Adverse Effects of Hydrocarbons Found in Crude Oil in the Marine Environment John S. French, PhD Pegasus Environmental Solutions – Alaska PO Box 1470 Seward, AK NW Tribal Water Rights Conference, October 2014 Anchorage, Alaska

Who I am

John S. French, PhD  Biochemist & Environmental Toxicologist  Retired Professor from UAF – School of Fisheries and Ocean Sciences  EVOSTC – Public Advisory Committee, Science & Technology Representative  PWS – Regional Citizens’ Advisory Council, Past Board Member representing City of Seward Past Board Member representing City of Seward Past Chair Oil Spill Prevention and Response Committee Past Chair Oil Spill Prevention and Response Committee Past Member Scientific Advisory Committee Past Member Scientific Advisory Committee  Member American Chemical Society & Society of Environmental Toxicology and Chemistry

A crucial first step is understanding the complex interactions between the ocean, the environment and specific ecosystems before deciding whether to hammer them with oil spill counter measures. What do we need to protect in the event of an oil spill?

A crucial first step is understanding the complex interactions between the ocean, the environment and specific ecosystems before deciding whether to hammer them with oil spill counter measures. What do we need to protect in the event of an oil spill?

Ocean Physics: The dynamic properties of the oceans which drive the distribution on nutrients within marine ecosystems, thereby influencing both primary and secondary production within those systems. Environmental Dynamics: The bioenergetics and trophic interactions among species within the context of an ecosystem

Upwelling from deep ocean currents provide most of the nutrients necessary for life both near-shore and off-shore in the Gulf of Alaska, Bering and Chukchi Seas.

Primary Productivity in North Pacific Measured as chlorophyll by Vertically Generalized Production Model by calendar month (mean mgC/m2/day)

Primary Productivity in Gulf of Alaska Calculated from Sea WiFS data for June 1999

Rivers & Lakes Deep Ocean Surface Shorezone Rivers & Lakes Deep Ocean Surface Shorezone Bottom-Up Driven Ecosystem (Gulf of Alaska) Onshore-Off Driven Ecosystem (Gulf of Mexico)

The high benthic biomass (>300 g m -2 ) and chlorophyll (>150 mg m -2 ) on the Chukchi Sea Shelf are known centers for deposition of reduced organic matter orginating on the Bering Sea shelf and carried north by the Anadyr and Bering Currents.

Spawning migration Adult Population Immature Population Spawning Site Nursery Area Migration in plankton Movement to offshore feeding areas Unlike salt marshes and other shorezone spawning and nursery grounds for on-shore off driven ecosystems, There may be substantial annual variation in the locations of these grounds in bottom-up driven ecosystems

Most environmental regulations in the United States assume that a substance is NOT toxic unless it has been PROVEN to be toxic beyond reasonable doubt.

Crude oil is complex mixture containing thousands of discrete compounds. Recent mass spectral studies report there may be more than 50,000 compounds of the general structure C c H h N n O o S s. The absolute structures of only a few hundred are known. Less than 1/3 of those have been rigorously tested for toxicity to the environment.

Elemental Composition of Crude Oils These are the ranges commonly seen in crude oils

A common fractionation of crude oils is by fractional distillation into Saturates, Aromatics, Resins and Asphaltenes (SARA) Further solvent extrations can separate the Resins and Asphaltenes into polar and non-polar subfractions.

From Fingas, 3012 Examples of Chemical Classes, Names, & Typical Compounds

Not knowing the toxicological properties of crude oil constituents does NOT mean that they are safe!

Precautionary Approach “In order to protect the environment, the precautionary approach shall be widely applied by States according to their capabilities. Where there are threats of serious or irreversible damage, lack of full scientific certainty shall not be used as a reason for postponing cost-effective measures to prevent environmental degradation.” Ratified as part of the Rio Declaration from the 1992 United Nations Conference on Environment and Development.

