dissolved-phase sample will contain primarily the more water- .... ~Ц> 8000 H. C. 6000 - .... surface microlayer effects (Hardy 1982; Hardy and Cleary 1992;.
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 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.
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
William B. Driskell 6536 2Cf Avenue NE Seattle, WA 98115
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.
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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 ìðé 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 ID) 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 IE) 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 ID), while the preferential uptake of the dissolved-phase naphthalenes (and to a lesser extent the other PAH) in the crabs (Figure IE) 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 IB (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 ID. 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 IE. 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
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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 & ENTRDC 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
RESPONSE MONITORING
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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. Conclusion 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 océanographie 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.
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.
References 1.
2.
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(51:415-439. 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. j_8:481 -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. 2K10):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 Π. 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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2003 INTERNATIONAL OIL SPILL CONFERENCE 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, r; ·;(] gonadal cell apoptosis, and cytochrome P4501A înaucuoii 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. Horn. 1983. Multi varíate analysis of petroleum hydrocarbon weathering in the subarctic