depot jetty 80.5 < off Texaco jetty 297 < off Hakin Point 124 < between Texaco & Elf jetties 68.5 < off Angle point 23.1 < Angle Bay < < Mid-channel Angle Peninsula 64.4 < < < off West Pill 41.3 < Dale Roads 24.2 < < 17 < 6.5 < 17 < between Dale Point & Thorn Pt < < 16 < Castle Beach Bay 19.1 < off St. Ann's Head < 5 < 25 < 5 < 5 < 5 < 5 < 5 < 5 < [Note: Station positions as given in Table ESI-1; Source: Sea Empress Environmental Evaluation Committee (SEEEC) 1996 survey; Levell 30 ]

7 Table ESI-3 Sediment contaminants at 15 intertidal stations (EU Habitats Directive) in Milford Haven, October 2007 (See Table 1 for stations and positions) Analyte, dry mass Units ISQG -TEL PEL 1 SHU 2 SHL 3 AH 4 AB 5 PRU Organic Carbon % <0.4 < < Mercury mg/kg Cadmium mg/kg < Chromium mg/kg Copper mg/kg Lead mg/kg Zinc mg/kg Acenaphthene µg/kg <10 < Acenaphthylene µg/kg < Anthracene µg/kg < B[a]anthracene µg/kg B[a]pyrene µg/kg B[b]anthracene µg/kg <10 <10.0 <22.6 < <20.0 <10.0 <40.6 <14.1 <16.4 <15.7 <10 <11.5 < B[b]fluoranthene µg/kg B[e]pyrene µg/kg < B[ghi]perylene µg/kg < B[j]fluoranthene µg/kg < B[k]fluoranthene µg/kg < Chrysene µg/kg Dibenzo[ah]anthracene µg/kg < Dibenzothiophene C1 µg/kg <10 < Dibenzothiophene C2 µg/kg Dibenzothiophene µg/kg <10 < Dibenzothiophene C3 µg/kg Fluoranthene µg/kg Fluorene µg/kg < Indeno[123-cd]Pyrene µg/kg < Naphthalene µg/kg Naphthalenes C1 µg/kg Naphthalenes C3 µg/kg <10 < < Perylene µg/kg < PRL 7 CPU 8 CPL 9 CARL 11 CRRU 12 CRRL 13 WCL 14 WCU 15 ECL 16 ECU

8 Analyte, dry mass Units ISQG -TEL PEL 1 SHU 2 SHL 3 AH 4 AB 5 PRU Phenanthrene µg/kg Phenanthrenes C1 µg/kg < Phenanthrenes C2 µg/kg Phenanthrenes C3 µg/kg Pyrene µg/kg PCB 028 µg/kg <0.1 < <0.1 <0.1 < <0.1 < <0.1 <0.1 <0.1 <0.1 <0.1 PCB 052 µg/kg <0.1 <0.1 <0.1 <0.1 <0.1 < <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 PCB 101 µg/kg <0.1 <0.1 <0.1 <0.1 <0.1 < <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 PCB 118 µg/kg <0.1 <0.1 <0.1 <0.1 <0.1 < <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 PCB 138 µg/kg <0.1 <0.1 <0.1 <0.1 <0.1 < <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 PCB 153 µg/kg <0.1 <0.1 <0.1 <0.1 <0.1 < <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 PCB 180 µg/kg <0.1 <0.1 <0.1 <0.1 <0.1 < <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 TBT: as cation µg/kg <3.0 < <3.0 < < <3.0 <3.0 <3.0 <3.0 < Methylnaphthalene µg/kg <50 < <50 <50 <50 <50 <50 <50 <50 <50 <50 <50 <50 <50 6 PRL 7 CPU 8 CPL 9 CARL 11 CRRU 12 CRRL 13 WCL 14 WCU 15 ECL 16 ECU [Note: ISQG-TEL is Interim sediment Quality Guidelines- Threshold Effects Level of Environment Canada, and PEL is Probable Effects Level of NOAA; Source: Contains Natural Resources Wales information Natural Resources Wales and database right]

