Long Term Monitoring Program (LTEMP) Sediments Mussel tissue - - PDF document

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Long Term Monitoring Program (LTEMP) Sediments Mussel tissue - - PDF document

Feb 17, 2024 33 likes •255 views

9/19/19 Long Term Monitoring Program (LTEMP) Sediments Mussel tissue ........... 1993 - Project Initiated by Kinnetic Labs (KLI) based on NOAA Status and Trends Program 2002 - PECI 1 9/19/19 Modified Van Veen grab sampler 2 9/19/19

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SLIDE 1

9/19/19 1

Long Term Monitoring Program (LTEMP)

Sediments Mussel tissue ........... 1993 - Project Initiated by Kinnetic Labs (KLI) based on NOAA Status and Trends Program 2002 - PECI

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SLIDE 2

9/19/19 2

Modified Van Veen grab sampler

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SLIDE 3

9/19/19 3 Mussel Samples

Port Valdez sediments and mussels are sampled annually in summer Beginning in 2009 mussels from the outer stations in PWS and the GOA are sampled in the summer every five years All stations were sampled in 2018

Sampling Design and Frequency

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SLIDE 4

9/19/19 4

Source Identifications and Concentrations

Interpret samples’ hydrocarbon patterns

  • PAH (polycyclic

aromatic hydrocarbons)

  • AHC (aliphatic

hydrocarbons)

  • Sterane/Triterpane

biomarkers

PAH – Polycyclic Aromatic Hydrocarbons

Naphthalene C1-Naphthalene C2-Naphthalene C3-Naphthalene C4-Naphthalene Biphenyl Acenaphthylene Acenaphthene Fluorene C1-Fluorene C2-Fluorene C3-Fluorene Dibenzothiophene C1-Dibenzothiophene C2-Dibenzothiophene C3-Dibenzothiophene Anthracene Phenanthrene C1-Phen/Anthracene C2-Phen/Anthracene C3-Phen/Anthracene C4-Phen/Anthracene Fluoranthene Pyrene C1-Fluor/Pyrene C2-Fluor/Pyrene C3-Fluor/Pyrene Benzo[a]anthracene Chrysene C1-Chrysene C2-Chrysene C3-Chrysene C4-Chrysene Benzo[b]fluoranthene Benzo[k]fluoranthene Benzo[e]pyrene Benzo[a]pyrene Perylene Indeno[1,2,3-c,d]pyrene Dibenzo[a,h]anthracene Benzo[g,h,I]perylene

S

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SLIDE 5

9/19/19 5

PAH – Polycyclic Aromatic Hydrocarbons

PAH 200 400 600 800 1000 1200 1400 1600 1800 N N1 N2 N3 N4 BI AC AE F F1 F2 F3 D D1 D2 D3 D4 A P P/A1 P/A2 P/A3 P/A4 FL PY F/P1 F/P2 F/P3 F/P4 BA C C1 C2 C3 C4 BB BK BEP BAP PER IP DA BP mg/Kg Alaska North Slope Crude

Naphthalene C1-Naphthalene C2-Naphthalene C3-Naphthalene C4-Naphthalene Biphenyl Acenaphthylene Acenaphthene Fluorene C1-Fluorene C2-Fluorene C3-Fluorene Dibenzothiophene C1-Dibenzothiophene C2-Dibenzothiophene C3-Dibenzothiophene Anthracene Phenanthrene C1-Phen/Anthracene C2-Phen/Anthracene C3-Phen/Anthracene C4-Phen/Anthracene Fluoranthene Pyrene C1-Fluor/Pyrene C2-Fluor/Pyrene C3-Fluor/Pyrene Benzo[a]anthracene Chrysene C1-Chrysene C2-Chrysene C3-Chrysene C4-Chrysene Benzo[b]fluoranthene Benzo[k]fluoranthene Benzo[e]pyrene Benzo[a]pyrene Perylene Indeno[1,2,3-c,d]pyrene Dibenzo[a,h]anthracene Benzo[g,h,I]perylene

