Hydrodynamic characterization of Corpus Christi Bay through modeling and observation.

Christi Bay is a relatively flat, shallow, wind-driven system with an average depth of 3-4 m and a mean tidal range of 0.3 m. It is completely mixed most of the time, and as a result, depth-averaged models have, historically, been applied for hydrodynamic characterization supporting regulatory decisions on Texas coastal management. The bay is highly stratified during transitory periods of the summer with low wind conditions. This has important implications on sediment transport, nutrient cycling, and water quality-related issues, including hypoxia which is a key water quality concern for the bay. Detailed hydrodynamic characterization of the bay during the summer months included analysis of simulation results of 2-D hydrodynamic model and high-frequency (HF) in situ observations. The HF radar system resolved surface currents, whereas an acoustic Doppler current profiler (ADCP) measured current at different depths of the water column. The developed model successfully captured water surface elevation variation at the mouth of the bay (i.e., onshore boundary of the Gulf of Mexico) and at times within the bay. However, large discrepancies exist between model-computed depth-averaged water currents and observed surface currents. These discrepancies suggested the presence of a vertical gradient in the current structure which was further substantiated by the observed bi-directional current movement within the water column. In addition, observed vertical density gradients proved that the water column was stratified. Under this condition, the bottom layer became hypoxic due to inadequate mixing with the aerated surface water. Understanding the disparities between observations and model predictions provides critical insights about hydrodynamics and physical processes controlling water quality.

Application of fractal flocculation and vertical transport model to aquatic sol-sediment systems.

In estuarine and coastal environments, flocculation occurs between particles of different fractal dimensions and of different densities. Questions remain concerning the level of detail required to model particle flocculation and settling in these heterogeneous systems. This paper compares the goodness of fit between two flocculation models, using measured time series particle size distribution data collected from clay, colloidal silica, emulsified crude oil, clay-crude oil, and silica-crude oil systems. The coalesced sphere (CS) flocculation model includes the effects of heterogeneous particle size and density; the modified coalesced fractal sphere (mCFS) model adds effects due to heterogeneous fractal dimension. Goodness of fit was quantified using values of a minimized objective function, the mean of the sum of the square of the relative residuals (MSSRR). For nearly all tested experimental conditions, MSSRR values varied less than 5% between the CS and mCFS flocculation models. Additionally, collision efficiency values for single-particle-type (alpha(HOMOO)) and dual-particle-type (alpha(HETT)) systems were obtained through parameter regression using the CS and mCFS models. Using the mCFS model, estimated fractal dimension (D) values obtained for clay and clay-oil systems were between 2.6 and 3.0, lower than that postulated by the CS model but higher than that estimated experimentally by the particle concentration technique. The Stokes settling velocity of a clay aggregate of a given mass is reduced with decreased fractal dimension. This results in clay-oil flocculation occurring faster than floc sedimentation in the studied hydrodynamic range. Thus, the mCFS model provides insights to the fate of spilled oil in inland and coastal waters.

Modeling crude oil droplet-sediment aggregation in nearshore waters.

This paper describes a modeling approach that simulates changes in particle size distribution and density due to aggregation by extending the Smoluchowski aggregation kinetic model to particles of different density. Batch flocculation studies were conducted for clay, colloidal silica, crude oil, clay-crude oil, and silica-crude oil systems. A parameter estimation algorithm was used to estimate homogeneous collision efficiencies (alphaHOMO) for single-particle-type systems and heterogeneous collision efficiencies (alphaHET) for two-particle-type systems. Homogeneous collision efficiency values (alphaHOMO) were greater for clay (0.7) and for crude oil (0.3) than for silica (0.01). Thus, clay and crude oil were classified as cohesive particles while silica was classified as noncohesive. Heterogeneous collision efficiencies were similar for oil-clay (0.4) and oil-silica (0.3) systems. Thus, crude oil increases the aggregation of noncohesive particles. Data from the calibrated aggregation model were used to estimate apparent first-order flocculation rates (K') for oil, clay, and silica and apparent second-order flocculation rates (K'') for oil and clay in oil-clay systems and for oil and silica in oil-silica systems. For oil or clay systems, aggregation Damköhler numbers ranged from 0.1 to 1.0, suggesting that droplet coalescence and clay aggregation can occur on the same time scales as oil resurfacing and clay settling, respectively. For mixed oil-clay systems, the relative time scales of clay settling and clay-oil aggregation were also within an order of magnitude. Thus, oil-clay aggregation should be considered when modeling crude oil transport in nearshore waters.