9 Table ESI-4 Sediment contaminants at 15 intertidal stations (EU Habitats Directive) in Milford Haven, 1 3 October 2012 (See Table 1 for stations and positions) Analyte, dry mass Units MRV 1 SHU 2 SHL Ammoniacal Nitrogen mg/kg Nitrate mg/kg 3 <3 <3 <3 <3 <3 <3 <3 Nitrite mg/kg 0.1 <0.1 < <0.1 <0.1 <0.1 <0.1 Nitrogen Total mg/kg 3 <3 <3 <3 <3 <3 <3 <3 Orthophosphate mg/kg 1 <7 <7 <10 <7 22 <10 56 Phosphorus mg/kg Organic Carbon % Nitrogen % Mercury mg/kg Cadmium mg/kg Chromium mg/kg Copper mg/kg Lead mg/kg Zinc mg/kg Benzo[b]anthracene µg/kg 10 <10 <10 <10 <10 <10 <10 <10 Benzo[e]pyrene µg/kg 10 <10 < Benzo[j]fluoranthene µg/kg 10 <10 < C1 Chrysene µg/kg 10 <10 < C1 Dibenzothiophene µg/kg 10 <10 < < C1 Fluoranthene µg/kg 10 < C1 Fluorene µg/kg 10 <10 < C1 Naphthalene µg/kg 10 < C1 Phenanthrene µg/kg 10 <10 < C2 Chrysene µg/kg 10 <10 < < C2 Dibenzothiophene µg/kg 10 <10 < C2 Fluorene µg/kg 10 <10 < AH 4 AB 5 PRU 6 PRL 7 CPU

10 Analyte, dry mass Units MRV 1 SHU 2 SHL C2 Naphthalene µg/kg 10 < C2 Phenanthrene µg/kg 10 < C3 Chrysene µg/kg 10 <10 < C3 Dibenzothiophene µg/kg 10 <10 <10 60 < C3 Fluorene µg/kg 10 <10 < C3 Naphthalene µg/kg 10 < C3 Phenanthrene µg/kg 10 < C4 Chrysene µg/kg 10 <10 < < C4 Naphthalene µg/kg 10 < C4 Phenanthrene µg/kg 10 < Dibenzothiophene µg/kg 10 <10 < < Perylene µg/kg 10 <10 < Acenaphthene µg/kg 2 < Acenaphthylene µg/kg 2 <2 < Anthracene µg/kg 2 < Benz[a]anthracene µg/kg Benzo[a]pyrene µg/kg Benzo[b]fluoranthene µg/kg 10 < Benzo[ghi]perylene µg/kg 10 <10 < Benzo[k]fluoranthene µg/kg 10 <10 < Chrysene µg/kg 3 < Dibenzo[ah]anthracene µg/kg 5 <5 < Fluoranthene µg/kg Fluorene µg/kg 10 <10 < Indeno[1,2,3-cd]pyrene µg/kg 10 <10 < Naphthalene µg/kg 30 <30 < Phenanthrene µg/kg 10 < Pyrene µg/kg AH 4 AB 5 PRU 6 PRL 7 CPU

11 Analyte, dry mass Units MRV 1 SHU 2 SHL PCB µg/kg 0.1 <0.1 < PCB µg/kg 0.1 <0.1 <0.1 <0.2 <0.1 <0.2 <0.1 <0.1 PCB µg/kg 0.1 <0.1 < < <0.3 <0.1 PCB µg/kg 0.1 <0.1 < < <0.1 PCB µg/kg 0.1 <0.1 < < <0.2 <0.1 PCB µg/kg 0.1 <0.1 < < PCB µg/kg 0.1 <0.1 < <0.1 < <0.1 Tributyl Tin as Cation µg/kg 3 <3 <3 <5 <3 <4 <4 <4 Dry Solids at 30 C % [Note: MRV is Measurement Reporting Verification; Source: CCW 2012 survey; contains Natural Resources Wales information Natural Resources Wales and database right] Table ESI-4 Continued 3 AH 4 AB 5 PRU 6 PRL 7 CPU Analyte, dry mass Units MRV 8 CPL 9 CARL 11 CRRU Ammoniacal Nitrogen mg/kg Nitrate mg/kg 3 <3 < <3 <3 <3 <3 <3 Nitrite mg/kg 0.1 < <0.1 <0.1 <0.1 <0.1 <0.1 Nitrogen Total mg/kg 3 <3 < <3 <3 <3 <3 <3 Orthophosphate mg/kg 1 < Phosphorus mg/kg Organic Carbon % Nitrogen % Mercury mg/kg Cadmium mg/kg Chromium mg/kg Copper mg/kg CRRL 13 WCL 14 WCU 15 ECL 16 ECU