S

Aliphatic Hydrocarbons (n-alkanes)

H H H—C—C—H H H H H H H—C—C—C—H H H H H H H H H—C—C—C—C—H H H H H H H H H H H—C—C—C—C—C—H H H H H H Average BWTP Water Sample 200 400 600 800 1000 1200 1400 1600 1800 C10 C11 C12 C13 C14 C15 C16 C17 Pristane C18 Phytane C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 n-Alkane (SE mean) ng/L 2001 Mixing Zone Program n=2 Avg TAlk = 17,290 ±3,040

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SLIDE 6

9/19/19 6 Hydrocarbon Biomarkers

well preserved “fossil tattoos”

Terpanes Hopanes Steranes Aromatic Steranes C23 tricyclic terpane T4 18α(H),21β(H)-22,29,30- trisnorhopane Ts Gammacerane T22a C22 5α(H),14β(H),17α(H)-sterane C26,20S TAS TAS0 C20 Pregnane Preg C24 tricyclic terpane T5 17α(H),21β(H)-22,29,30- trisnorhopane Tm 22S-17α(H),21β(H)-30,31- bishomohopane T26 C27 20S-13β(H),17α(H)-diasterane (diacholestane) S4 C26,20R+C27,20S TAS TAS1 C21 20-Methylpregnane MPreg C25 tricyclic terpane (a) T6 17α(H),18α(H),21β(H)-28,30- bisnorhopane 14a 22R-17α(H),21β(H)-30,31- bishomohopane T27 C27 20R-13β(H),17α(H)-diasterane (diacholestane) S5 C28,20S TAS TAS2 C22 20-Ethylpregnane (a) EPregA C25 tricyclic terpane (b) T6 17α(H),21β(H)-25-norhopane 14b 22S-17α(H),21β(H)-30,31,32- trishomohopane T30 C27 20S-5α(H),14α(H),17α(H)- cholestane S12 C27,20R TAS TAS3 C22 20-Ethylpregnane (b) EPregB C24 tetracyclic terpane T6a 17α(H),21β(H)-30-norhopane T15 22R-17α(H),21β(H)-30,31,32- trishomohopane T31 C27 20R-5α(H),14β(H),17β(H)- cholestane S14 C28,20R TAS TAS4 5b(H)-C27 (20S) MAS+ MAS1 C26 tricyclic terpane (a) T6c 18α(H),21β(H)-30- norneohopane T16 22S-17α(H),21β(H)-30,31,32,33- tetrakishomohopane T32 C27 20S-5α(H),14β(H),17β(H)- cholestane S15 C29,20S TAS TAS5 5b(H)-C27 (20R) MAS+ MAS2 C26 tricyclic terpane (b) T6b 17β(H),21α(H)-30-norhopane (normoretane) T17 22R-17α(H),21β(H)-30,31,32,33- tetrakishomohopane T33 C27 20R-5α(H),14α(H),17α(H)- cholestane S17 C29,20R TAS TAS6 5a(H)-C27 (20S) MAS MAS3 C28 tricyclic terpane (a) T8 18α(H) and 18β(H)-oleanane T18 22S-17α(H),21β(H)-30,31,32,33,34- pentakishomohopane T34 C28 20S-5α(H),14α(H),17α(H)-ergostane (methylcholestane) S20 5b(H)-C28 (20S) MAS+ MAS4 C28 tricyclic terpane (b) T7 17α(H),21β(H)-hopane T19 22R-17α(H),21β(H)-30,31,32,33,34- pentakishomohopane T35 C28 20R-5α(H),14β(H),17β(H)-ergostane (methylcholestane) S22 5a(H)-C27 (20R) MAS MAS5 C29 tricyclic terpane (a) T10 17α(H)-30-nor-29- homohopane C28 20S-5α(H),14β(H),17β(H)-ergostane (methylcholestane) S23 5a(H)-C28 (20S) MAS MAS6 C29 tricyclic terpane (b) T9 17β(H),21α(H)-hopane (moretane) T20 C28 20R-5α(H),14α(H),17α(H)-ergostane (methylcholestane) S24 5b(H)-C28 (20R) MAS+ MAS7 22S-17α(H),21β(H)-30- homohopane T21 C29 20S-5α(H),14α(H),17α(H)- stigmastane (ethylcholestane) S25 5b(H)-C29 (20S) MAS+ MAS8 22R-17α(H),21β(H)-30- homohopane T22 C29 20R-5α(H),14β(H),17β(H)- stigmastane (ethylcholestane) S26 5a(H)-C29 (20S) MAS MAS9 C29 20S-5α(H),14β(H),17β(H)- stigmastane (ethylcholestane) S27 5a(H)-C28 (20R) MAS MAS10 C29 20R-5α(H),14α(H),17α(H)- stigmastane (ethylcholestane) S28 5b(H)-C29 (20R) MAS+ MAS11 5a(H)-C29 (20R) MAS MAS12

