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Laboratory experiments demonstrate that adding clay to crude oil pollution generally has a positive effect on the bacterial degradation of hydrocarbons, largely by maintaining nutrient supply. The objective of this investigation was to constrain the influence of nontronite (Fe-smectite) based clay flakes on the biodegradation of Mississippi Canyon (MC 252) crude oil from the Deepwater Horizon spill in the presence of Alcanivorax borkumensis: a dominant alkane degrader of oil pollution. Containing large amounts of Fe, dioctahedral nontronite is of particular interest as a potential source for this nutrient. Based on 37 day (888 h) long agitated batch experiments containing oil-polluted nutrient-poor seawater, the addition of nontronite clay increased the bacteria population by a factor of up to 5, reduced alkane compounds by 57.7% compared to the 45.3% reduction achieved without clay additives and stimulated the breakdown of C13-C28 molecules by oxygenase reactions. With the exception of naphthalene compounds, which were depleted largely by evaporation, a reduction in alkylated polycyclic aromatic hydrocarbons was also observed suggestive of additional biodegradation reactions. In contrast, the non-alkylated polycyclic aromatic hydrocarbons were little influenced by the presence of the clay. Although control experiments indicate that Fe2+ did not act as a limiting nutrient under the oxygenated conditions of experimentation, our results confirm that nontronite clay represents a useful amendment for enhancing the biodegradation and acts in a similar way to other smectites by sustaining nutrient supply.

Adding clay to marine oil pollution represents a promising approach to enhance bacterial hydrocarbon degradation in nutrient poor waters. In this study, three types of regionally available clays (Ca-bentonite, Fuller's Earth and kaolin) were tested to stimulate the biodegradation of source and weathered oil collected from the Deepwater Horizon spill. The weathered oil showed little biodegradation prior to experimentation and was extensively degraded by bacteria in the laboratory in a similar way as the alkane-rich source oil. For both oils, the addition of natural clay-flakes showed minor enhancement of oil biodegradation compared to the non-clay bearing control, but the clay-oil films did limit evaporation. Only alkanes of a molecular weight (MW) > 420 showed significant reduction by enhanced biodegradation following natural clay treatment. In contrast, all fertilized clay flakes showed major bacterial degradation of the oil, with a 6–10 times reduction in alkane content, and an up to 8 fold increase in the rate of O2 consumption. Compared to the control, such treatment showed particular reduction of longer chained alkanes (MW > 226). The application of natural and fertilized clay flakes also showed selective reduction of PAHs, mainly in the MW range of 200–300, but without significant change in the toxicity indices measured. These results imply that a large variety of clays may be used to boost oil biodegradation by aiding attachment of fertilizing nutrients to the oil.

Author Posting. © The Oceanography Society, 2016. This article is posted here by permission of The Oceanography Society for personal use, not for redistribution. The definitive version was published in Oceanography 29, no. 3 (2016): 126–135, doi:10.5670/oceanog.2016.77.

Approximately 4.9 million barrels of crude oil and gas were released into the Gulf of Mexico (GoM) from April to July 2010 during the Deepwater Horizon (DWH) spill. This resulted in the possible contamination of marine organisms with polycyclic aromatic hydrocarbons (PAHs), USEPA identified constituents of concern. To determine the impact of the DWH oil spill, Gulf menhaden (Brevoortia patronus), a commercially harvested and significant trophic grazing species, was sampled from two Louisiana coastal regions between the years 2011-2013. Tissue extraction and GC/MS analysis demonstrated measurable concentrations of PAH within menhaden. Analysis yielded total PAHs, carcinogenic equivalents (BaP-TEQ), and mutagenic equivalents (BaP-MEQ) which provided an initial toxic potential assessment of this GoM Fishery. Gulf menhaden contained less total PAH concentrations in 2012 and significantly less in 2013 as compared to 2011 (p < 0.05) ranging from 7 ug/g tissue dry weight to 3 ng/g tissue dry weight. Carcinogenic and mutagenic PAHs were also significantly reduced (p < 0.05) over the three year period. The reduction of total PAH concentrations and the reduction of BaP-TEQs and MEQs between 2011 and 2013 indicates a diminished input of new source PAHs along with a reduction of carcinogenic and mutagenic PAHs in menhaden populations. The use of Gulf menhaden was successful in determining the acute toxic potential of PAHs contaminating the GoM in the years directly following the DWH spill event.

Gas chromatography/mass spectrometry analysis of over 700 near-surface sediments and sediments cores collected from Louisiana coastal salt marshes has provided an insight into the unique effects that these environments have on the Deepwater Horizon (DWH) oil residues deposited in them after the accidental release in April 2010. The weathering of oil residues was dependent on whether it was deposited on the surface, incorporated just below the sediment surface, or buried in the anoxic soil layer that can be typically found in these environments. One of the primary effects observed was a predictable weathering pattern of the biomarkers found in these oil residues, particularly changes in the diasterane and regular sterane biomarkers. Qualitative and quantitative oil source fingerprinting techniques were employed to determine if any oil residues detected were from the DWH oil spill (i.e., MC252 oil). The redistribution of buried oil residues in some of the impacted marshes by tropical weather events remains a concern 6 years after the DWH spill.

