The Importance of Distinguishing Dissolved- Versus ...

THE IMPORTANCE OF DISTINGUISHING DISSOLVED- VERSUS OIL-DROPLET PHASES IN ASSESSING THE FATE, TRANSPORT, AND TOXIC EFFECTS OF MARINE OIL POLLUTION1 James R. Payne Payne Environmental Consultants, Incorporated 317 N. El Camino Real, Suite 201 Encinitas, CA 92024

William B. Driskell 6536 20th Avenue NE Seattle, WA 98115

ABSTRACT: For years, it has been known that oil released in seawater partitions into dissolved and oil-droplet phases; however, there has been little effort to discriminate between the phases in oil spill Natural Resource Damage Assessment (NRDA) programs. In 1999, portable field equipment was built for this task. By filtering 3.5 L volumes of seawater at the time of collection, method detection limits are improved and it is possible to discriminate between the phases, thereby improving understanding of oil fate and transport processes and providing more accurate toxicological assessments. First utilized in response to the M/V New Carissa oil spill at Coos Bay, Oregon, this approach proved highly successful in discriminating the phase signatures. The resulting data demonstrated that while the dissolved-phase signal appeared in places such as crab tissue and interstitial water on an otherwise clean beach, the oil-droplet phase appeared in tissues of filter-feeding Coos Bay mussels and oysters. In Port Valdez, Alaska, the portable sampler was used to assess the phase signatures in effluent from the Ballast Water Treatment Facility (BWTF) at the Alyeska Marine Terminal. The signatures were then used to reveal differential seasonal uptake in mussels at several sites within the port. During the winter, when the water column is unstratified, both dissolved- and oildroplet phase contaminants from the BWTF diffuser can reach the upper water column, where they are transported as a surface microlayer by winds and surface currents throughout much the fjord. In the late spring, summer, and fall, when the water column is highly stratified, only the dissolved-phase components are observed in the mussels along the shoreline, as the oil droplets are preferentially trapped below the thermocline. These findings have compelled a reassessment of monitoring methods for oil spill NRDA efforts, National Pollutant Discharge Elimination System (NPDES) permitting, and general environmental monitoring.

PAH components and aliphatic hydrocarbons (AHC) remain in the dispersed oil droplets. Thus, in an oil-contaminated water sample, PAH and AHC histogram plots of dispersed oil droplets will resemble the fresh (or perhaps weathered) source oil. The dissolved-phase sample will contain primarily the more watersoluble alkylated naphthalenes with lesser amounts of fluorenes, dibenzothiophenes and phenanthrenes/anthracenes, and only traces of the less water-soluble higher-molecular-weight PAH and aliphatic (n-alkane) components. The dissolved phase is also the most important in assessing the toxicological water-column impacts from a spill, because the slightly water-soluble PAH components are bioavailable and thereby exhibit the greatest potential to bioaccumulate and impart toxicity to exposed organisms (French-McCay 2002). The much more water-soluble benzene, toluene, ethylbenzene, and xylene (BTEX) components along with other alkyl-substituted benzenes will also initially be present in the dissolved phase in the event of fresh crude oil and some distillate product (gasoline) spills, but they are rapidly lost by evaporation from both the surface oil slick and the upper water column (Payne et al. 1984). As a result, they generally do not persist long enough to be a significant contributor to longer-term toxicity or bioaccumulation (French-McCay 2002). To more accurately assess the levels of water-born contaminants during oil-spill events, Payne et al. (1999) constructed a portable field sampler designed to filter out the dispersed oil droplets at the time of collection and thus provide samples for discrete analyses of both dissolved- and oil-droplet phase components. Whereas in the past, an investigator assessing oil contamination would be attuned to just the droplet or whole oil signature, now having the complementary signature from the dissolved phase expands the insights into fate and effects of released oil. In this paper, we present three examples where discrete phase data were important for assessing the fate and behavior of oil in the marine environment: (1) the M/V New Carissa oil spill in 1999 near Coos Bay, Oregon; (2) a ballast water treatment facility (BWTF) diffuser/mixing zone assessment at the Alyeska Pipeline Services Company terminal in Port Valdez, Alaska; and (3) the Prince William Sound Regional Citizens Advisory Council’s Long Term Environmental Monitoring Program (LTEMP, 19932000). In light of these results, data from the T/V Exxon Valdez oil spill (EVOS) archival database are then presented to demonstrate the differential partitioning of dissolved- and discrete oil-phase components into herring egg and mussel samples collected in 1989-1991.

