Red Lion Scientifics LLC, Environmental Products Sea ReClaim TM Recovering the oil, reclaiming the Sea. Sorbent

Transcription

1 Sorbent Earth s Natural Buoyant Oil-Binding Materials for Immediate and Effective Reclamation of Oil Spills TECHNICAL BULLETIN #7 STRANDED OIL CLEAN-UP Thornmint Rd., Suite 111 Page 1 of 10

2 Stranded Oil Clean-up With Sea Reclaim Weathering of Spilled Oil The severity of an oil spill is affected by natural environmental processes (weathering) 1 in addition to any physical or chemical clean-up efforts undertaken. These chemical, physical, and biological processes are illustrated in the figure below (from Zhu et al. 2 ). In addition to spreading oil over the water surface, which is influenced by viscosity and surface tension, weathering includes the processes listed below. Evaporation Biodegradation Emulsification Photooxidation Fine Particle Interaction Spreading Dispersion Adsorption and Penetration Migration And Release Dissolution Biodegradation Sinking & Sedimentation Figure 1. Major Weathering Processes after an Oil Spill 1 United States Environmental Protection Agency. (1999). Understanding Oil Spills and Oil Spill Response. EPA 540-K Zhu, X., A.D. Venosa, M.T. Suidan, and K. Lee. (2001). Guidelines for the Bioremediation of Marine Shorelines and Freshwater Wetlands. United States Environmental Protection Agency Thornmint Rd., Suite 111 Page 2 of 10

3 Spreading: The spreading of oil on water is one of the most important processes during the first hours of a spill provided that the oil pour point is lower than the ambient temperature. The principal forces influencing the spreading of oil include factors such as viscosity and surface tension. This process increases the overall surface area of the spill, thus enhancing mass transfer by means of other processes. Evaporation is the most significant weathering process right after a spill occurs. Evaporation removes the volatile substances in the oil mixture including the more toxic low molecular weight compounds. For crude oil, this can include 20-50% of the oil spilled. For Number 2 fuel oil, the volatile components may be about 75% of the oil mixture. Gasoline and kerosene are made up of 100% volatile components. Dissolution: Although dissolution is less important from the viewpoint of mass loss during an oil spill, dissolved hydrocarbon concentrations in water are particularly important due to their potential influence on bioremediation and the effect of toxic material on biological systems. The low molecular weight aromatics are the most soluble oil components, and they are also the most toxic components in crude and refined oils. Although many of the low molecular weight aromatics may be removed through evaporation, their impact on the environment is much greater than simple mass balance considerations would imply. Photooxidation occurs when sunlight transforms complex high molecular weight petroleum compounds into simpler compounds. These are usually more soluble in water and potentially more available to vulnerable biological organisms. Dispersion: When the water column is agitated, oil can break into droplets that are dispersed throughout the water column. Also, interaction of the oil with fine (micron-sized) particles on the surface can reduce its adhesion to sediments or rocks, resulting in the formation of oil droplets that disperse into the water column. This process may be accelerated by chemical dispersants which add some toxic material to the already contaminated water. Emulsification: Waves can further disperse oil droplets into an emulsion, a thick, sticky mixture of water trapped in viscous oil that can linger in the environment for years. This thick, sticky mixture may contain up to 80% water and is commonly called chocolate mousse. The formation and stability of emulsions Thornmint Rd., Suite 111 Page 3 of 10

