Fluorescence-estimated oil concentration (Foil) in the Deepwater Horizon subsea oil plume.

Tracking the subsea oil plume during the 2010 Deepwater Horizon Oil Spill (DWH) was conducted using in situ fluorescence via vertical profilers (n = 1157) and discrete sample chemical analyses (n = 7665). During monitoring efforts, discrete samples provided a coarse picture of the oil plume footprint, but the majority of the samples were below standard analytical detection limits for petroleum hydrocarbons. In situ fluorescence data improved the spatial and temporal resolution of the subsea oil plume characterization. Here we synthesized millions of continuous fluorescence data points from hundreds of contemporaneously discrete samples collected to demonstrate how fluorescence could serve as a proxy for Benzene-Toluene-Ethylbenzene-Xylene (BTEX) concentration. Data mined from Gulf Science Data repository were well correlated, and geographically and temporally aligned to provide direct comparisons. Described here are the methods used to calibrate the fluorescence data and to spatially approximate the three-dimensional geographic extent of the oil plume.

Autonomous Water Sampler for Oil Spill Response.

A newly developed water sampling system enables autonomous detection and sampling of underwater oil plumes. The Midwater Oil Sampler collects multiple 1-L samples of seawater when preset criteria are met. The sampler has a hydrocarbon-free sample path and can be configured with several modules of six glass sample bottles. In August 2019, the sampler was deployed on an autonomous underwater vehicle and captured targeted water samples in natural oil seeps offshore Santa Barbara, CA, USA.

Towards integrated modeling of the long-term impacts of oil spills.

Although great progress has been made to advance the scientific understanding of oil spills, tools for integrated assessment modeling of the long-term impacts on ecosystems, socioeconomics and human health are lacking. The objective of this study was to develop a conceptual framework that could be used to answer stakeholder questions about oil spill impacts and to identify knowledge gaps and future integration priorities. The framework was initially separated into four knowledge domains (ocean environment, biological ecosystems, socioeconomics, and human health) whose interactions were explored by gathering stakeholder questions through public engagement, assimilating expert input about existing models, and consolidating information through a system dynamics approach. This synthesis resulted in a causal loop diagram from which the interconnectivity of the system could be visualized. Results of this analysis indicate that the system naturally separates into two tiers, ocean environment and biological ecosystems versus socioeconomics and human health. As a result, ocean environment and ecosystem models could be used to provide input to explore human health and socioeconomic variables in hypothetical scenarios. At decadal-plus time scales, the analysis emphasized that human domains influence the natural domains through changes in oil-spill related laws and regulations. Although data gaps were identified in all four model domains, the socioeconomics and human health domains are the least established. Considerable future work is needed to address research gaps and to create fully coupled quantitative integrative assessment models that can be used in strategic decision-making that will optimize recoveries from future large oil spills.

Integrating Inland and Coastal Water Quality Data for Actionable Knowledge.

Water quality measures for inland and coastal waters are available as discrete samples from professional and volunteer water quality monitoring programs and higher-frequency, near-continuous data from automated in situ sensors. Water quality parameters also are estimated from model outputs and remote sensing. The integration of these data, via data assimilation, can result in a more holistic characterization of these highly dynamic ecosystems, and consequently improve water resource management. It is becoming common to see combinations of these data applied to answer relevant scientific questions. Yet, methods for scaling water quality data across regions and beyond, to provide actionable knowledge for stakeholders, have emerged only recently, particularly with the availability of satellite data now providing global coverage at high spatial resolution. In this paper, data sources and existing data integration frameworks are reviewed to give an overview of the present status and identify the gaps in existing frameworks. We propose an integration framework to provide information to user communities through the the Group on Earth Observations (GEO) AquaWatch Initiative. This aims to develop and build the global capacity and utility of water quality data, products, and information to support equitable and inclusive access for water resource management, policy and decision making.

Toxicity of oil spill response agents and crude oils to five aquatic test species.

The majority of aquatic toxicity data for petroleum products has been limited to a few intensively studied crude oils and Corexit chemical dispersants, and acute toxicity testing in two standard estuarine test species: mysids (Americamysis bahia) and inland silversides (Menidia beryllina). This study compared the toxicity of two chemical dispersants commonly stock piled for spill response (Corexit EC9500A®, Finasol®OSR 52), three less studied agents (Accell Clean®DWD dispersant; CytoSol® surface washing agent; Gelco200® solidifier), and three crude oils differing in hydrocarbon composition (Dorado, Endicott, Alaska North Slope). Consistent with listings on the U.S. National Contingency Plan Product Schedule, general rank order toxicity was greatest for dispersants and lowest for the solidifier. The results indicate that freshwater species can have similar sensitivity as the conventionally tested mysids and silversides, and that the sea urchin (Arbacia punctulata) appears to be a reasonable addition to increase taxa diversity in standardized oil agent testing.

Microbial degradation of Cold Lake Blend and Western Canadian select dilbits by freshwater enrichments.