50 100 150 200 250 300 350 400 450 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 mg/kg

WG1134235-1-ANS

Data analysis

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SLIDE 7

9/19/19 7 BWTF Sampling

2004, 2005, 2016, 2017

Ballast water treatment biological digestion tank Outflow from BWTF to

  • ffshore diffuser

Characterizing the BWTF Effluent

Teflon stopper with Viton “O”-ring Vacuum Pump In-Line Charcoal Filter and Water Trap Portable 110 VAC Power Supply Wooden cruise box serves as support stand/work station 3.8 L (1 gal) amber glass water-sampling bottle 0.7 µm glass- fiber filter in stainless steel Millipore filter holder Flexible vacuum tubing

Utilization of the Portable Large- Volume Water Sampling System (PLVWSS)

sample fluid Filtered oil droplets

Separately analyze the dissolved and particulate phase samples

Dissolved phase hydrocarbons in water Dissolved fraction

filter Raw sample Dissolved fraction

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SLIDE 8

9/19/19 8 BWTF Effluent Phase Profiles – Mar 2017

500 1000 1500 2000 2500 3000 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ng/L

Partic Effluent

TPAH 2,084 Hopane 133

0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 µg/L

Partic Effluent

TSHC 10

50 100 150 200 250 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 ng/L

Partic Effluent

500 1000 1500 2000 2500 3000 3500 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ng/L

Dissolved Effluent

TPAH 11,080 Hopane

0.5 1 1.5 2 2.5 3 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 µg/L

Dissolved Effluent

TSHC 8

0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 ng/L

Dissolved Effluent

Particulate Phase (filter)

PAH* SHC

Dissolved Phase (filtrate)

Biomarkers * PAH with raw BWTF effluent

  • verlay scaled to hopane

BWTF discharge Berth 5 Spill

200 400 600 800 1000 1200 1400 1600 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ng/L

Raw Effluent

TPAH 7,571 Hopane 74

0.5 1 1.5 2 2.5 3 3.5 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 µg/L

Raw Effluent

TSHC 20

200 400 600 800 1000 1200 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP mg/kg

BAR-1709-1

TPAH 6,756 Hopane 138

500 1000 1500 2000 2500 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 mg/kg

BAR-1709-1

TSHC 31,25 2

Fresh ANS crude

  • il overlay

PAH SHC

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SLIDE 9

9/19/19 9

BWT discharge Berth 5 Spill

20 40 60 80 100 120 140 160 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 ng/L

Raw Effluent

50 100 150 200 250 300 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 mg/kg

BAR-1709-1

Fresh ANS crude overlay

Biomarkers

W Driskell

APDES – periodic review of AMT Discharge Permit

Primary contention pertains to Alyeska’s reporting insufficient monitoring data

  • Currently report using 1970’s

era analyte list, the EPA 16 priority pollutants.

  • EVOS 1989 set new standard

to include alkylated PAH (n=44). Current practice is 50 PAH (TPAH50).

