Accelerated marsh erosion following the Deepwater Horizon oil spill confirmed, ameliorated by planting.

Multiple studies have examined the effects of the Deepwater Horizon oil spill on coastal marsh shoreline erosion. Most studies have concluded that the spill increased shoreline erosion (linear retreat) in oiled marshes by ~ 100-200% for at least 2-3 years. However, two studies have called much of this prior research into question, due to potential study design flaws and confounding factors, primarily tropical cyclone influences and differential wave exposure between oiled (impact) and unoiled (reference) sites. Here we confirm that marsh erosion in our field experiment was substantially increased (112-233%) for 2 years in heavily oiled marsh after the spill, likely due to vegetation impacts and reduced soil shear strength attributed to the spill, rather than the influences of hurricanes or wave exposure variation. We discuss how our findings reinforce prior studies, including a wider-scale remote sensing analysis with similar study approach. We also show differences in the degree of erosion among oil spill cleanup treatments. Most importantly, we show that marsh restoration planting can drastically reduce oiled marsh erosion, and that the positive influences of planting can extend beyond the immediate impact of the spill.

Vegetation recovery in an oil-impacted and burned Phragmites australis tidal freshwater marsh.

In-situ burning of oiled marshes is a cleanup method that can be more effective and less damaging than intrusive manual and mechanical methods. In-situ burning of oil spills has been examined for several coastal marsh types; however, few published data are available for Phragmites australis marshes. Following an estimated 4200gallon crude oil spill and in-situ burn in a Phragmites tidal freshwater marsh at Delta National Wildlife Refuge (Mississippi River Delta, Louisiana), we examined vegetation impacts and recovery across 3years. Oil concentrations in marsh soils were initially elevated in the oiled-and-burned sites, but were below background levels within three months. Oiling and burning drastically affected the marsh vegetation; the formerly dominant Phragmites, a non-native variety in our study sites, had not fully recovered by the end of our study. However, overall vegetation recovery was rapid and local habitat quality in terms of native plants, particularly Sagittaria species, and wildlife value was enhanced by burning. In-situ burning appears to be a viable response option to consider for future spills in marshes with similar plant species composition, hydrogeomorphic settings, and oiling conditions. In addition, likely Phragmites stress from high water levels and/or non-native scale insect damage was also observed during our study and has recently been reported as causing widespread declines or loss of Phragmites stands in the Delta region. It remains an open question if these stressors could lead to a shift to more native vegetation, similar to what we observed following the oil spill and burn. Increased dominance by native plants may be desirable as local patches, but widespread loss of Phragmites, even if replaced by native species, could further acerbate coastal erosion and wetland loss, a major concern in the region.

Shoreline oiling from the Deepwater Horizon oil spill.

We build on previous work to construct a comprehensive database of shoreline oiling exposure from the Deepwater Horizon (DWH) spill by compiling field and remotely-sensed datasets to support oil exposure and injury quantification. We compiled a spatial database of shoreline segments with attributes summarizing habitat, oiling category and timeline. We present new simplified oil exposure classes for both beaches and coastal wetland habitats derived from this database integrating both intensity and persistence of oiling on the shoreline over time. We document oiling along 2113km out of 9545km of surveyed shoreline, an increase of 19% from previously published estimates and representing the largest marine oil spill in history by length of shoreline oiled. These data may be used to generate maps and calculate summary statistics to assist in quantifying and understanding the scope, extent, and spatial distribution of shoreline oil exposure as a result of the DWH incident.

Impacts of the Deepwater Horizon Oil Spill on Salt Marsh Periwinkles (Littoraria irrorata).

Deepwater Horizon was the largest marine oil spill in U.S. waters, oiling large expanses of coastal wetland shorelines. We compared marsh periwinkle (Littoraria irrorata) density and shell length at salt marsh sites with heavy oiling to reference conditions ∼16 months after oiling. We also compared periwinkle density and size among oiled sites with and without shoreline cleanup treatments. Densities of periwinkles were reduced by 80-90% at the oiled marsh edge and by 50% in the oiled marsh interior (∼9 m inland) compared to reference, with greatest numerical losses of periwinkles in the marsh interior, where densities were naturally higher. Shoreline cleanup further reduced adult snail density as well as snail size. Based on the size of adult periwinkles observed coupled with age and growth information, population recovery is projected to take several years once oiling and habitat conditions in affected areas are suitable to support normal periwinkle life-history functions. Where heavily oiled marshes have experienced accelerated erosion as a result of the spill, these habitat impacts would represent additional losses of periwinkles. Losses of marsh periwinkles would likely affect other ecosystem processes and attributes, including organic matter and nutrient cycling, marsh-estuarine food chains, and multiple species that prey on periwinkles.

Heavily Oiled Salt Marsh following the Deepwater Horizon Oil Spill, Ecological Comparisons of Shoreline Cleanup Treatments and Recovery.