Treatability experiments were conducted to determine the biodegradation of diluted bitumen (dilbit) at 5 and 25 °C for 72 and 60 days, respectively. Microbial consortia obtained from the Kalamazoo River Enbridge Energy spill site were enriched on dilbit at both 5 (cryo) and 25 (meso) ºC. On every sampling day, triplicates were sacrificed and residual hydrocarbon concentrations (alkanes and polycyclic aromatic hydrocarbons) were determined by GCMS/MS. The composition and relative abundance of different bacterial groups were identified by 16S rRNA gene sequencing analysis. While some physicochemical differences were observed between the two dilbits, their biodegradation profiles were similar. The rates and extent of degradation were greater at 25 °C. Both consortia metabolized 99.9% of alkanes; however, the meso consortium was more effective at removing aromatics than the cryo consortium (97.5 vs 70%). Known hydrocarbon-degrading bacteria were present in both consortia (Pseudomonas, Rhodococcus, Hydrogenophaga, Parvibaculum, Arthrobacter, Acidovorax), although their relative abundances depended on the temperatures at which they were enriched. Regardless of the dilbit type, the microbial community structure significantly changed as a response to the diminishing hydrocarbon load. Our results demonstrate that dilbit can be effectively degraded by autochthonous microbial consortia from sites with recent exposure to dilbit contamination.

Photochemical oxidation reduced the efficacy of aerial dispersants applied in response to the Deepwater Horizon spill.

Chemical dispersants are one of many tools used to mitigate the overall environmental impact of oil spills. In principle, dispersants break up floating oil into small droplets that disperse into the water column where they are subject to multiple fate and transport processes. The effectiveness of dispersants typically decreases as oil weathers in the environment. This decrease in effectiveness is often attributed to evaporation and emulsification, with the contribution of photochemical weathering assumed to be negligible. Here, we aim to test this assumption using Macondo well oil released during the Deepwater Horizon spill as a case study. Our results indicate that the effects of photochemical weathering on Deepwater Horizon oil properties and dispersant effectiveness can greatly outweigh the effects of evaporative weathering. The decrease in dispersant effectiveness after light exposure was principally driven by the decreased solubility of photo-oxidized crude oil residues in the solvent system that comprises COREXIT EC9500A. Kinetic modeling combined with geospatial analysis demonstrated that a considerable fraction of aerial applications targeting Deepwater Horizon surface oil had low dispersant effectiveness. Collectively, the results of this study challenge the paradigm that photochemical weathering has a negligible impact on the effectiveness of oil spill response and provide critical insights into the "window of opportunity" to apply chemical dispersants in response to oil spills in sunlit waters.

Mobile device application for monitoring cyanobacteria harmful algal blooms using Sentinel-3 satellite Ocean and Land Colour Instruments.

Cyanobacterial harmful algal blooms (cyanoHAB) cause human and ecological health problems in lakes worldwide. The timely distribution of satellite-derived cyanoHAB data is necessary for adaptive water quality management and for targeted deployment of water quality monitoring resources. Software platforms that permit timely, useful, and cost-effective delivery of information from satellites are required to help managers respond to cyanoHABs. The Cyanobacteria Assessment Network (CyAN) mobile device application (app) uses data from the European Space Agency Copernicus Sentinel-3 satellite Ocean and Land Colour Instrument (OLCI) in near realtime to make initial water quality assessments and quickly alert managers to potential problems and emerging threats related to cyanobacteria. App functionality and satellite data were validated with 25 state health advisories issued in 2017. The CyAN app provides water quality managers with a user-friendly platform that reduces the complexities associated with accessing satellite data to allow fast, efficient, initial assessments across lakes.

Toxicity of Cold Lake Blend and Western Canadian Select dilbits to standard aquatic test species.

Dilbits are blends of bitumen and natural gas condensates or crude oils with only limited toxicity data. Two dilbits, Cold Lake Blend and Western Canadian Select, were tested as either unweathered or weathered oils for acute and chronic toxicity to standard freshwater and estuarine organisms. Water accommodated fractions of the dilbits were characterized for total petroleum hydrocarbons (TPH), polycyclic aromatic hydrocarbons (PAHs), and monoaromatics (BTEX). Acute toxicity of unweathered and weathered dilbits ranged from 4 to 16 mg/L TPH, 8 to 40 µg/L total PAHs, and 0.7 to 16 mg/L BTEX in Ceriodaphnia dubia, Pimephales promelas, Americamysis bahia, and Menidia beryllina. Concentrations of weathered dilbits causing impaired growth (A. bahia) and reproduction (C. dubia) ranged from 0.8 to 3.5 mg/L TPH and 6 to 16 µg/L PAHs. The two dilbits had generally similar acute and short term chronic toxicity expressed as TPH or total PAHs as other crude oils and other petroleum products.

Characterizing light attenuation within Northwest Florida Estuaries: Implications for RESTORE Act water quality monitoring.