12 Analyte, dry mass Units MRV 8 CPL 9 CARL 11 CRRU Lead mg/kg Zinc mg/kg Benzo[b]anthracene µg/kg 10 <10 <10 <10 <10 <10 <10 < Benzo[e]pyrene µg/kg Benzo[j]fluoranthene µg/kg C1 Chrysene µg/kg C1 Dibenzothiophene µg/kg C1 Fluoranthene µg/kg C1 Fluorene µg/kg C1 Naphthalene µg/kg C1 Phenanthrene µg/kg C2 Chrysene µg/kg C2 Dibenzothiophene µg/kg C2 Fluorene µg/kg C2 Naphthalene µg/kg C2 Phenanthrene µg/kg C3 Chrysene µg/kg C3 Dibenzothiophene µg/kg C3 Fluorene µg/kg C3 Naphthalene µg/kg C3 Phenanthrene µg/kg C4 Chrysene µg/kg C4 Naphthalene µg/kg C4 Phenanthrene µg/kg Dibenzothiophene µg/kg Perylene µg/kg Acenaphthene µg/kg CRRL 13 WCL 14 WCU 15 ECL 16 ECU

13 Analyte, dry mass Units MRV 8 CPL 9 CARL 11 CRRU Acenaphthylene µg/kg Anthracene µg/kg Benz[a]anthracene µg/kg Benzo[a]pyrene µg/kg Benzo[b]fluoranthene µg/kg Benzo[ghi]perylene µg/kg Benzo[k]fluoranthene µg/kg Chrysene µg/kg Dibenzo[ah]anthracene µg/kg Fluoranthene µg/kg Fluorene µg/kg Indeno[1,2,3- cd]pyrene µg/kg Naphthalene µg/kg Phenanthrene µg/kg Pyrene µg/kg PCB µg/kg PCB µg/kg 0.1 <0.2 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 PCB µg/kg 0.1 < <0.3 <0.2 < < PCB µg/kg < <0.1 <0.2 PCB µg/kg < < PCB µg/kg PCB µg/kg 0.1 <0.1 <0.1 <0.2 <0.1 <0.1 <0.1 <0.1 <0.1 Tributyl Tin as Cation µg/kg 3 <4 <4 <5 <4 <5 <6 <4 <5 Dry Solids at 30 C % CRRL 13 WCL 14 WCU 15 ECL 16 ECU [Note: MRV is Measurement Reporting Verification; Source: CCW 2012 survey; contains Natural Resources Wales information Natural Resources Wales and database right]

14 70 Cardiff Σ40 PAH ng/m ng/m3 Q Figure ES1-1 Annual mean Σ40 PAH concentrations in air samples (left) at up to 25 monitoring stations in UK from , and (right) quarterly mean at Cardiff monitoring station from ; Q (Buncefield incident 11 December 2005) indicated in red (Defra 40 ) Port Talbot Σ40 PAH ng/m 3 Newport Σ40 PAH ng/m Figure ES1-2 Quarterly mean Σ40 PAH concentrations in air samples at (left) Newport and (right) Port Talbot monitoring stations from ; Q (Buncefield incident 11 December 2005) indicated in red (Defra 40 )

15 Bioaccumulation of Σ16 PAH (µg/kg) in mussel (top) and ragworm (bottom) at Angle Harbour (AH), Pennar (PRU), 2010 Figure ESI-3 Concentrations Σ16 PAH (µg/kg) at MHWESG bioaccumulation monitoring sites (top) in mussel Mytilus edulis from early and (bottom) in ragworm Hediste diversicolor from late 2007 to 2010; Angle Harbour and Pennar (Pembroke River Upper) in 2010 shown in red (after Langston 38 their Figures 22 and 23 respectively) Plate 1 Contemporary photograph showing the Admiralty Llanreath fuel depot fire after Luftwaffe bombing raid of 19 August 1940 (Source:

16 Plate 2 West Williamston marsh-front at the Carew and Cresswell Rivers confluence, oiled by the El Omar incident, photograph 7 December 1988 (Source: Little 4 )

17 Plate ESI-1 Contemporary photograph showing the Admiralty Llanreath fuel depot fire after Luftwaffe bombing raid of 19 August 1940 (Source:

18 Plate ESI-2 West Williamston marsh-front at the Carew and Cresswell Rivers confluence, oiled by the El Omar incident, photograph 7 December 1988 (Source: Little 4 )