Introduction The dissolution behavior of petroleum in seawater reflects a basic principle of equilibrium partitioning which holds true for dissolved-oil components regardless of the absolute oil source or mixture of sources (NRC 1985; Payne et al. 1983; 1984; Payne and McNabb 1984). In any petroleum-water mixture, the more water-soluble, lower-molecular-weight polynuclear aromatic hydrocarbon (PAH) fractions tend to dissolve to a limited extent into the water, while the less soluble, higher-molecular-weight

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2003 INTERNATIONAL OIL SPILL CONFERENCE

Methods The Portable Large Volume Water Sampling System (PLVWSS) used for these studies was described previously by Payne et al. (1999). The PLVWSS filters a 3.5 L sample through a 0.7 µm glass fiber filter thus allowing separate examination of the dispersed-oil droplets (trapped on the filter) and the dissolvedphase components collected in a standard, 1-gallon (3.8 L) amber-glass bottle. Following the M/V New Carissa spill event, PLVWSS samples were obtained from the surf-zone along the coast line, along sub-surface transects near several commercial oyster beds within Coos Bay, and from near-surface (-1 m) and near-bottom (+1 m) samples collected using a Go-Flo Bottle® at three offshore stations up to 5 km away from the M/V New Carissa (Payne and Driskell 1999). In the Alyeska BWTF diffuser/mixing zone study, samples were collected with a Go-Flo Bottle® at a variety of depths at stations surrounding the mixing zone and processed with the PLVWSS before solvent extraction and analysis (Salazar et al. 2002).

Results and discussion M/V New Carissa oil spill. During a storm on 4 February 1999, the bulk cargo ship M/V New Carissa ran aground north of the harbor entrance to Coos Bay, Oregon, spilling approximately 70,000 gallons of an unknown mixture of four fuel oils into the coastal environment. Figures 1 and 2 show the PAH and AHC histograms of a mixed-source oil sample collected from the beach immediately adjacent to the stricken vessel, from the dissolvedand physically dispersed oil-droplet phase constituents in PLVWSS water samples collected from the surf zone near the vessel, from mussels collected from the outside northern jetty leading into Coos Bay, and from one of 10 Dungeness crab samples collected in and around the entrance to Coos Bay during the first two weeks following the spill. The data show two different mechanisms of hydrocarbon uptake into affected organisms: (1) accumulation by filter-feeding organisms of primarily intermediate-molecular-weight PAH (Figure 1D) constituents from well-weathered dispersed oil droplets and oiled suspended particulate material (SPM), and (2) direct uptake in crabs of lower-molecular-weight dissolved-phase PAH (primarily naphthalenes – Figure 1E) from the water column with only trace accumulations of the higher-molecular- weight components (and no fluoranthenes/pyrenes or chrysenes). The weathering effects from very rapid evaporation/dissolution in the finely-dispersed oil droplets ingested by the mussels are evidenced by the loss of the naphthalenes (Figure 1D), while the preferential uptake of the dissolved-phase naphthalenes (and to a lesser extent the other PAH) in the crabs (Figure 1E) shows naphthalenes’ persistence in the water column and/or lack of rapid depuration in the organisms after being adsorbed. The absence of the fluoranthenes/pyrenes and chrysenes in the crabs (compared to the mussels) also confirms that the crabs were not accumulating PAH from free oil droplets or oil-contaminated SPM (Payne and Driskell 1999, 2001). From a combined statistical and fingerprinting approach, it was possible to differentiate M/V New Carissa oil from background combustionderived (and sediment-associated) PAH in selected clam and oyster tissue samples from inside Coos Bay (Payne and Driskell 2000). Also documented was interstitial water contamination of

otherwise clean and unoiled sandy beach substrates by offshore dissolved-phase PAH, and the accumulation of hydrocarbons from the surface microlayer by diatoms. PWS RCAC environmental studies in Port Valdez. The Federally-mandated duties of Prince William Sound Regional Citizens’ Advisory Council (PWS RCAC) include conducting a Long-Term Environmental Monitoring Program (LTEMP) for Alaska North Slope crude oil at selected sites throughout Prince William Sound and the nearby Gulf of Alaska since 1993 (KLI 2000 and references therein; Payne et al. 1998). The program is similar to the National Oceanic and Atmospheric Administration (NOAA) Mussel Watch program including seasonal sampling (March and July) and analyses of intertidal mussels (Mytilus trossulus) and marine sediments. Other PWS RCAC studies in Port Valdez have included special event samplings following the T/V Eastern Lion oil spill in May 1994 (KLI 1994) and a Ballast Water Treatment Facility (BWTF) spill in January 1997 (KLI 1997). Also in 1997, a pilot caged-mussel monitoring study was successfully demonstrated in the vicinity of the mixing zone surrounding the offshore diffuser for the Alyeska BWTF (Applied Biomonitoring 1999). Subsequently, in spring 2001, a fully-integrated BWTF mixing-zone study was deployed utilizing caged mussel samples, PLVWSS water samples, and passive plastic-membrane devices (Salazar et al. 2002). During that program, the PLVWSS water-column sample collected closest to the BWTF diffuser had the same lowermolecular-weight, naphthalene-enriched, dissolved-phase PAH profile as the M/V New Carissa contaminated surf-zone sample in Figure 1B (except the total PAH concentration was two orders of magnitude less at 122 ng/L). Further from the BWTF diffuser, the dissolved-phase PAH concentrations in Port Valdez were considerably lower, ranging only from 5 to 36 ng/L (Salazar et al. 2002). From the mussel tissue analyses, it was apparent that several sets of caged mussels at specific depths (~30-75 m) close to the BWTF diffuser and at a depth of 75 m at one station along the edge of mixing zone were exposed to a discrete oil-droplet plume. This was reflected by their PAH patterns, which were similar to that shown in Figure 1D. At the same time, the caged mussels below the 75 m depth near the diffuser and at all depths except 75 m at other stations around the mixing zone and at more distant stations up to 8 km away exhibited dissolved-phase naphthalene-enriched patterns similar to that shown in Figure 1E. While reviewing the 1993-2000 LTEMP database for Port Valdez, Payne et al. (2001) observed that there was a distinct seasonal dissolved- versus oil-droplet-phase pattern for the PAH and AHC histograms from the intertidal mussels collected at both the Alyeska Marine Terminal site and the Gold Creek control station, 6 km across the port. As shown in Figure 3, the summer replicates had a predominantly dissolved-phase signal while the spring replicates had a predominantly oil-droplet-phase signal. While these data are not absolutely consistent (i.e., over the eight years of the program there were occasionally samples in the spring that showed a dissolved-phase signal and there were occasionally samples in the summer that had an oil-droplet-phase signal), this summer versus winter pattern of dissolved- versus oil-droplet phases is highly significant (chi sq = 6.93, corrected for continuity; p < 0.01; Sokal and Rohlf 1969) for both the Alyeska Marine Terminal site and the control station across the port.