Water Quality (WQ) condition is based on ecosystem stressor indicators (e.g. water clarity) which are biogeochemically important and critical when considering the Deepwater Horizon oil spill restoration efforts under the 2012 RESTORE Act. Nearly all of the proposed RESTORE projects list restoring WC as a goal, but 90% neglect water clarity. Here, dynamics of optical constituents impacting clarity are presented from a 2009-2011 study within Pensacola, Choctawhatchee, St. Andrew and St. Joseph estuaries (targeted RESTORE sites) in Northwest Florida. Phytoplankton were the smallest contribution to total absorption (at-wPAR) at 412nm (5-11%), whereas colored dissolved organic matter was the largest (61-79%). Estuarine at-wPAR was significantly related to light attenuation (KdPAR), where individual contributors to clarity and the influence of climatic events were discerned. Provided are conversion equations demonstrating interoperability of clarity indicators between traditional State-measured WQ measures (e.g. secchi disc), optical constituents, and even satellite remote sensing for obtaining baseline assessments.

Effect of dispersants on the biodegradation of South Louisiana crude oil at 5 and 25 °C.

This article reports biodegradation rates for a commercial dispersant, JD-2000, South Louisiana crude oil (SLC) alone, and SLC dispersed with JD-2000 at 5 and 25 °C. Results from the biodegradation experiments revealed that Component X, a chemical marker for JD-2000, rapidly degraded at both temperatures. The application of JD-2000 decreased by half the overall biodegradation rate of aliphatic compounds at 25 °C. At 5 °C, a residual fraction consisting of iso- and n-alkanes (C29-C35) persisted after 56 d. The combination of dispersant and higher temperature resulted in faster removal rates for 2- and 3-ring polycyclic aromatic hydrocarbons. When compared with Corexit 9500, our results suggest that the chemistry of the surfactant (or surfactants) in JD-2000 might have favored oil dissolution (substrate transport to the aqueous phase) as an uptake mechanism over adhesion, which requires direct contact of the biomass with the oil.

Submersible optical sensors exposed to chemically dispersed crude oil: wave tank simulations for improved oil spill monitoring.

In situ fluorometers were deployed during the Deepwater Horizon (DWH) Gulf of Mexico oil spill to track the subsea oil plume. Uncertainties regarding instrument specifications and capabilities necessitated performance testing of sensors exposed to simulated, dispersed oil plumes. Dynamic ranges of the Chelsea Technologies Group AQUAtracka, Turner Designs Cyclops, Satlantic SUNA and WET Labs, Inc. ECO, exposed to fresh and artificially weathered crude oil, were determined. Sensors were standardized against known oil volumes and total petroleum hydrocarbons and benzene-toluene-ethylbenzene-xylene measurements-both collected during spills, providing oil estimates during wave tank dilution experiments. All sensors estimated oil concentrations down to 300 ppb oil, refuting previous reports. Sensor performance results assist interpretation of DWH oil spill data and formulating future protocols.

An approach to developing numeric water quality criteria for coastal waters using the SeaWiFS Satellite Data Record.

Human activities on land increase nutrient loads to coastal waters, which can increase phytoplankton production and biomass and associated ecological impacts. Numeric nutrient water quality standards are needed to protect coastal waters from eutrophication impacts. The Environmental Protection Agency determined that numeric nutrient criteria were necessary to protect designated uses of Florida's waters. The objective of this study was to evaluate a reference condition approach for developing numeric water quality criteria for coastal waters, using data from Florida. Florida's coastal waters have not been monitored comprehensively via field sampling to support numeric criteria development. However, satellite remote sensing had the potential to provide adequate data. Spatial and temporal measures of SeaWiFS OC4 chlorophyll-a (Chl(RS)-a, mg m(-3)) were resolved across Florida's coastal waters between 1997 and 2010 and compared with in situ measurements. Statistical distributions of Chl(RS)-a were evaluated to determine a quantitative reference baseline. A binomial approach was implemented to consider how new data could be assessed against the criteria. The proposed satellite remote sensing approach to derive numeric criteria may be generally applicable to other coastal waters.

Organic and inorganic matter in Louisiana coastal waters: Vermilion, Atchafalaya, Terrebonne, Barataria, and Mississippi regions.

Chromophoric dissolved organic matter (CDOM) spectral absorption, dissolved organic carbon (DOC) concentration, and the particulate fraction of inorganic (PIM) and organic matter (POM) were measured in Louisiana coastal waters at Vermilion, Atchafalaya, Terrebonne, Barataria, and Mississippi River locations, in 2007-2008. The range of CDOM was 0.092 m⁻¹ at Barataria in June 2008 to 11.225 m⁻¹ at Mississippi in February 2008. An indicator of organic matter quality was predicted by the spectral slope of absorption coefficients from 350 to 412nm which was between 0.0087 m⁻¹ at Mississippi in May 2008 and 0.0261 m⁻¹ at Barataria in June 2008. CDOM was the dominant component of light attenuation at Terrebonne and Barataria. Detritus and CDOM were the primary components of light attenuation at Vermilion, Atchafalaya, and Mississippi. DOC ranged between 65 and 1235 µM. PIM ranged between 1.1 and 426.3 mg L⁻¹ and POM was between 0.3 and 49.6 mg L⁻¹.