Much oil spill research has focused on fertilizing hydrocarbon oxidising bacteria, but a primary limitation is the rapid dilution of additives in open waters. A new technique is presented for bioremediation by adding nutrient amendments to the oil spill using thin filmed minerals comprised largely of Fullers Earth clay. Together with adsorbed N and P fertilizers, filming additives, and organoclay, clay flakes can be engineered to float on seawater, attach to the oil, and slowly release contained nutrients. Our laboratory experiments of microbial activity on weathered source oil from the Deepwater Horizon spill in the Gulf of Mexico show fertilized clay treatment significantly enhanced bacterial respiration and consumption of alkanes compared to untreated oil-in-water conditions and reacted faster than straight fertilization. Whereas a major portion (up to 98%) of the alkane content was removed during the 1 month period of experimentation by fertilized clay flake interaction; the reduced concentration of polyaromatic hydrocarbons was not significantly different from the non-clay bearing samples. Such clay flake treatment could offer a way to more effectively apply the fertilizer to the spill in open nutrient poor waters and thus significantly reduce the extent and duration of marine oil spills, but this method is not expected to impact hydrocarbon toxicity.

Measurements using several exposure metrics were carried out in a restaurant and a die casting plant to compare the spatial distributions of particle surface area (SA), number, and mass concentrations and rank exposures in different areas by those metrics. The different exposure metrics for incidental nanoparticle and fine particle exposures were compared using the concentration rankings, statistical differences between areas, and concentration ratios between different areas. In the die casting plant, area concentration rankings and spatial distributions differed by the exposure metrics chosen. Surface area and fine particle number concentrations were greatest near incidental nanoparticle sources and were significantly different between three areas. However, mass and coarse particle number concentrations were similar throughout the facility, and rankings of the work areas based on these metrics were different from those of SA and fine number concentrations. In the restaurant, concentrations in the kitchen for all metrics except respirable mass concentration were significantly greater than in the serving area, although SA and fine particle number concentrations showed larger differences between the two areas than either the mass or coarse particle number concentrations. Thus, the choice of appropriate exposure metric has significant implications for exposure groupings in epidemiologic and occupational exposure studies.

A novel optical instrument has been developed that estimates size segregated aerosol mass concentration (i.e., PM 10 , PM 4 , PM 2.5 , and PM 1 ) over a wide concentration range (0.001–150 mg/m 3 ) in real time. This instrument combines photometric measurement of the particle cloud and optical sizing of single particles in a single optical system. The photometric signal is calibrated to approximate the PM 2.5 fraction of the particulate mass, the size range over which the photometric signal is most sensitive. The electrical pulse heights generated by light scattering from particles larger than 1 micron are calibrated to approximate the aerodynamic diameter of an aerosol of given physical properties, from which the aerosol mass distribution can be inferred. By combining the photometric and optical pulse measurements, this instrument can estimate aerosol mass concentrations higher than typical single particle counting instruments while providing size information and more accurate mass concentration informat...

Histopathologic lesions were observed in the commercially important filter-feeding fish, Brevoortia patronus (Gulf menhaden), along the Louisiana Gulf Coast. Menhaden collected from Louisiana waters in 2011 and 2012, 1 and 2 years following the Deepwater Horizon oil spill, showed varying severities of gill lesions as well as an unusual accumulation of black particulates visible at necropsy in the heart and stomach vasculature. The PAH derived particulates were typically 1–4 µm in diameter, but larger aggregates were observed in the coronary vessels on the ventricle surfaces and their location and size was confirmed by light microscopy. Composited particulate composition was consistent with weathered petrogenic polycyclic aromatic hydrocarbon (PAH) mixtures based on GC–MS analysis. Particulates were present in 63 and 80 % of fish hearts and 70 and 89 % of stomach muscularis collected in 2011 and 2012, respectively. Tissue embedded particulates can lead to localized cellular damage from bioavailable compounds, as well as chronic effects from occlusion of sensitive tissues’ blood flow. The PAH derived particulates appeared to act as emboli in small capillaries, and could associated with localized inflammation, focal necrosis and inappropriate collagen and fibroblast tissue repair. We believe large volume filter feeding teleosts, such as menhaden (up to 3 million gallons per year/fish) with high lipid content, have a higher exposure risk and greater potential for toxicity from toxic particulates than other higher trophic level finfish. Suspended PAH derived particulates following an oil spill therefore, should be considered when assessing long-term ecological impacts and not be limited to physical contact (coating) or water soluble fractions for assessing toxicity (gill and neurologic).

Body burdens of PAHs were compared to histological effects in menhaden (Family: Clupeidae, Genus: Brevoortia) collected in fall 2010 from Barataria Bay, LA (BBLA) and Delaware Bay, NJ (DBNJ). Barataria Bay was heavily oiled during the DeepWater Horizon (DWH) oil spill, while Delaware Bay although urbanized had no reported recent oil spills. GCMS analyses of pre-spill 2009, BBLA and DBNJ fish found predominantly C2/C3 phenanthrene (1.28-6.52 ng/mg). However, BBLA also contained five higher molecular weight PAHs (0.06-0.34 ng/mg DW). Fluorescent aromatic compound spectroscopy (FACS) of gastrointestinal (GI) tract tissue showed statistically higher levels of hydroxypyrene-like PAHs in DBNJ than BBLA fish. Histopathologic lesions were more prevalent in BBLA than DBNJ fish. The lesion prevalence (gill, trunk kidney, epidermis, stomach) in the BBLA menhaden were significantly higher and more severe than observed in the DBNJ menhaden. Reversible lesions included gill lamellar hyperplasia, adhesions, edema, and epidermal hyperplasia. The increased pigmented macrophage centers were indicative of activated macrophages responding to connective tissue damage or other antigens. The liver hepatic necrosis and renal tissue mineralization may well have undergone repair, but damage to the kidney nephrons and hepatic/biliary regions of the liver would be slower to resolve and apparently remained after elimination of PAHs. Therefore, a direct cause and effect between DWH oil spill and increased lesion prevalence in BBLA menhaden could not be established.