RESPONSE MONITORING

TPAH FFPI

7757 84.50

CRUDE

6,886

C2N/ C2F

4.21

C2DB/ C2P

1.11

C2C/ C2P

0.26

CPI

1.11

C3N/ C3F

2.82

C3DB/ C3P

1.33

C3C/ C3P

0.31

900 800 700 600 500 400 300 200 100 0

TPAH

45360

CRUDE

99A1254

FFPI

94.70

CPI

C2N/ C2F

24.56

C2DB/ C2P

0.59

C2C/ C2P

0.00

C3N/ C3F

26.36

C3DB/ C3P

0.75

C3C/ C3P

0.00

BP

IP

BAP

BK

C4

C2

C

F/P3

F/P1

FL

D2

D

P/A3

43000

16000 14000 12000 10000 8000 6000 4000 2000 0

NC038-NOAA

TPAH

563824

CRUDE

500140

C2N/C2F

3.25

C2DB/ C2P

0.58

C2C/ C2P

0.14

99A1262

FFPI

88.70

CPI

0.85

C3N/C3F

4.63

C3DB/ C3P

0.96

C3C/ C3P

0.24

BP

IP

BAP

BK

C4

C2

C

F/P3

F/P1

FL

D2

D

P/A3

P/A1

A

F2

F

AE

N4

N2

B

N

ng/L

NC030-NOAA

P/A1

A

F2

F

AE

N4

N2

A

N

mg/kg

ET-2 99A2742

3

100000

C

ng/L

80000 60000 40000 20000

M ussels Tissue

TPAH

99A1315

FFPI

41080 74.07

CRUDE

C2N/ C2F

0.20

C2DB/ C2P

0.91

C2C/ C2P

0.28

CPI

C3N/ C3F

0.49

C3DB/ C3P

1.10

C3C/ C3P

0.19

BP

IP

BAP

BK

C4

C2

C

F/P3

F/P1

FL

D2

D

P/A3

P/A1

A

F2

F

AE

N4

N

N2

0

6000

ug/Kg

5000

D

4000 3000 2000 1000

519

TPAH

99A1549

FFPI

72 92.80

CRUDE

C2N/ C2F

3.55

C2DB/ C2P

CPI

C3N/ C3F

2.44

C3DB/ C3P

0.70 0.83

C2C/C2P

0.00

C3C/ C3P

0.00

BP

IP

BAP

BK

C4

C2

C

F/P3

F/P1

FL

D2

D

P/A3

P/A1

A

F2

F

AE

N4

N

N2

0

12

ug/Kg

10

E

8 6 4 2

BP

IP

BAP

BK

C4

C2

C

F/P3

F/P1

FL

D2

D

P/A3

P/A1

A

F2

F

AE

N4

N2

N

0

Figure 1. PAH histograms for: (A) mixed M/V New Carissa source oil “blend” (ET-2) collected from the beach adjacent to the vessel on 2/11/99; (B) dissolved- and (C) oil-droplet phase samples collected in the surf zone with the PLVWSS on 2/12/99; (D) mussels collected from the outside north jetty entrance to Coos Bay on 2/14/99; and (E) Dungeness crab collected inside Coos Bay midway up the main channel on 2/19/99. The diamonds connected by the horizontal line in these and other histograms represent the sample-specific method detection limits.