Evaluation of bioremediation strategies of a controlled oil release in a wetland.

A controlled petroleum release was conducted to evaluate bioremediation in a wetland near Houston, Texas. The 140-day study was conducted using a randomized, complete block design to test three treatments with six replicates per treatment. The three treatment strategies were inorganic nutrients, inorganic nutrients with an alternative electron acceptor, and a no-action oiled control. Samples were analyzed for petroleum chemistry and inorganic nutrients. These results are discussed in the context of our related research involving toxicology and microbiology at the site during the experiment. To evaluate biodegradation, the targeted compounds were normalized to the conservative compound C3017alpha, 21beta-[H]hopane, thus reducing the effects of spatial heterogeneity and physical transport. The two biostimulation treatments demonstrated statistically-higher rates of biodegradation than the oiled no-action control. For the majority of the experiment, target nutrient levels were maintained. Further research may be warranted to optimize these bioremediation strategies as well as evaluating additional treatment strategies for wetlands and other shoreline systems.

Chemical dispersant effectiveness testing: influence of droplet coalescence.

Thermodynamic and kinetic investigations were performed to determine the influence of coalescence of chemically dispersed crude oil droplets in saline waters. For the range of pH (4-10) and salinity (10 per thousand, 30 per thousand, 50 per thousand ) values studied, zeta-potential values ranged from -3 to -10 mV. As the interaction potential values calculated using Derjaguin-Landau-Verway-Overbeek (DLVO) theory were negative, the electrostatic barrier did not produce significant resistance to droplet coalescence. Coalescence kinetics of premixed crude oil and chemical dispersant were determined within a range of mean shear rates (Gm = 5, 10, 15, 20 s(-1)) and salinity (10 per thousand, 30 per thousand ) values. Coalescence reaction rates were modeled using Smoluchowski reaction kinetics. Measured collision efficiency values (alpha = 0.25) suggest insignificant resistance to coalescence in shear systems. Experimentally determined dispersant efficiencies (alpha = 0.35) were 10-50% lower than that predicted using a non-interacting droplet model (alpha = 0.0). Unlike other protocols in which the crude oil and dispersant are not premixed, salinity effects were not significant in this protocol. This approach allowed the effects of dispersant-oil contact efficiency eta(contact) to be separated from those of water column transport efficiency (eta(transport)) and coalescence efficiency (eta(coalescence)).

Characterizing aquatic sediment-oil aggregates using in situ instruments.

The effects of emulsified crude oil and salinity (15, 30 per thousand ) on the steady state aggregate volume distributions and fractal dimensions were determined for a range of mean velocity gradients, (G(m) =5-50 s(-1)). Aggregation was performed in a 40-L cylindrical tank with a 4-blade paddle mixer. Three-dimensional fractal dimensions (D3) and volume distributions were determined using a procedure integrating data from an electrozone and an in situ light scattering instrument. Two-dimensional fractal dimensions (D2) and derived volume distributions were determined using a recently developed submersible flow cytometer equipped with a digital camera and image analysis software. For latex beads or emulsified crude oil systems, the above listed instruments yielded consistent size distributions and fractal dimensions (D2=1.92 +/- 0.16, D3=2.94 +/- 0.12). Mean volume aggregate diameters determined using the FlowCAM were consistently larger that those determined using the LISST-100 or Coulter Multisizer due to aggregate orientations during measurements. With increasing G(m) values, all colloidal aggregates showed increasing D3 values due to reduced aggregate length. Because of the compactness of all the aggregates (D3 >2), D2 values remained constant at 2. Neither salinity nor sediment type significantly affected D2 values calculated for sediment-crude oil aggregates. However, clay-oil aggregates showed higher D3 values than clay aggregates. This suggests that colloidal oil and mixing shear are the more dominant factors influencing aggregate morphology in nearshore waters. Overall, the data suggests that the analysis methods provide consistent size distribution results. However, because of the shear and salinity of coastal waters, resulting aggregates are too compact to estimate their D3 values using image analysis alone.