The Deepwater Horizon oil spill affected hundreds of kilometers of coastal wetland shorelines, including salt marshes with persistent heavy oiling that required intensive shoreline "cleanup" treatment. Oiled marsh treatment involves a delicate balance among: removing oil, speeding the degradation of remaining oil, protecting wildlife, fostering habitat recovery, and not causing further ecological damage with treatment. To examine the effectiveness and ecological effects of treatment during the emergency response, oiling characteristics and ecological parameters were compared over two years among heavily oiled test plots subject to: manual treatment, mechanical treatment, natural recovery (no treatment, oiled control), as well as adjacent reference conditions. An additional experiment compared areas with and without vegetation planting following treatment. Negative effects of persistent heavy oiling on marsh vegetation, intertidal invertebrates, and shoreline erosion were observed. In areas without treatment, oiling conditions and negative effects for most marsh parameters did not considerably improve over two years. Both manual and mechanical treatment were effective at improving oiling conditions and vegetation characteristics, beginning the recovery process, though recovery was not complete by two years. Mechanical treatment had additional negative effects of mixing oil into the marsh soils and further accelerating erosion. Manual treatment appeared to strike the right balance between improving oiling and habitat conditions while not causing additional detrimental effects. However, even with these improvements, marsh periwinkle snails showed minimal signs of recovery through two years, suggesting that some ecosystem components may lag vegetation recovery. Planting following treatment quickened vegetation recovery and reduced shoreline erosion. Faced with comparable marsh oiling in the future, we would recommend manual treatment followed by planting. We caution against the use of intensive treatment methods with lesser marsh oiling. Oiled controls (no treatment "set-asides") are essential for judging marsh treatment effectiveness and ecological effects; we recommend their use when applying intensive treatment methods.

Predictive modeling of subsurface shoreline oil encounter probability from the Exxon Valdez oil spill in Prince William Sound, Alaska.

To better understand the distribution of remaining lingering subsurface oil residues from the Exxon Valdez oil spill (EVOS) along the shorelines of Prince William Sound (PWS), AK, we revised previous modeling efforts to allow spatially explicit predictions of the distribution of subsurface oil. We used a set of pooled field data and predictor variables stored as Geographic Information Systems (GIS) data to generate calibrated boosted tree models predicting the encounter probability of different categories of subsurface oil. The models demonstrated excellent predictive performance as evaluated by cross-validated performance statistics. While the average encounter probabilities at most shoreline locations are low across western PWS, clusters of shoreline locations with elevated encounter probabilities remain in the northern parts of the PWS, as well as more isolated locations. These results can be applied to estimate the location and amount of remaining oil, evaluate potential ongoing impacts, and guide remediation. This is the first application of quantitative machine-learning based modeling techniques in estimating the likelihood of ongoing, long-term shoreline oil persistence after a major oil spill.

Part I: the development of the catalytic Wittig reaction.

We have developed the first catalytic (in phosphane) Wittig reaction (CWR). The utilization of an organosilane was pivotal for success as it allowed for the chemoselective reduction of a phosphane oxide. Protocol optimization evaluated the phosphane oxide precatalyst structure, loading, organosilane, temperature, solvent, and base. These studies demonstrated that to maintain viable catalytic performance it was necessary to employ cyclic phosphane oxide precatalysts of type 1. Initial substrate studies utilized sodium carbonate as a base, and further experimentation identified N,N-diisopropylethylamine (DIPEA) as a soluble alternative. The use of DIPEA improved the ease of use, broadened the substrate scope, and decreased the precatalyst loading. The optimized protocols were compatible with alkyl, aryl, and heterocyclic (furyl, indolyl, pyridyl, pyrrolyl, and thienyl) aldehydes to produce both di- and trisubstituted olefins in moderate-to-high yields (60-96%) by using a precatalyst loading of 4-10 mol%. Kinetic E/Z selectivity was generally 66:34; complete E selectivity for disubstituted α,ß-unsaturated products was achieved through a phosphane-mediated isomerization event. The CWR was applied to the synthesis of 54, a known precursor to the anti-Alzheimer drug donepezil hydrochloride, on a multigram scale (12.2 g, 74% yield). In addition, to our knowledge, the described CWR is the only transition-/heavy-metal-free catalytic olefination process, excluding proton-catalyzed elimination reactions.

Extent and degree of shoreline oiling: Deepwater Horizon oil spill, Gulf of Mexico, USA.

The oil from the 2010 Deepwater Horizon spill in the Gulf of Mexico was documented by shoreline assessment teams as stranding on 1,773 km of shoreline. Beaches comprised 50.8%, marshes 44.9%, and other shoreline types 4.3% of the oiled shoreline. Shoreline cleanup activities were authorized on 660 km, or 73.3% of oiled beaches and up to 71 km, or 8.9% of oiled marshes and associated habitats. One year after the spill began, oil remained on 847 km; two years later, oil remained on 687 km, though at much lesser degrees of oiling. For example, shorelines characterized as heavily oiled went from a maximum of 360 km, to 22.4 km one year later, and to 6.4 km two years later. Shoreline cleanup has been conducted to meet habitat-specific cleanup endpoints and will continue until all oiled shoreline segments meet endpoints. The entire shoreline cleanup program has been managed under the Shoreline Cleanup Assessment Technique (SCAT) Program, which is a systematic, objective, and inclusive process to collect data on shoreline oiling conditions and support decision making on appropriate cleanup methods and endpoints. It was a particularly valuable and effective process during such a complex spill.

Recovery of interior brackish marshes seven years after the chalk point oil spill.

Seven years after the April 2000 spill of 140,000 gallons of a mixture of No. 6 and No. 2 fuel oils in the Patuxent River, Maryland, heavily oiled brackish marshes showed continuing effects. Stem density and stem height were significantly lower in oiled versus unoiled sites for Spartina alterniflora but not Spartina cynosuroides habitats. In contrast, belowground biomass was significantly lower in S. cynosuroides habitats but not S. alterniflora habitats. Total PAH concentrations were up to 453 mg/kg in surficial soils (0-10 cm) and 2921 mg/kg with depth (10-20 cm). The oil had lost 22-76% of its initial PAH content after seven years, although the oil in marsh soils has undergone little to no additional weathering since Fall 2000. Based on amphipod acute toxicity tests and sediment quality guidelines, 25% of the soils in the marsh are expected to be toxic (ESB-TU(FCV) values>3.0; P(Max)>0.65).