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ET-2

TAH res

76

CRUDE

6886

TA lk

37 .2

99A2742

UCM

334

CPI

1.11

TP H

41 0

Oil

2.5

A

mg/g

2 1.5 1 0.5

TA H r es

10 0

CRUDE

99 A12 54

UCM

60

CPI

1.3

TPH

160

C39

C37

C35

C33

C31

C29

C27

C25

C23

C21

C19

TAl k

1.50

Water

TAH r es

2400

CRUDE

99A 1262

UCM

6600

CPI

50014 0 0.85

TA lk

935.5

TP H

9000

C39

C37

C35

C33

C31

C29

C27

C25

C23

C21

C19

C18

C17

C16

1470

1380

C12

C10

B

NC038-NOA A

FILTER

80 70 60 50 40 30 20 10 0

C39

C37

C35

C33

C31

C29

C27

C25

C23

C21

C19

C18

C17

C16

1470

1380

C12

C10

C

C8

ug/L

4 3000

0.6 0.5 0.4 0.3 0.2 0.1 0

C8

ug/L

NC030-NOA A

C18

C17

C16

1470

1380

C12

C10

C8

0

Figure 2. AHC histograms for: (A) mixed M/V New Carissa source oil “blend" (ET-2) collected from the beach adjacent to the vessel on 2/11/99; and (B) dissolved- and (C) oil-droplet phase samples collected in the surf zone with the PLVWSS on 2/12/99. Unfortunately, AHC data were not obtained on either the mussel or crab tissue samples (D and E) shown in Figure 1. From these data and earlier studies by Colonell (1980) on the seasonal water-column stratification within Port Valdez, Payne et al. (2001) concluded that the observed hydrocarbon distributions in the LTEMP intertidal mussel samples may be explained by a combination of the seasonal development and subsequent breakdown of a stratified water column within the port and surface microlayer effects (Hardy 1982; Hardy and Cleary 1992; Hardy et al. 1987a,b). During the period of stable water stratification in the port (late spring, summer, and fall), the dispersed oil droplets released from the BWTF effluent are primarily entrained beneath the pycnocline in the middle-watercolumn regions where they are advected and diluted into the receiving waters of Port Valdez without ever reaching the upper water column and surface layer to any significant extent. As a result, only the dissolved-phase signal is observed in the LTEMP intertidal mussels collected in the summer period. During the winter and early spring, however, when the water column is not stratified, the warmer and less-saline BWTF effluent can reach the water surface where it is likely to form a surface microlayer containing higher levels of weathered oil-droplet-phase AHC and PAH components (Hardy 1982; Hardy et al. 1987b). We hypothesize that wind- and current-driven transport of this explains the predominant weathered oil-phase PAH signal observed in the LTEMP mussels collected each March. Thus, these physical oceanographic features would directly control the

position (and fate) of the dispersed oil-droplet fraction from the BWTF diffuser plume within the water column as demonstrated by several dye and plume-modeling studies (Colonell 1980; Woodward Clyde & ENTRIX 1987) and the caged-mussel studies of Salazar et al. (2002). The surface layer is also host to developing eggs and larval forms of numerous marine organisms that utilize the port and thus, the juxtaposition of oil-phase PAH and the rapidly developing eggs and larvae also may be of special concern (Hardy et al. 1987a,b). Because this surface-microlayer forms in the port at a time when reproduction and other biological activities are intensifying, these findings may significantly alter the assessment of potential toxicological effects in the future. To date, however, this phenomenon has not been confirmed in Port Valdez. Mussel and herring contamination and exposure routes from the Exxon Valdez oil spill. Brown et al. (1996) utilized mussels in Prince William Sound following the T/V Exxon Valdez oil spill in 1989 to indirectly corroborate the exposure of herring egg to oil in the water column. For this purpose, the data showed a statistically significant correlation between mussel hydrocarbon burdens and anaphase aberrations in herring eggs collected from the intertidal zone in oiled areas. Their results have led some investigators to propose that mussels may be a good surrogate for

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RESPONSE MONITORING

Dissolved Phase PAH from AMT Spring Mytilus

Oil-Droplet Phase PAH from AMT Spring Mytilus n=3

Average PAH (±SE mean)


IP

BP

BAP

C4

BK

C

C2

F/P4

PYR

P/A4

F/P2

BP

IP

BAP

C4

BK

C2

C

F/P4

F/P2

PYR

P/A4

P/A2

P

D4

D

D2

BP

IP

BAP

C4

BK

C2

C

F/P4

F/P2

PYR

P/A4

P/A2

P

D4

D

D2

F

F2

N4

AC

N

0

F

10

F2

20

N4

30

AC

40

Average TPAH = 1580.7 ±290.6

N

ng/g dry wt.

50

n=3

450 400 350 300 250 200 150 100 50 0

N2

Average TPAH = 379.0 ±54.8

N2

P

Oil-Droplet Phase PAH from AMT Summer Mytilus n=14

70

ng/g dry wt.