Partitioning of crude oil polycyclic aromatic hydrocarbons in aquatic systems.

This paper investigates the hypothesis that observed polycyclic aromatic hydrocarbon (PAH) concentrations in an aqueous system are equal to the sum of the organic phase and soluble phase molar concentrations. While the organic phase concentrations are proportional to the PAH mole fraction in the oil, the soluble phase molar concentrations are estimated using Raoult's law. A batch laboratory mixing vessel with a scalable mixing energy was loaded initially at various oil layer thicknesses (0.4-3.2 mm) which correspond to oil surface loadings (40-310 mg/cm2). The vessel was agitated at constant mean shear rates (Gm = 5, 20 s(-1)). Total petroleum hydrocarbon (TPH) samples were taken periodically to estimate the entrainment rate as a function of initial oil layer thickness. TPH concentrations were measured in-situ using a laser scattering instrument (LISST-100) and ex-situ using gravimetric analysis. At a steady-state TPH concentration (>72 h), additional samples were analyzed for PAH concentration using GC/MS analysis. TPH concentrations increased over time according to a first-order kinetic model. Generally, the first-order rate constant and steady-state concentration both increased with increased oil loading and with increased Gm. In addition, measured PAH concentrations correlated well (r2 > 0.96) with those predicted by a partitioning model. These results are useful for assessing the effects of mixing and oil loading conditions on crude oil entrainment and PAH partitioning.

Intrinsic bioremediation of a petroleum-impacted wetland.

Following the 1994 San Jacinto River flood and oil spill in southeast Texas, a petroleum-contaminated wetland was reserved for a long-term research program to evaluate bioremediation as a viable spill response tool. The first phase of this program, presented in this paper, evaluated the intrinsic biodegradation of petroleum in the contaminated wetland. Sediment samples from six test plots were collected 11 times over an 11-month period to assess the temporal and spatial petroleum concentrations. Petroleum concentrations were evaluated using gas chromatography-mass spectrometer analyses of specific target compounds normalized to the conservative biological marker, C(30)17alpha,21beta(H)-hopane. The analyses of specific target compounds were able to characterize that significant petroleum biodegradation had occurred at the site over the one-year period. Total resolved saturate and total resolved aromatic hydrocarbon data indicated the petroleum was degraded more than 95%. In addition, first-order biodegradation rate constants were calculated for the hopane-normalized target compounds and supported expected biodegradation patterns. The rapid degradation rates of the petroleum hydrocarbons are attributed to conditions favorable to biodegradation. Elevated nutrient levels from the flood deposition and the unconsolidated nature of the freshly deposited sediment possibly provided a nutrient rich, oxic environment. Additionally, it is suggested that an active and capable microbial community was present due to prior exposure to petroleum. These factors provided an environment conducive for the rapid bioremediation of the petroleum in the contaminated wetland.

Behavior of a chemically dispersed oil in a wetland environment.

An experiment was conducted at a wetland research facility, investigating the behavior and effects of chemically dispersed oil (CDO) using an oil-spill dispersant. The research site is located on the San Jacinto River near Houston, TX. The replicated treatments included oiled control, "high-dose" CDO (1:10 dispersant-to-oil ratio (DOR)), "low-dose" CDO (1:20 DOR), as well as an unoiled control. Known amounts of oil or dispersed oil were added to the respective plots. Sediment samples were taken over a 99-day period using a 5-cm-diameter coring device. The GC/MS results for both "total target saturate hydrocarbons" and "total target aromatic hydrocarbons" were plotted over time and data were modeled using nonlinear regression. The overall (including abiotic and biotic) petroleum loss rates for the dispersed-oil treatments were not statistically different when compared to the oiled control. However, the initial concentrations for the dispersed-oil treatments were statically lower (95% confidence) than for the oiled control. From this, it can be inferred that the dispersed oil was more prone to flush off the sediments, as was visually observed. Biodegradation rates were also determined for all treatments; it was concluded that there were no differences when comparing each dispersed-oil treatment to the oiled control. The sediments from each plot were also analyzed for microbial population numbers (most-probable-number) and acute toxicity (Microtox 100% Test). Statistical analyses for both sets of data found no significant differences for the dispersed-oil treatments when compared to the oiled control.