Meso-scale testing and development of test procedures to maintain mass balance

The Conrad Blucher Institute for Surveying and Science (Texas A&M University––Corpus Christi) has conducted numerous petroleum experiments at the Shoreline Environmental Research Facility (Corpus Christi, Texas, USA). The meso-scale facility has multiple wave tanks, permitting some control in experimental design of the investigations, but allowing for real-world conditions. This paper outlines the evolution of a materials balance approach in conducting petroleum experiments at the facility. The first attempt at a materials balance was during a 1998 study on the fate/effects of dispersant use on crude oil. Both water column and beach sediment samples were collected. For the materials balance, the defined environmental compartments for oil accumulation were sediments, water column, and the water surface, while the discharge from the tanks was presumed to be the primary sink. The “lessons learned” included a need to quantify oil adhesion to the tank surfaces. This was resolved by adhering strips of the polymer tank lining to the tank sides that could be later removed and extracted for oil. Also, a protocol was needed to quantify any floating oil on the water surface. A water surface (oil slick) quantification protocol was developed, involving the use of solid-phase extraction disks. This protocol was first tested during a shoreline cleaner experiment, and later refined in subsequent dispersant effectiveness studies. The effectiveness tests were designed to simulate shallow embayments which created the need for additional adjustments in the tanks. Since dispersant efficacy is largely affected by hydrodynamics, it was necessary to scale the hydrodynamic conditions of the tanks to those expected in our prototype system (Corpus Christi Bay, Texas). The use of a scaled model permits the experiment to be reproduced and/or evaluated under different conditions. To minimize wave reflection in the tank, a parabolic wave dissipater was built. In terms of materials balance, this design reduced available surface area as a sink for oil adsorption.     

Investigation of OMA formation and the effect of minerals

Oil-mineral-aggregates (OMA) have been shown to be effective in oil spills cleanup. Experimental work was carried out to study the effects of physical-chemical properties of natural minerals and chemically modified minerals on OMA formation and oil removal. The results showed that the hydrophobicity, particle sizes and specific surface of minerals played an important role in OMA formation. Appropriate hydrophobicity of minerals can enhance the formation of OMA. The surface property of minerals can also influence the shape of OMA. Spherical mineral-oil aggregates were frequently formed with hydrophilic minerals while irregular shaped OMA were observed with hydrophobic minerals. The sizes of OMA also increased when the minerals changed from hydrophilic to hydrophobic. The effects of dispersant and mixing energy were also carefully studied. The results showed that dispersant were a dominant factor. When dispersant was applied, effects of other factors became minimal.     

Large-scale cold water dispersant effectiveness experiments with Alaskan crude oils and Corexit 9500 and 9527 dispersants

There continues to be reluctance in some jurisdictions to use chemical dispersants as a viable countermeasure for accidental oil spills. One argument used by some opponents to dispersant use is that “chemical dispersants do not work effectively in cold water”. To address this issue, the U.S. Minerals Management Service (MMS) funded and conducted two series of large-scale dispersant experiments in very cold water at Ohmsett - The National Oil Spill Response Test Facility, located in Leonardo, New Jersey in February-March 2006 and January-March 2007. Alaska North Slope, Endicott, Northstar and Pt. McIntyre crude oils and Corexit 9500 and Corexit 9527 dispersants were used in the two test series. The crude oils were tested both when fresh and after weathering. Results demonstrated that both Corexit 9500 and Corexit 9527 dispersants were 85-99% effective in dispersing the fresh and weathered crude oils tested at cold temperatures. The MMS expects that results from these test series will assist government regulators and responders in making science based decisions on the use of dispersants as a response tool for oil spills in the Arctic.     

纳米氢氧化镁的合成方法

以氯化镁和氨水为原料,进行各种工艺条件的试验,在此基础上通过加入各种分散剂获得过滤、洗涤性能良好的氢氧化镁沉淀,并加一定的CaCl2作为添加剂大大提高了产品的收率。根据试验得到最佳的工艺条件,制备出纯度高、成本低的纳米氢氧化镁。     

消油剂和120#燃料油对海胆DNA损伤及甲基化影响

利用120#燃料油分散液和消油剂处理的乳化液测定海胆急性毒性和慢性DNA损伤及全基因组甲基化水平变化,确定消油剂处理的120#燃料油对海胆的毒性影响。结果表明:消油剂单独使用对海胆的影响微乎其微,经消油剂处理的燃料油乳化液中的多环芳烃质量浓度明显高于分散液中的质量浓度;乳化液和分散液对海胆都有明显的毒性作用,其96h半数效应浓度(EC50)值分别为12.03g/L和29.15g/L;DNA损伤研究表明,乳化液处理的海胆肠细胞彗星拖尾情况比同质量浓度分散液中拖尾情况更加严重;全基因组甲基化水平比分散液中更低,表明乳化液的急性毒性更大,所造成的DNA损伤更加严重。结果提示消油剂的使用会增大燃料油对海胆的毒性效应。     