  • 16 PAH are inadequate to

distinguish between crude oil and distillates, combustion or biological sources.

  • EPA 16 comprises ~16% of

TPAH44

Alaska North Slope Crude Oil

200 400 600 800 1000 1200 1400 1600 N N1 N2 N3 N4 BI AC AE F F1 F2 F3 D D1 D2 D3 D4 A P P/A1 P/A2 P/A3 P/A4 FL PYR F/P1 F/P2 F/P3 F/P4 BA C C1 C2 C3 C4 BB BK BEP BAP PER IP DA BP mg/Kg PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP

EPA 16 priority pollutants in yellow

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9/19/19 10

2018 Results

2018 Sediments

Gold Creek (GOC) Alyeska Marine Terminal (AMT)

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9/19/19 11

5 10 15 20 25 30 N N1 N2 N3 N4 BI ACY ACN F F1 F2 F3 F4 A Ph PA1 PA2 PA3 PA4 RET DBT DBT1 DBT2 DBT3 DBT4 BBF Fl Py FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C C1 C2 C3 C4 BBF BKF BAF BEP BAP PER INDP DAHA BGHI mg/kg GOC-S-18-2-3 L1825419-07 21 SO TPAH 6/29/2018 2 Hopane 2 4 6 8 10 12 14 T4 T5 T6 TR25b T6a T6b T6c T7 T8 T9 T10 T11 T11a T11b T12 T14a T14b T15 T16 X T17 T18 T19 Nor30H T20 T21 T22 T22A T26 T27 T30 T31 T32 T33 T34 T35 S22 S4 S5 S8 S12 S17 S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS1 TAS2 TAS3 TAS4 mg/kg GOC-S-18-2-3 6/29/2018 0.05 0.1 0.15 0.2 0.25 0.3 0.35 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 1650 C17 Pris C18 Phyt C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 mg/kg 1 TSHC GOC-S-18-2-3 1 2 3 4 5 6 7 N N1 N2 N3 N4 BI ACY ACN F F1 F2 F3 F4 A Ph PA1 PA2 PA3 PA4 RET DBT DBT1 DBT2 DBT3 DBT4 BBF Fl Py FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C C1 C2 C3 C4 BBF BKF BAF BEP BAP PER INDP DAHA BGHI mg/kg GOC-S-18-2-3 L1825419-07 21 SO TPAH 6/29/2018 2 Hopane

Hopane normalized NBT2 normalized

50 100 150 200 250 300 N N1 N2 N3 N4 BI ACY ACN F F1 F2 F3 F4 A Ph PA1 PA2 PA3 PA4 RET DBT DBT1 DBT2 DBT3 DBT4 BBF Fl Py FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C C1 C2 C3 C4 BBF BKF BAF BEP BAP PER INDP DAHA BGHI mg/kg AMT-S-18-2-1 L1825419-01 87 SO TPAH 6/29/2018 22 Hopane 5 10 15 20 25 T4 T5 T6 TR25b T6a T6b T6c T7 T8 T9 T10 T11 T11a T11b T12 T14a T14b T15 T16 X T17 T18 T19 Nor30H T20 T21 T22 T22A T26 T27 T30 T31 T32 T33 T34 T35 S22 S4 S5 S8 S12 S17 S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS1 TAS2 TAS3 TAS4 mg/kg AMT-S-18-2-1 6/29/2018 0.05 0.1 0.15 0.2 0.25 0.3 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 1650 C17 Pris C18 Phyt C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 mg/kg 1 TSHC AMT-S-18-2-1 5 10 15 20 25 N N1 N2 N3 N4 BI ACY ACN F F1 F2 F3 F4 A Ph PA1 PA2 PA3 PA4 RET DBT DBT1 DBT2 DBT3 DBT4 BBF Fl Py FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C C1 C2 C3 C4 BBF BKF BAF BEP BAP PER INDP DAHA BGHI mg/kg AMT-S-18-2-1 L1825419-01 87 SO TPAH 6/29/2018 22 Hopane