There does not have to be visible oiling for oil to have adverse impacts. Direct Impacts without visible oiling Narcosis Narcosis Organ failure Organ failure Other physiological impairments Other physiological impairments Indirect impacts without visible oiling Starvation due to loss of prey species Starvation due to loss of prey species Immune impairment Immune impairment

The Marine Food Web in the Northern Seas is Particularly Susceptible to Disruption at the Primary to Secondary Productivity Level leading to the Forage Fish Complex

What Hydrocarbons in Crude Oil are Toxic ? Abstracted from NRC, 1985

Weathering of Alaska North Slope Oil PAH Fraction Fresh Seven Years Natural Weathering BSD & Related PathologiesCancer

Factors Determining Toxicity of Compound & Mixtures Structure of the Compound(s) Structure of the Compound(s) Species & Life Stages Exposed Species & Life Stages Exposed Route of Exposure Route of Exposure Dose & Duration of Exposure Dose & Duration of Exposure Uptake & Bioaccumulation Uptake & Bioaccumulation Metabolism & Removal of Toxic Substances Metabolism & Removal of Toxic Substances

Environmental Exposure BioaccumulationMetabolism Adverse Effects Adverse effects of crude oil in the environment may be amplified by bioaccumulation either within individuals, or up the food chain. Many PAH require metabolic transformation to either their toxic form, or to detoxify them prior to removal from the body.

Dose Response & Chemical Specificity for On-set of “Blue Sac Disease” (a) Short and Springman, 2007(b) Incardona, 2007

Cetaceans Stranded Phase of Oil Spill Response Dates 114 cetaceans stranded prior to the response phase for the oil spill February 1, April 29, cetaceans stranded or were reported dead offshore during the initial response phase to the oil spill April 30, November 2, cetaceans strand ed* after the initial response phase ended November 3, March 16, 2014** Bottlenose Dolphin Unusual Mortality Event (UME) Northern Gulf of Mexico ( ). Summary of strandings

Bottlenose Dolphin Unusual Mortality Event (UME) in Northern Gulf of Mexico ( ). BP/Deepwater Horizon NRDA Cummulative Oiling NOAA ERMA website Northern GOM UME All Species All Years NOAA OPR Website

Calendar Quarters have been shifted one month so Q2:10 begins May 01, 2010 Normalized Strandings Data for UME February 2010-January 2014 Actual Strandings / Average non-UME Strandings

Proportion of dolphins categorized as having normal (green), mild (yellow-green), moderate (yellow), and severe (red) (A) alveoloar interstitial syndrome and (B) overall lung disease. Numbers inside bars represent number of cases in each category. Schwacke, L.H., et al (2013) Health of Common Bottlenose Dolphins (Tursiops truncatus) in Barataria Bay, Louisiana, Following the Deepwater Horizon Oil Spill. Environ. Sci. Technol.

How do Chemical Dispersants Work as Oil Spill Response Counter Measures? Application of chemical dispersants does not remove any oil from the environment. Application of chemical dispersants does not remove any oil from the environment. Neither does the dispersant per se cause degradation of any oil. Neither does the dispersant per se cause degradation of any oil. Dispersant applications in major oil spills have never prevented all oil from reaching the shorezone. Dispersant applications in major oil spills have never prevented all oil from reaching the shorezone. Dispersants facilitate the action of wave energy in temporarily suspending small oil droplets in the water column. Dispersants facilitate the action of wave energy in temporarily suspending small oil droplets in the water column.

Dilution Degradation Most adverse environmental effects resulting from use of chemical dispersants are caused by increasing the concentration and bioavailability of toxic hydrocarbons in proximity to sensitive species. These impacts may be partially mitigated by prompt dilution and degradation. Effectiveness of Dispersants & Toxicity of Dispersed Hydrocarbons

Susceptibility of Petroleum Hydrocarbons to Biodegradation from Most Susceptible to Least Modified from Prince and Walters, 2007.

Summary of recent findings: 1.The chronic toxicity of aromatic hydrocarbons in crude oil is largely due to 3- to 4- ringed alkyl-substituted polycyclic aromatic hydrocarbons (PAH). 2.Use of chemical dispersants increases the concentration of PAH in the seawater phase approximately 100 fold. 3.Three to 4-ringed PAH are less likely to remain within dispersants-containing droplets than are smaller aromatic hydrocarbons. Effectiveness of Dispersants & Toxicity of Dispersed Hydrocarbons

Summary of recent findings (Slide 2): 4.The depth of the mixing layer is more important than total water depth in estimating dilution. 5.Short term exposures of <24 hr will cause longer term chronic impacts. 6.Concentrations of <300 ppb have been shown to have the following adverse impacts on one or more of the fish species studied: 1. abnormal embryo development, 2. abnormal cardio-skeletal development of fry, 3. decreased burst swimming speed in exposed adults Effective ness of Dispersants & Toxicity of Dispersed Hydrocarbons

Not all the tools always belong in every tool box

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