P/A2


Dissolved Phase PAH from AMT Summer Mytilus

60

D4

D

N

IP

BP

BAP

C4

BK

C

C2

F/P4

PYR

F/P2

P/A4

P

P/A2

D4

D

D2

F

F2

N4

AC

N

N2

0

D2

5

F

10

F2

15


N4

ng/g dry wt.

ng/g dry wt.

20

n=22

80 70 60 50 40 30 20 10 0

AC


N2

25


Figure 3. Average PAH histograms from 1993-2000 LTEMP intertidal mussel samples from Alyeska Marine Terminal. The samples are separated vertically by season and horizontally by physical state of the hydrocarbon source. The number of samples contributing to each composite illustrates the predominant oil-droplet phase signal in the spring (22 out of 25 samples) and the predominant dissolved-phase signal in the summer (14 out of 17 samples). predicting effects in other species, but as Baumard et al. (1999a,b) emphasized, it is important to recognize the route of exposure in interpreting such assessments. Brown et al. (1996) used mussel tissue residues to corroborate hydrocarbon exposure only because of the limited herring egg sample sizes available. In chemical analyses, small sample sizes increase the method detection limits (MDLs) and reduce the concomitant sensitivity to detect specific analytes of interest – i.e., results from the small samples of eggs would fall below detection limits. In reviewing the EVOS Trustees Database, however, we discovered that herring egg samples were in fact analyzed, and even though the MDLs were higher that the original investigators would have liked, the PAH profiles clearly showed that the route of PAH exposure to the herring eggs was completely different from the mussels exposed at the same time. Figure 4 presents the average PAH and AHC histogram plots for 50 mussel samples collected from Cabin Bay on Naked Island in Prince William Sound in May and June 1989 and 11 samples collected from the same location in the spring and summer of 1990 and 1991 (data are from the EVOS Trustees Database, accessible at www.afsc.noaa.gov/abl/OilSpill/evthd.htm). Figure 5 presents the average PAH and AHC data for 44 separate herring egg samples collected from Cabin Bay in May 1989. In 1989, the mussels clearly accumulated PAH and AHC from both the dissolved- and oil-droplet phases to which they were exposed; however, the dispersed oil droplet phase was the predominant source for the accumulated higher molecular weight PAH (C2-dibenzothiophenes through the phenanthrenes/anthracenes and chrysenes) and the aliphatics (phytane plus n-alkanes from n-C19 through n-C34). As noted above, these higher molecular weight components have only limited water solubilities and have long been associated with the whole-oil droplet phase.

In contrast, the plots for the herring eggs collected in 1989 (Figure 5), reflect the selective uptake of only the dissolved-phase (primarily the naphthalene homologues), which are the most water-soluble PAH derived from fresh ANS crude oil (Payne and McNabb 1984; Payne et al. 1983, 1984, 1991a,b). The AHC profiles for the exposed herring eggs show primarily lowermolecular-weight biogenic alkanes, which accumulate from the lipids in the phytoplankton (n-C15 and n-C17) and calanoid copepods (pristane) that make up the majority of the diet of female herring before depositing their eggs (pers. comm., Jeff Short; Cooney 1993; Blumer et al. 1964). These data demonstrate that the eggs accumulated PAH only from the dissolved phase. By 1990 and 1991, the mussels were also accumulating primarily dissolved-phase PAH (at significantly reduced overall concentrations) from the more water-soluble hydrocarbons still leaching from the intertidal zone. This is evident in the histogram plots at the bottom of Figure 4 by the predominant naphthalenes in greater relative abundance compared to the other PAH. Likewise, the AHC profile for the mussel samples in 19901991 was characterized primarily by lower molecular weight biogenic components (n-C15, n-C17, and pristane) with little or no contribution of phytane and higher molecular weight n-alkanes from dispersed oil droplets. In later controlled laboratory experiments using gravel contaminated with lightly- and heavily-weathered ANS oil (where the naphthalenes and fluorenes had been significantly reduced), it has been confirmed that herring and salmon eggs exposed to the water fraction accumulated only components from the dissolved phase (Carls et al. 1999; Heintz et al. 1999; Heintz et al. 1995; Marty et al. 1997). It was also shown that the same PAH patterns were obtained when salmon eggs were either exposed directly to the oiled gravel or only to the aqueous phase. The only shift in PAH accumulation occurred when extremely weathered oil was used in those studies. In those instances, the

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Oil-Droplet Phase TPAH in 1989 EVOS-Exposed Whole Mussel Tissue

Oil-Droplet Phase AHC in 1989 EVOS-Exposed Whole Mussel Tissue n=50

120

n=50

(1,545)