4 are primarily related to the chemical composition of the oils and are enhanced by wax and asphaltic materials. Biodegradation: The process of biodegradation of petroleum occurs when microorganisms consume the hydrocarbons in oil as food. This process is enhanced by warmer water temperatures. When oil is spilled onto or washes onto the beach, it can be biodegraded or can enter the sediment through adsorption to soil particles. There it may migrate through the sediments and/or eventually be released. Oil that is spread up onto a beach may be buried under the sand during the next tidal cycle, and then subsequently uncovered and released back into the ocean. Oil and Shoreline Interactions When oil spills occur near marine or freshwater shoreline (e.g., freshwater wetlands) environments, interactions between the spilled oil and the shore further complicate the weathering processes. The behavior of spilled oil in shoreline environments is primarily dependent on the properties of the shoreline, such as the porosity of the shoreline material and the energy of the waves acting on a shoreline. High wave action enhances both physical removal and weathering processes. Wave-swept rocky shores tend to recover within a matter of months whereas mangroves and marshes may require years. Tidal pumping is also a factor promoting oil penetration into the sediments. Interactions of oil with tidal action, waves, and shoreline material may also form asphalt-like oil-sediment that is resistant to any form of clean-up. Natural recovery is basically a no-action option that allows oil to be removed and degraded by natural means. For some spills, it is probably more cost-effective and ecologically sound to leave an oil-contaminated site to recover naturally than to attempt to intervene 3. Examples of such cases are spills at remote or inaccessible locations where natural removal rates are fast, or spills at sensitive sites where cleanup actions may cause more harm than good. 3 American Petroleum Institute Environmental Considerations for Marine Oil Spill Response Publ Thornmint Rd., Suite 111 Page 4 of 10

5 Many studies have shown that the interactions between oil and fine mineral particles play an important role in natural oil cleansing of shorelines 4,5,6. This process of oil and fine particle interaction reduces the adhesion of oil to intertidal shoreline materials through the formation of oil mineral aggregates that are easily dispersed by tidal action and currents. Oil mineral aggregates are microscopic entities composed of oil and mineral phases that are stable over long periods in the aqueous environment. They have different structures, but in all cases the fine mineral particles (<62 um) 7,8 prevent the oil from re-coalescing or adhering on surfaces. More importantly, oil mineral aggregates enhance the availability of oil for dispersion, photooxidation, and accelerate biodegradation 9. Studies on oil mineral aggregate formation have demonstrated that mineral fines can stabilize oil droplets within the water column. Various types of aggregates can be formed depending on the physicochemical properties of the particles, the type of oil and the environmental conditions 10,11. Both controlled laboratory 4 Bragg, J.R. and Owens, E. H. (1995) Shoreline cleansing by interactions between oil and fine mineral particles. Proceedings of 1995 International Oil Spill Conference. American Petroleum Institute, Washington DC, pp Lee, K., Tremblay, G.H., and Gauthier, J., Cobanli, S.E., Griffin, M. (1997) Bioaugmentation and biostimulation: a paradox between laboratory and field results. Proceedings of 1997 International Oil Spill Conference. American Petroleum Institute, Washington DC, pp Owens, E.H. (1999). The interaction of fine particles with stranded oil. Pure Appl. Chem. 71 (1): Lee, K., and P. Stoffyn-Egli, (2001). Characterization of Oil-Mineral-Aggregates, in Proceedings of the 2001 International Oil Spill Conference, Tampa, Florida, pp Ajijolaiya, L. O., Hill, P. S., Khelifa, A., Islam, R. M., and Lee, K. (2006) Laboratory investigation of the effects of mineral size and concentrations on the formation of oil-mineral aggregates. Marine Pollution Bulletin, Vol. 52, Iss. 8, August 2006, pp Lee, K., Weise, A.M., St. Pierre, S. (1997) Enhanced oil biodegradation with mineral fine interaction. Spill Science & Technology Bulletin, 3(4), Lee, K., Blaise, C. and Wells, P. G. (1998) Microscale testing in aquatic toxicology: Conclusions and future directions. In: Microscale Aquatic Toxicology: Advances Techniques and Practice, P.G. Wells, K. Lee and C. Blaise (eds.), CRC Press, Incorporated. pp Thornmint Rd., Suite 111 Page 5 of 10