Hopane normalized NBT2 normalized PAH SHC biomarkers

AMT sediment GOC sediment

Sediment Trends

1 10 100 1000 10000 Apr-92 Jun-93 Aug-94 Oct-95 Dec-96 Feb-98 Apr-99 Jun-00 Aug-01 Oct-02 Dec-03 Feb-05 Apr-06 Jun-07 Aug-08 Oct-09 Dec-10 Feb-12 Apr-13 Jun-14 Aug-15 Oct-16 Dec-17 Feb-19 TPAH ng/g dry wt AMT-S GOC-S 81 20 2018 avg max min count ± SE AMT-S 80.7 89.7 66.4 3 7.25 GOC-S 19.8 23.6 14.9 3 2.55

Time series of log(TPAH43) in sediments at Alyeska Terminal (AMT) and Gold Creek (GOC). Error bars are + SE of means.

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9/19/19 12

W Driskell

2018 Tissues

2018 Port Valdez Tissues

Gold Creek (GOC) Jackson Point (JAP) Alyeska Marine Terminal, Saw Island (AMT)

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SLIDE 13

9/19/19 13

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ug/kg AMT-B-18-2-2 TPAH 5 Hopane 6 0.02 0.04 0.06 0.08 0.1 0.12 0.14 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 mg/kg AMT-B-18-2-2 TSHC 1 2 3 4 5 6 7 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 ug/kg AMT-B-18-2-2 0.2 0.4 0.6 0.8 1 1.2 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ug/kg JAP-B-18-2-2 TPAH 4 Hopane 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 mg/kg JAP-B-18-2-2 TSHC 1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 ug/kg JAP-B-18-2-2 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ug/kg GOC-B-18-2-1 TPAH 7 Hopane 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 mg/kg GOC-B-18-2-1 TSHC 1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 ug/kg GOC-B-18-2-1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ug/kg WG1142725-1-BLANK TPAH 4 Hopane #N/A 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 #N/A WG1142725-1-BLANK TSHC #N/A 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 #N/A WG1142725-1-BLANK 0.005 0.01 0.015 0.02 0.025 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 mg/kg WG1146625-1-BLANK TSHC

Port Valdez

PAH < MDL (red trace) and generally match those in the Method Blank Traces of pyrogenic PAH at AMT & GOC Only marine and terrestrial input in SHC AMT JAP GOC PAH with MDL SHC Biomarkers Method Blank

2016 Diesel signal in GOC Mussels

Diesel spills were detected at GOC in 2005 and 2016 SHC data differentiate crude oil vs. distillate product (gasoline, diesel, fuel oil) sources

TR T1 T1 T1 T1 Nor T2 T T T T 0.5 1 1.5 2 2.5 3 T4 T5 T6 TR25b T6a T6b T6c T7 T8 T9 T10 T11 T11a T11b T12 T14a T14b T15 T16 X T17 T18 T19 Nor30H T20 T21 T22 T22A T26 T27 T30 T31 T32 T33 T34 T35 S22 S4 S5 S8 S12 S17 S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS1 TAS2 TAS3 TAS4 ng/g dry wt GOC-B-16-2-3 7/6/2016 DB DB DB DB N N N N IN DA B 1380 1470 1650 Ph 5 10 15 20 25 30 35 N N1 N2 N3 N4 BI ACY ACN F F1 F2 F3 F4 A Ph PA1 PA2 PA3 PA4 RET DBT DBT1 DBT2 DBT3 DBT4 BBF Fl Py FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C C1 C2 C3 C4 BBF BKF BAF BEP BAP PER INDP DAHA BGHI ng/g dry wt