Average TPAH = 596.4 ± 91.5

200

Average TAlk = 2693.4 ±386.1

160

ng/g dry wt

80 60 40

120 80 40

20

Dissolved Phase TPAH in 1990-91 EVOS-Exposed Whole Mussel Tissue

C34

C32

C30

C28

C26

C24

Biogenic Background AHC in 1990-91 EVOS Whole Mussel Tissue n=11

n=11

( 282 ) 100

Average TPAH = 9.6 ± 1.8

Average TAlk =464.9 ±114.6 ng/g dry wt

2 ng/g dry wt

C22

Average n-Alkane (SE mean)

Average TPAH (SE mean)

2.5

C20

Phytane

Pristane

C16

IP

BP

BAP

C4

BK

C

C2

F/P4

PYR

F/P2

P/A4

P

P/A2

D4

D

D2

F

F2

N4

AC

N

N2

C14

C10

0

0

C12

ng/g dry wt

100

1.5 1

75 50 25

0.5

Average TPAH (SE mean)

C34

C32

C30

C28

C26

C24

C22

C20

Phytane

Pristane

C16

C14

BP

IP

BAP

C4

BK

C2

C

F/P4

F/P2

PYR

P/A4

P/A2

P

D4

D

D2

F

F2

N4

AC

N

N2

C12

C10

0 0


Figure 4. Average PAH and AHC histograms of whole mussel extracts from samples collected from oiled areas of Cabin Bay, Naked Island in Prince William Sound in May 1989 after the Exxon Valdez oil spill and again in May/June, 1990 and 1991. Data are from the online EVOS Trustees Database (www.afsc.noaa.gov/abl/OilSpill/evthd.htm). Dissolved Phase T PAH in 1989 EVOS-Exposed Herring Eggs n=42 Average TPAH = 48.4 ± 5.5

10

ng/g dry wt

8 6 4 2

BP

IP

BAP

BK

C4

C2

C

F/P4

F/P2

PYR

P/A4

P/A2

P

D4

D2

D

F2

F

AC

N4

N2

N

0

Average T PAH (SE mean)

Background Biogenic AHC in 1989 EVOS-Exposed Herring Eggs (1,049)

600

n=42

(7,780)

Average TAlk = 3286.2 ±389.9

ng/g dry wt

500 400 300 200 100

C34

C32

C30

C28

C26

C24

C22

C20

Phytane

Pristane

C16

C14

C12

C10

0


Figure 5. Average PAH and AHC histograms of herring egg extracts from samples collected from oiled areas of Cabin Bay, Naked Island (collocated with the mussel samples in Figure 4) in Prince William Sound in May 1989 after the EVOS. Data are from the online EVOS Trustees Database (www.afsc.noaa.gov/abl/OilSpill/evthd.htm).

RESPONSE MONITORING

PAH distribution was skewed to the residual higher molecular weight components, which can still partition into the aqueous phase (although at slower rates) when seawater percolates through contaminated gravel. PAH profiles from crab egg samples in the EVOS Trustees Database analyzed immediately following the spill revealed that PAH adsorption was again exclusively through the dissolvedphase, which is in agreement with the crab tissue results from the M/V New Carissa (Payne and Driskell 1999, 2000, 2001). As noted above, filter-feeding mussels and clams collected at the same time, showed accumulation of hydrocarbons that were primarily associated with the dispersed oil-droplet phase.

3.

4. 5.

Conclusion 6. Filter-feeding species (e.g., mussels, oysters, clams) primarily accumulate petrogenic hydrocarbons from contaminated suspended particulate material or the discrete oil-droplet phase when available; otherwise, the signal from dissolved-phase components will predominate. Biota with passive uptake (e.g., lipid-rich eggs) will primarily accumulate dissolved-phase components from the water column. Clearly, it is important to acknowledge phase partitioning when using mussels as surrogates or indicator organisms for monitoring marine pollution, and to exercise caution when attempting to extrapolate from one species to another, particularly when different modes of exposure are involved. Likewise, the data from the PWS RCAC studies in Port Valdez demonstrate that dissolved- versus oil-droplet phase exposure will vary with the point of contaminant release (surface versus subsurface) and the local physical oceanographic processes. Such factors are now being considered in NPDES assessments and permitting activities in Port Valdez. It is only through the separate collection and analyses of dissolved- and discrete oil-phase samples with approaches such as that provided by the PLVWSS, that accurate exposure assessments can be obtained during NRDA efforts following an oil spill and/or the NPDES permitting process for treatment facilities where multi-phase discharges are involved.

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Biography Dr. James R. Payne has 29 years experience in oil pollution studies and services. He is President of Payne Environmental Consultants, Inc., which currently assists NOAA, the Prince William Sound and Cook Inlet Regional Citizens’ Advisory Councils, and California’s Office of Oil Spill Prevention and Response (OSPR) with NRDA issues.