6 experiments 12,13,14 and shoreline field trials 15 have demonstrated that oil mineral aggregates enhances the natural dispersion of oil spilled in the environment and reduces its environmental persistence. Oil mineral aggregate formation has been observed in numerous field sites that have ranged from the rivers of Bolivia 14 to the shores of Svalbard Island in the high Arctic 15. The oil mineral aggregates occurrence covers the range of natural variance for temperature, salinity, oil types and mineral composition. Oil mineral aggregates formation enhanced the biodegradation rates of the residual oil 13 as the stabilization of oil droplets by mineral fines increased the oil-water interface where microbial activity primarily occurs. Thus, this remediation process not only dilutes oil spilled into the environment, it may effectively eliminate many components of environmental concern. In terms of protection of the fisheries and fisheries habitat, oil mineral aggregates formation and its dispersion minimize environmental impacts. Since oil spills most frequently occur near shore and in estuarine waters 16, where the suspended sediment load is usually high, the interaction of physically and chemically-dispersed oil is inevitable. Oil mineral aggregation can occur with both 11 Stoffyn-Egli, P., and K. Lee, (2002) Formation and Characterization of Oil-Mineral Aggregates, Spill Science & Technology Bulletin, 8:1, Khelifa, A., Stoffyn-Egli, P., Hill, P.S., Lee, K. (2005). Effects of salinity and clay type on oil mineral aggregation, Marine Environmental Research, 59, Lee, K., Lunel, T., Wood, P., Swannell, R., and Stoffyn-Egli, P. (1997). Shoreline cleanup by acceleration of clay-oil flocculation processes. Proceedings of 1997 International Oil Spill Conference. American Petroleum Institute, Washington DC, pp Lee, K., and P. Stoffyn-Egli, (2001). Characterization of Oil-Mineral-Aggregates, in Proceedings of the 2001 International Oil Spill Conference, Tampa, Florida, pp Owen, E.H., and K. Lee, (2003) Interaction of Oil and Mineral Fines on Shorelines: Review and Assessment, Marine Pollution Bulletin, 49:9-12, NRC, (2005). National Research Council: Understanding Oil Spill Dispersants: Efficacy and Effects. National Academies Press, Washington, DC Thornmint Rd., Suite 111 Page 6 of 10

7 physically and chemically-dispersed oil 17. The effect of dispersants reduces oil and oil mineral aggregate particle size distribution. The effect of mineral fines increases the suspended particle concentration in the water column and oil mineral aggregate stability. Oil mineral aggregates do not readily breakup further or re-coalesce after dispersion 18. The synergistic effect of dispersants and mineral fines enhances the transfer of oil from the surface downward into the water column. However, the smaller particles of oil mineral aggregates tend to be suspended in the water column rather than settle down to the bottom. This impacts the overall fate and toxicity of the oil, as well as the biodegradation rate 19. Sea ReClaim and Oil Mineral Aggregate Formation Sea ReClaim is composed of an admixture of natural and modified-natural scoriaceous material derived from the earth. Sea ReClaim is derived from earth s natural scoriaceous material that is both highly porosive and buoyant. The materials comprising Sea ReClaim are, by their very nature, minerals which are capable of forming oil mineral aggregates. The physicochemical characteristics of mineral fine particles that promote oil mineral aggregation includes particle size, surface area, and in particular hydrophobicity. Sea ReClaim has small particle size, extremely high surface area and is both oleophilic and hydrophobic thereby meeting the requirements for aggregate formation. 17 Li, Z., P. Kepkay, K. Lee, T. King, M.C. Boufadel, and A.D. Venosa, (2007) Effects of Chemical Dispersants and Mineral Fines on Crude Oil Dispersion in a Wave Tank under Breaking Waves, Marine Pollution Bulletin, Khelifa, A., B. Fieldhouse, Z. Wang, C. Yang, M Landriault, M. F. Fingas, C. E. Brown, and L. Gamble (2007). A Laboratory Study on the Formation of Oil-SPM Aggregates using the NIST Standard Reference Material 1941b. In Proceedings of the Thirtieth Arctic and marine Oil Spill Program Technical Seminar, Environment Canada, Ottowa, Ontario, pp Lee, K., and Merlin, F.X. (1999) Bioremediation of oil on shoreline environments: development of techniques and guidelines. Pure Appl. Chem., 71(1), Thornmint Rd., Suite 111 Page 7 of 10