GOC-B-15-2-2

20150705 39 Tissue TPAH 7/2/2015 50 100 150 200 250 300 350 400 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 1650 C17 Pris C18 Phyt C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 ng/g dry wt 784 TSHC GOC-B-15-2-2 2 4 6 8 10 12 14 N N1 N2 N3 N4 BI ACY ACN F F1 F2 F3 F4 A Ph PA1 PA2 PA3 PA4 RET DBT DBT1 DBT2 DBT3 DBT4 BBF Fl Py FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C C1 C2 C3 C4 BBF BKF BAF BEP BAP PER INDP DAHA BGHI ng/g dry wt

GOC-B-16-2-3

1607006-06 53 Tissue TPAH 7/6/2016 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 1650 C17 Pris C18 Phyt C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 ng/g dry wt
  • TSHC
GOC-B-16-2-3

PAH SHC 2015 2016 2016

Biomarkers

distilled petrogenic PA pattern diesel-derived descending T4-T6 triterpane pattern

C15 C17 C16 C18 C20 C23 C24 GOC 2016

m/z 85 plot

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SLIDE 14

9/19/19 14

Mussels after 2017 Berth 5 Spill

Pre-spill: Valdez LTEMP mussels were clean with only background pyrogenic signals 1 week post-spill: mussels at AMT & JAP showed ANS oil 10 weeks post-spill: mussels at all three sites had returned to exceptionally clean background levels

0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 N N1 N2 N3 N4 BI ACY ACN F F1 F2 F3 F4 A Ph PA1 PA2 PA3 PA4 RET DBT DBT1 DBT2 DBT3 DBT4 BBF Fl Py FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C C1 C2 C3 C4 BBF BKF BAF BEP BAP PER INDP DAHA BGHI µg/Kg AMT-B-17-2-1 1707006-01 7 Tissue TPAH 7/8/2017 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 T4 T5 T6 TR25b T6a T6b T6c T7 T8 T9 T10 T11 T11a T11b T12 T14a T14b T15 T16 X T17 T18 T19 Nor30H T20 T21 T22 T22A T26 T27 T30 T31 T32 T33 T34 T35 S22 S4 S5 S8 S12 S17 S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS1 TAS2 TAS3 TAS4 µg/Kg AMT-B-17-2-1 7/8/2017 5 10 15 20 25 30 35 40 45 50 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 CARB FLA BBF PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ug/kg SAW-1709-1 TPAH 158 Hopane 6.17 1 2 3 4 5 6 7 8 9 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 Preg MPreg EPregA EPregB TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 ug/kg SAW-1709-1 1 2 3 4 5 6 7 8 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 CARB FLA BBF PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ug/kg SAW-1712-1 TPAH 10 Hopane 1.03 2 4 6 8 10 12 14 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 Preg MPreg EPregA EPregB TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 ug/kg SAW-1712-1

AMT pre spill AMT 1 week post spill AMT 10 weeks post spill PAH Biomarkers

Station Location 2008 2009 2013 2018 Port Valdez AMT Alyeska Marine Terminal 43 38 17 5 GOC Gold Creek 62 54 20 6 Eastern PWS KNH Knowles Head 13 17 12 4 SHB Sheep Bay 15 16 9 5 Central PWS SLB Sleepy Bay 17 15 28 4 DII Disk Island 20 13 30 4 ZAB Zaikof Bay 5 11 33 5 Seward AIB Aialik Bay 13 10 18 5 Western Gulf of AK WIB Windy Bay 9 11 59 4 SHH Shuyak Harbor 15 9 73 5

Beyond the Port

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SLIDE 15

9/19/19 15

0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ug/kg KNH-B-18-2-2 TPAH 4 Hopane 0.02 0.04 0.06 0.08 0.1 0.12 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 mg/kg KNH-B-18-2-2 TSHC 1 0.5 1 1.5 2 2.5 3 3.5 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 ug/kg KNH-B-18-2-2 0.2 0.4 0.6 0.8 1 1.2 1.4 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ug/kg SHB-B-18-2-2 TPAH 4 Hopane 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 mg/kg SHB-B-18-2-2 TSHC 1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 ug/kg SHB-B-18-2-2 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ug/kg WG1142725-1-BLANK TPAH 4 Hopane #N/A 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 #N/A WG1142725-1-BLANK TSHC #N/A 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 #N/A WG1142725-1-BLANK 0.005 0.01 0.015 0.02 0.025 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 mg/kg WG1146625-1-BLANK TSHC