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Applied Biomonitoring. 1999. Caged mussel pilot study, Port Valdez, Alaska, 1997. Kirkland, Washington. Final Report for Prince William Sound Regional Citizens’ Advisory Council, Contract Number 631.1.97, 96 pp plus appendices. Baumard, P., H. Budzinski, P. Garrigues, T. Burgeot, X. Michel, and J. Bellocq. 1999a. Polycyclic aromatic hydrocarbon (PAH) burden of mussels (Mytilus sp.) in different marine environments in relation with sediment

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PAH contamination and bioavailability. Mar Environ Res. 47(5):415-439. Baumard, P., H. Budzinski, P. Garrigues, H. Dizer, and P. D. Hansen. 1999b. Polycyclic aromatic hydrocarbon (PAH) in recent sediment and mussels (Mytilus edulis) from the Western Baltic Sea: occurrence, bioavailability, and seasonal variations. Mar. Environ. Res. 47:17-47. Blumer, M., M. Mullin, and D.W. Thomas. 1964. Pristane in the marine environment. Helgolander Wissenshcaftliche Meeresuntersuchungen 10:187-201. Brown, E.D., T.T. Baker, J.E. Hose, R. M Kocan, G.D. Marty, M.D. McGurk, B.L. Norcross, and J. Short. 1996. Injury to the early life history stages of Pacific Herring in Prince William Sound after the Exxon Valdez oil spill. American Fisheries Society Symposium 18:448-462. Carls, M.G., S.D. Rice, and J.E. Hose. 1999. Sensitivity of fish embryos to weathered crude oil: Part I. Low level exposure during incubation causes malformations, genetic damage, and mortality in larval Pacific herring (Clupea pallasi). Environ. Toxicol. Chem. 18:481-493. Colonell, J.M. 1980. Physical Oceanography. Ballast Water Dispersal. In J.M. Colonell (Ed.), Port Valdez, Alaska: Environmental Studies 1976-1979. Institute of Marine Science, University of Alaska, Fairbanks. Occasional Publication No. 5. 373 pp. Cooney, R. T. 1993. A theoretical evaluation of the carrying capacity of Prince William Sound, Alaska for juvenile Pacific salmon. Fisheries Research 18:77-87. French-McCay, D.P. 2002. Development and application of an oil toxicity and exposure model, OilToxEx. Environ. Toxicol. Chem. 21(10):2080-2094. Hardy, J.T. 1982. The sea-surface microlayer: biology, chemistry and anthropogenic enrichment. Prog. Oceanog. 11:307-328. Hardy, J.T. and J. Cleary. 1992. Surface microlayer contamination and toxicity in the German Bight. Mar. Ecol. Prog. Ser. 91:203-210. Hardy, J.T., S.L. Kiesser, L.D. Antrim, A.I. Stubin, R. Kocan and J.A. Strand. 1987a. The sea-surface microlayer of Puget Sound: Part I. Toxic effects on fish eggs and larvae. Marine Environ. Res. 23:227-249. Hardy, J.T., E.A. Crecelius, L.D. Antrim, V.L. Broadhurst, C.W. Apts, J.M. Gurtisen, and T.J. Fortman. 1987b. The sea-surface microlayer of Puget Sound: Part 2. Concentrations of contaminants and relation to toxicity. Mar. Environ. Res. 23:251-271. Heintz, R., M. Wiedmer, and S.D. Rice. 1995. Laboratory evidence for short and long-term damage to Pink Salmon incubating in oiled gravel. Proceedings of the 17th Northeast Pacific Pink and Chum Salmon Workshop. March 1-3, 1995. Bellingham, Washington. pp. 142-146. Heintz, R.A., J.W. Short, and S.D. Rice. 1999. Sensitivity of fish embryos to weathered crude oil: Part II. Increased mortality of pink salmon (Onchorhynchus gorbuscha) embryos incubating downstream from weathered Exxon Valdez crude oil. Environ. Toxicol. Chem. 18:494-503. KLI. (Kinnetic Laboratories, Inc.) 1994. Letter report on sampling at Alyeska Marine Terminal LTEMP station in response to the T/V Eastern Lion oil spill. Prepared for the Prince William Sound Regional Citizens’ Advisory Council Long-Term Environmental Monitoring Program. 4 pp and attachments. KLI. (Kinnetic Laboratories, Inc.) 1997. Letter report on the Ballast Water Treatment Plant spill at Alyeska Marine