Biodegradation of petroleum hydrocarbons at low temperature in the presence of the dispersant Corexit 9500

Our study examined the effects of Corexit 9500 and sediment on microbial mineralization of specific aliphatic and aromatic hydrocarbons found in crude oil. We also measured gross mineralization of crude oil, dispersed crude oil and dispersant by a marine microbial consortium in the absence of sediment. When provided as carbon sources, our consortium mineralized Corexit 9500 the most rapidly, followed by fresh oil, and finally weathered oil or dispersed oil. However, mineralization in short term assays favored particular components of crude oil (2-methyl-naphthalene > dodecane > phenanthrene > hexadecane > pyrene) and was not affected by addition of nutrients or sediment (high sand, low organic carbon). Adding dispersant inhibited hexadecane and phenanthrene mineralization but did not affect dodecane and 2-methyl-naphthalene mineralization. Thus, the effect of dispersant on biodegradation of a specific hydrocarbon was not predictable by class. The results were consistent for both high and low oiling experiments and for both fresh and weathered oil. Overall, our results indicate that environmental use of Corexit 9500 could result in either increases or decreases in the toxicity of residual oil through selective microbial mineralization of hydrocarbons.     

Evolution of droplets in subsea oil and gas blowouts: Development and validation of the numerical model VDROP-J

The droplet size distribution of dispersed phase (oil and/or gas) in submerged buoyant jets was addressed in this work using a numerical model, VDROP-J. A brief literature review on jets and plumes allows the development of average equations for the change of jet velocity, dilution, and mixing energy as function of distance from the orifice. The model VDROP-J was then calibrated to jets emanating from orifices ranging in diameter, D, from 0.5 mm to 0.12 m, and in cross-section average jet velocity at the orifice ranging from 1.5 m/s to 27 m/s. The d₅₀/D obtained from the model (where d₅₀ is the volume median diameter of droplets) correlated very well with data, with an R² = 0.99. Finally, the VDROP-J model was used to predict the droplet size distribution from Deepwater Horizon blowouts. The droplet size distribution from the blowout is of great importance to the fate and transport of the spilled oil in marine environment.     

Hydrodynamics of oil jets without and with dispersant: Experimental and numerical characterization

In this paper, we present the analysis of an underwater horizontal oil jet experimental measurement and Computational Fluid Dynamics (CFD) using the Reynolds Averaged Navier Stokes (RANS) equations. Two oil subsurface releases were conducted: one with crude oil and another with crude oil premixed with dispersant at the dispersant to oil ratio (DOR) of 1:20. The jet profile was captured by a camera at moderate resolution, and the instantaneous velocity was measured by a Vectrino Profiler. The velocity components, turbulence kinetic energy, and turbulence dissipation rate from the experiment agreed well with those from the CFD simulation using the k-epsilon turbulence model. The spread angle of the jet was found to be around 21° and 24° from the experiment measurement, for oil without dispersant and oil with dispersant, respectively. The latter is close to the angle of miscible jets at 23°. The jet profile of oil with dispersant had a smaller buoyancy than that without dispersant, which is probably due to the large water entrainment for the oil with dispersant jet. The cross sections of the jet for both cases gradually became flattened with distance, as the plume turned upward.     

Large-scale dispersant leaching and effectiveness experiments with oils on calm water

The use of dispersants to treat oil spills in calm seas is discouraged because there is insufficient ‘mixing energy’ to cause immediate dispersion of the oil. However, dispersants might be applied while the seas are calm, in the expectation that they would work later when sea states increase. The present study examined the persistence of dispersants in treated oil slicks on calm water in a large outdoor wave tank. Test slicks, pre-mixed with dispersant, were allowed to stand on static and flowing water for up to six days, after which their dispersibility was tested by exposing them to breaking waves. Results showed that thicker slicks exposed to calm water for up to six days dispersed completely with the addition of breaking waves. Thinner slicks and slicks exposed to water movement became less dispersible within two days. The loss of dispersibility was caused by dispersant loss rather than by oil weathering.     

Oil spill treatment products approval: the UK approach and potential application to the Gulf region

The environmental threat from oil spills remains significant across the globe and particularly in regions of high oil production and transport such as the Gulf. The ultimate damage caused can be limited by mitigation actions that responders deploy. The responsible and appropriate use of oil spill treatment products (e.g. dispersants, sorbents etc.) can offer response options that can result in substantial net environmental benefit. However, the approval and choice of what products to use needs careful consideration. The United Kingdom has had in place a statutory approval scheme for oil spill treatment products for 30 years. It is based on measures of efficiency and environmental acceptability. Two toxicity tests form an integral part of the assessment, the Sea test and the Rocky Shore test, and work on the premise that approved products will not make the situation significantly worse when added to spilled oil. This paper outlines the UK approach and how its rationale might be applied to the approval of products specific for the Gulf region. Issues such as species choice, higher temperatures and salinity and regional environmental conditions are considered.