Eastern PWS

All PAH < MDL and similar to MBlks SHC patterns are different and 10X higher than MBlks no pyrogenic PAH SHC show only marine and terrestrial input SHC Biomarkers Knowles Head Sheep Bay Method Blanks ANS Crude PAH with MDL

0.2 0.4 0.6 0.8 1 1.2 1.4 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ug/kg DII-B-18-2-2 TPAH 4 Hopane 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 mg/kg DII-B-18-2-2 TSHC 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 ug/kg DII-B-18-2-2 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ug/kg SLB-B-18-2-2 TPAH 4 Hopane 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 mg/kg SLB-B-18-2-2 TSHC 1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 ug/kg SLB-B-18-2-2 0.2 0.4 0.6 0.8 1 1.2 1.4 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ug/kg ZAB-B-18-2-3 TPAH 5 Hopane 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 mg/kg ZAB-B-18-2-3 TSHC 1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 ug/kg ZAB-B-18-2-3 0.1 0.2 0.3 0.4 0.5 0.6 0.7 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ug/kg WG1144161-1-BLANK TPAH 2 Hopane #N/A 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 #N/A WG1144161-1-BLANK TSHC #N/A 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 #N/A WG1144161-1-BLANK 0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 mg/kg WG1149741-1-BLANK TSHC

Central PWS

SHC Biomarkers Disk Island Sleepy Bay Zaikof Bay Method Blank PAH with MDL

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9/19/19 16

0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ug/kg AIB-B-18-2-2 TPAH 4 Hopane 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 mg/kg AIB-B-18-2-2 TSHC 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 ug/kg AIB-B-18-2-2 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ug/kg SHH-B-18-2-1 TPAH 4 Hopane 0.05 0.1 0.15 0.2 0.25 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 mg/kg SHH-B-18-2-1 TSHC 1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 ug/kg SHH-B-18-2-1 0.2 0.4 0.6 0.8 1 1.2 1.4 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ug/kg WIB-B-18-2-3 TPAH 3 Hopane 0.05 0.1 0.15 0.2 0.25 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 mg/kg WIB-B-18-2-3 TSHC 1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 ug/kg WIB-B-18-2-3 0.1 0.2 0.3 0.4 0.5 0.6 0.7 DEC DEC1 DEC2 DEC3 DEC4 BT0 BT1 BT2 BT3 BT4 N0 N1 N2 N3 N4 BP DBF ACY ACN F F1 F2 F3 ANT PHN PA1 PA2 PA3 PA4 RET DBT0 DBT1 DBT2 DBT3 DBT4 BF FLA PYR FP1 FP2 FP3 FP4 NBT NBT1 NBT2 NBT3 NBT4 BAA C0 C1 C2 C3 C4 BBF BJKF BAF BEP BAP PER IP DAHA BGHIP ug/kg WG1144161-1-BLANK TPAH 2 Hopane #N/A 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 #N/A WG1144161-1-BLANK TSHC #N/A 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 T4 T5 T6 T6a T6b T6c T7 T8 T9 T10 Ts TR30a TR30b Tm 14a 14b T15 T16 T17 T18 OL T19 T20 T21 T22 Gamm T26 T27 T30 T31 T32 T33 T34 T35 S4 S5 S8 DIA29S DIA29R S18 S19 S20 S24 S25 S28 S14 S15 S22 S23 S26 S27 TAS0 TAS1 TAS2 TAS3 TAS4 TAS5 TAS6 Preg MPreg EPregA EPregB MAS1 MAS2 MAS3 MAS4 MAS5 MAS6 MAS7 MAS8 MAS9 MAS10 MAS11 MAS12 #N/A WG1144161-1-BLANK 0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016 C9 C10 C11 C12 C13 1380 C14 1470 C15 C16 Npris C17 Pris C18 Phy C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 mg/kg WG1149741-1-BLANK TSHC