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Terminal. Prepared for the Prince William Sound Regional Citizens’ Advisory Council. 12 pp. KLI. (Kinnetic Laboratories, Inc.) 2000. 1999-2000 Annual LTEMP Monitoring Report. Prepared for the Prince William Sound Regional Citizens’ Advisory Council Long-Term Environmental Monitoring Program. 84 pp and appendices. Marty, G.C., J.W. Short, D.M. Dambach, N.H. Willits, R.A. Heintz, S.D. Rice, J.J. Stegeman, and D.E. Hinton. 1997. Ascites, premature emergence, increased gonadal cell apoptosis, and cytochrome P4501A induction in pink salmon larvae continuously exposed to oil-contaminated gravel during development. Can. J. Zool. 75:989-1007. National Research Council (NRC). 1985. Oil in the sea: Inputs, fates, and effects. National Academy Press, Washington, D.C. 601 pp. Payne, J.R., B.E. Kirstein, G.D. McNabb, Jr., J.L. Lambach, C. de Oliveira, R.E. Jordan and W. Hom. 1983. Multivariate analysis of petroleum hydrocarbon weathering in the subarctic marine environment. Proceedings, 1983 International Oil Spill Conference. American Petroleum Institute, Washington, D.C. pp 423434. Payne, J.R., B.E. Kirstein, G.D. McNabb, Jr., J.L. Lambach, R. Redding, R.E. Jordan, W. Hom, C. de Oliveira, G.S. Smith, D.M. Baxter, and R. Geagel. 1984. Multivariate analysis of petroleum weathering in the marine environment - subarctic. Final Reports of Principal Investigators, Vol. 21 and 22. February 1984, U.S. Department of Commerce, NOAA, Ocean Assessment Division, Juneau, Alaska. 690 pp. Payne, J.R. and G.D. McNabb, Jr. 1984. Weathering of petroleum in the marine environment. Marine Technology Society Journal, 18(3):24-42. Payne, J.R., L.E. Hachmeister, G.D. McNabb, Jr., H.E. Sharpe, G.S. Smith, and C.A. Manen. 1991a. Brineinduced advection of dissolved aromatic hydrocarbons to arctic bottom waters. Environ. Sci. Technol. 25(5):940951. Payne, J.R., G.D. McNabb, Jr., and J.R. Clayton, Jr. 1991b. Oil-weathering behavior in arctic environments. Polar Research 10(2):631-662. Payne, J.R., W.B. Driskell, and D.C. Lees. 1998. Long Term Environmental Monitoring Program Data Analysis of Hydrocarbons in Intertidal Mussels and Marine Sediments, 1993-1996. Final Report Prepared for Prince William Sound Regional Citizens’ Advisory Council,

This research was supported by a contract (No. 50-DSNC-790032) from the National Oceanic and Atmospheric Administration (NOAA) and Industrial Economics, Incorporated (IEc) and contracts (Nos. 633.01.1 and 956.02.1) from the Prince William Sound Regional Citizens’ Advisory Council (PWS RCAC). The views expressed herein are those of the authors and do not necessarily reflect the views of NOAA (or any of its subagencies), IEc, or the PWS RCAC.

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Contract No. 611.98.1. March 16, 1998. 97 pp plus Appendices. Payne, J.R., T.J. Reilly, and D.P. French. 1999. Fabrication of a portable large-volume water sampling system to support oil spill NRDA efforts. Proceedings, 1999 International Oil Spill Conference, American Petroleum Institute, Washington, D.C. pp. 1179-1184. Payne, J.R. and W.B. Driskell. 1999. Preassessment data report: Analyses of water samples collected in support of the M/V New Carissa oil spill natural resource damage assessment. Submitted to NOAA pursuant to Task Order 20016 of Contract No. 50-DSNC-7-90032 by Payne Environmental Consultants, Inc., Encinitas, CA and Industrial Economics, Inc., Cambridge, MA. July 22, 1999. 31 pp plus Appendices. Payne, J.R. and W.B. Driskell. 2000. Preassessment data report: Source characterization of oil, sediment, and tissue samples collected in support of the M/V New Carissa oil spill natural resource damage assessment. Submitted to NOAA pursuant to Task Order 20016 of Contract No. 50DSNC-7-90032 by Payne Environmental Consultants, Inc., Encinitas, CA and Industrial Economics, Inc., Cambridge, MA. February 16, 2000. 69 pp plus Appendices. Payne, J.R. and W.B. Driskell. 2001. Source characterization and identification of New Carissa oil in NRDA environmental samples using a combined statistical and fingerprinting approach. Proceedings, 2001 International Oil Spill Conference, American Petroleum Institute, Washington, D.C. pp. 1403-1409. Payne, J.R., W.B. Driskell, M.G. Barron, D.C. Lees. 2001. Assessing transport and exposure pathways and potential petroleum toxicity to marine resources in Port Valdez, Alaska. Final Report Prepared for Prince William Sound Regional Citizens' Advisory Council, Contract No. 956.02.1. December 21, 2001. 64 pp plus appendices. Salazar, M., J.W. Short, S.M. Salazar, and J.R. Payne. 2002. 2001 Port Valdez integrated monitoring report. Prince William Sound Regional Citizens' Advisory Council, Contract No. 633.01.1. February 7, 2002. 109 pp plus appendices. Sokal, R. R. and F. J. Rohlf. 1969. Biometry: The Principles and Practice of Statistics in Biological Research. San Francisco, W.H. Freeman and Co. 776 pp. Woodward-Clyde Consultants and ENTRIX, Inc. 1987. Ballast water treatment facility effluent plume behavior. A synthesis of findings. Prepared for Alyeska Pipeline Service Company. Walnut Creek, California. March 1987.