8 Sea ReClaim uses macroporous to mesoporous material. Macroporous materials are large granular porosive material that can vary in particle diameter and/or mesh size. Sea ReClaim uses macroporous scoria of mm diameter. Microporous material generally has pore sizes > 50 nm. Mesoporous materials have pore sizes from 2 to 50 nm. Both microporous and mesoporous structures are considered nature s natural nanotechnology. Mesoporous materials, which comprise ~25-30% of Sea ReClaim, are composed of particles in the range needed to maximize oil-mineral aggregate formation. About 5 gm of natural nanomaterial as used in Sea Reclaim has the surface area of 10 football fields. Sea ReClaim particles are naturally buoyant. Any aggregate formed stays on the surface, further exposing the oil, through enhanced availability of oil for dispersion, photooxidation, and accelerated biodegradation. Since Sea ReClaim spontaneously aggregates together upon contact with oil, the formation of oil mineral aggregates is enhanced. After contact with oil, the materials spontaneously combine with the oil forming an aggregate. Unlike most chemical dispersants which are toxic to the environment, Sea ReClaim forms an aggregate that is made from natural material and is less toxic than the oil itself. Sea ReClaim spread on a soiled shore-line will naturally combine with the oil and solidify for easy clean-up. Any residual oil and Sea ReClaim buried under the surface, will combine and form an oil mineral aggregate for further breakdown. Other Unique Functions (see Technical Bulletin #1 for full Discussion) Sea ReClaim uses buoyant materials that are either naturally highly porosive, or modified nanoparticulate material that has been rendered hydrophobic and buoyant. All materials are derived from scoria except for one man-made ceramic material. There are six oil binding components in Sea ReClaim. One of the main components is naturally mined scoria that is inherently buoyant due to its high porosiveness. This material is highly oleophilic (oil-binding) and hydrophobic (water-repellant) at the same time. It ranges from macroporous to mesoporous in natural nanostructure Thornmint Rd., Suite 111 Page 8 of 10

9 The next three (3) components in Sea ReClaim are modified natural scoria mined from rock that is made to be hydrophobic rendering it perpetually buoyant. When added to water, Sea ReClaim is self coalescing and buoyant. These three natural materials contain unassembled non-porous nanoparticulate subassemblies with a hydrocarbon-like surface that are naturally physically attracted to oil as like seeks like. This material increases crude oil viscosity upon contact and aids in immediate aggregation of the crude oil into an aggregated solidified mass. Hence, Sea ReClaim has the benefits of a sorbent with the properties of a solidifier. There is no chemical transformation of the oil into a new (non-oil) substance with Sea ReClaim as seen with solidifiers. The fifth component in Sea ReClaim is another modified natural scoria which has an extremely strong affinity for the hydrogen atom found on hydrocarbons in that it cross links them. This aids directly in stabilizing the solid mass again through a natural physical process. The last component in Sea ReClaim is a man-made microporous hollow sphere which is comprised of a nano-cage structure that is selective for binding toxic heavy metals that are found in crude oil and which get absorbed into the sea. Toxic heavy metal binding within the nano-cage is permanent and irreversible hence removing the toxic heavy metals from the environment In addition to being oleophilic (oil-binding) and hydrophobic (water-repellant), Sea ReClaim has two additional features differentiating it from all other sorbents on the market. One of the modified natural nano materials in Sea ReClaim is extremely effective at malodor elimination. Sea ReClaim uses the patent pending proprietary technology of Red Lion Chem Tech, LLC. Oil from oil spills is notorious for binding with organic matter readily found in the ocean, which putrefies over time yielding malodors. Another unique feature of Sea ReClaim is the permanent removal of toxic heavy metals found naturally in crude oil. These include lead, mercury, arsenic and chromium among others. These toxic heavy metals, are found in crude oil. Toxic heavy metals in crude oil readily contaminate seawater Thornmint Rd., Suite 111 Page 9 of 10

10 Sea ReClaim as a Dispersant These features are complemented by the ability of Sea ReClaim to form oil mineral aggregates from the mesoporous materials of nano particulate material used in the formulation. This makes Sea ReClaim unique. It is a material with the true properties of a Sorbent but also with the properties of both a Solidifier and a Dispersant. The advantages of Sea ReClaim as a dispersant by means of oil mineral aggregation include: 1) enhanced dispersion of oil slicks; 2) stabilization of dispersed oil droplets in the water column; 3) reduction of oil concentrations below toxic levels; 4) reduced re-coalescence of droplets; 5) reduction of the adhesion properties of oil, and; 6) enhanced oil biodegradation rates Thornmint Rd., Suite 111 Page 10 of 10