Gulf of Alaska

SHC Biomarkers Aialik Bay Windy Bay Shuyak Harbor Method Blank PAH with MDL

Tissue Trends

1 10 100 1000 10000 100000 Apr-92 Apr-94 Apr-96 Apr-98 Apr-00 Apr-02 Apr-04 Apr-06 Apr-08 Apr-10 Apr-12 Apr-14 Apr-16 Apr-18 Apr-20 TPAH ng/g dry wt All sites AMT-B GOC-B JAP-B tanker spill diesel spill 6 5 4

Jul-08 Sep-08 Apr-09 Jul-09 Jul-10 Jul-11 Jul-12 Jul-13 Jul-15 Jul-16 Jul-17 Jul-18 Mean TPAH AMT 43 20 38 20 17 29 33 17 70 9 7 5 GOC 62 34 54 25 22 29 46 20 43 31 9 6 JAP 14 9 4 +SE of means AMT 5.8 1.9 6.8 0.8 0.9 2.2 3.1 2.9 8.6 1.9 0.3 0.5 GOC 6.3 3.5 2.8 1.2 1.4 3.3 6.6 2.4 3.6 15.7 0.5 0.6 JAP 1.6 2.6 0.2

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9/19/19 17

Passive Sampling Devices

from Auke Bay protocols retrieving Saw Island PSD retrieving Jackson Point PSD

Passive Sampling Devices -- Port Valdez 2016-2018

JAP AMT GOC 2016 2017 2018

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9/19/19 18 2018 Passive Sampling Devices: JAP, KNH, AMT, DII, GOC

JAP KNH AMT DII GOC

2002 Dissolved PAH Nearshore Knight Island (Payne et al., 2005d)

All Years and Stations show similar patterns No correlation to known oil sources (DII or AMT) Don’t match leaching oil patterns 13 years after EVOS

2018 Results – interpretive highlights

Sediments

All PAH and SHC above MDLs AMT PAH trending from primarily petrogenic (oil) to pyrogenic (combustion) source patterns AMT a mixture of petrogenic, terrestrial and marine biogenic SHC components AMT PAH decreasing but biomarkers still show Alyeska Ballast Water Treatment Tank discharges Historically, GOC PAH show background and pyrogenic sources with concentrations 4-10 times lower than AMT 2018 PAH patterns at GOC cannot be attributed to Terminal operations but biomarker data in 2011 – 2017 demonstrate low-level BWTF source

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9/19/19 19

2018 Results – interpretive highlights

Tissues

PAH at trace levels < MDL s PAH patterns & concentrations generally match those in the Method Blanks (MBlks) Trace pyrogenic HC at AMT & GOC and chrysene only at KNH, SHB, DII, SLB & ZAB Traces of petrogenic biomarkers at AMT & GOC SHC show marine and terrestrial input Crude oil and diesel spills detected in 1994, 2005, 2015, and 2017

Entire study area is exceptionally clean relative to past (1993- 2003) measurements

Take-Home Messages

  • LTEMP has successfully tracked hydrocarbon contamination

and sources for over 25 years

  • Mussel tissue samples are incredibly clean at PWS and GOA

stations (including previously EVOS-oiled sites)

  • Mussels within Port Valdez (including immediately next to

the Terminal) are also exceptionally clean

  • Presumably due to reduced TAP oil flow, segregated tanker ballast,

and improved BWTF treatment

  • Sediments at AMT still show residual hydrocarbons from

treated BWTF discharges

  • Both mussel and passive sampling approaches document

that the region is exceptionally pristine

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9/19/19 20

Massive Thanks

to all those who have made this work possible Supporting staff, colleagues, families and friends

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9/19/19 21

SAC

Vessel support

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9/19/19 22

Questions?