Constraining the spatial extent of Marine Oil Snow Sedimentation and

May 14, 2017 - Following the Deepwater Horizon (DWH) event in 2010, there were several lines of evidence indicating the presence of Marine Oil Snow Se...
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Constraining the spatial extent of Marine Oil Snow Sedimentation and Flocculent Accumulation (MOSSFA) following the Deepwater Horizon Event using an excess 210Pb flux approach Patrick Thomas Schwing, Gregg R. Brooks, Rebekka Larson, Charles Holmes, Bryan O'Malley, and David J. Hollander Environ. Sci. Technol., Just Accepted Manuscript • Publication Date (Web): 14 May 2017 Downloaded from http://pubs.acs.org on May 22, 2017

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Constraining the spatial extent of Marine Oil Snow Sedimentation and Flocculent Accumulation (MOSSFA) following the Deepwater Horizon Event using an excess 210Pb flux approach Authors: Schwing, P.T.1 (corresponding author), Brooks, G.R.2, Larson, R.A.1,2, Holmes, C.W.3, O’Malley, B.J.1, Hollander, D.J.1 1. University of South Florida, College of Marine Science. 140 7th Ave. S., Saint Petersburg, FL 33701, U.S.A. Phone 001-720-394-7592, Fax 001727-553-1109, Email: [email protected] 2. Eckerd College, 4200 54th Ave. S., Saint Petersburg, FL 33711, U.S.A. 3. Environchron, 3988 Emerald Chase Dr., Tallahassee, FL, 32308, U.S.A Keywords: radioisotopes, sedimentation, oil spill, deepwater horizon, gulf of mexico, MOSSFA, marine snow

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Abstract Following the Deepwater Horizon (DWH) event in 2010, there were several lines of evidence indicating the presence of Marine Oil Snow Sedimentation and Flocculent Accumulation (MOSSFA). A significant amount of marine oil snow formed in the water column of the northern Gulf of Mexico (nGoM), settled rapidly and ultimately accumulated in the sediments of the nGoM. This study utilized a commonly used radioisotope tracer (excess 210Pb, 210Pbxs) from 32 sediment cores collected from 2010-2013 to characterize the spatial extent of MOSSFA on the seafloor. Relative to pre-DWH conditions, an increase in 210Pbxs flux, occurred in two distinct regions: 1) in the western portion of the study area on an east-northeast to west-southwest axis, stretching 230 km southwest and 140 km northeast of the DWH wellhead, and 2) in the eastern portion of the study area on a 70 km northeast to southwest axis near the DeSoto Canyon. The total sedimentary spatial extent of MOSSFA, as calculated by increased 210Pbxs flux after 2010, ranged from 12,805-35,425 km2. 210Pbxs flux provides a valuable tool for documenting the spatial extent of MOSSFA following DWH and will continue to aid in the determination of advective transport and ultimate depocenters of MOSSFA material.

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Introduction

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The Deepwater Horizon (DWH) event released over 600 million liters of

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petroleum into the Gulf of Mexico over the course of 87 days in 2010 (Atlas and

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Hazen, 2011). Formation of oiled flocculent material, predominantly at the surface

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and throughout the water column, was facilitated by the secretion of exopolymeric

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substances as a biological stress response from microbes and phytoplankton

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(Passow et al., 2012; Ziervogel et al., 2012). The oiled flocculent material including

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oil mineral aggregates began to sink at rates on the order of hundreds-of-meters per

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day (Daly et al., 2016). The increase in flocculent hydrocarbon deposition has been

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termed Marine Oil Snow Sedimentation and Flocculent Accumulation (MOSSFA).

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MOSSFA caused a 4-10 fold increase in sedimentary mass accumulation rates

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(Brooks et al., 2015), a three-fold increase in sedimentary polycyclic aromatic

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hydrocarbons (PAH)(Romero et al. 2015), as well as a persistent intensification of

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reducing conditions at the sediment water interface until 2013 (Hastings et al.,

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2016), which severely impacted benthic faunal density and diversity (Montagna et

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al., 2013; Schwing et al., 2015; Schwing et al., 2016A).

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Constraining the spatial scale of MOSSFA is necessary from an oil budget

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perspective and for determining how much petroleum was deposited in the

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sediments following DWH. A few studies have constrained the spatial extent of the

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petroleum fraction of MOSSFA using radiocarbon proxies or direct measurements of

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petroleum compounds in the surface sediments relative to down-core

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concentrations (Valentine et al., 2014; Chanton et al., 2015). Valentine et al., (2014)

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identified an area of approximately 3,200 km2 with elevated hopane concentrations

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in surface sediments surrounding the wellhead, which by proxy accounts for 4-31%

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of the petroleum budget deposited in the sediments of the northern Gulf of Mexico

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(nGoM). However, they attribute this increase in hopanes primarily to petroleum

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intrusions in the water column and not necessarily to MOSSFA. Chanton et al.,

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(2015) found that 3.0-4.9% of the oil was deposited on the seafloor throughout a

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24,000 km2 area in the northern Gulf of Mexico using a radiocarbon mass balance

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approach. While these studies focused on determining the petroleum fraction

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deposited in the sediments, it is also necessary to constrain the total spatial extent

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of increased flux of flocculent material from the water column. This study utilized

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sedimentary inventories and fluxes of a commonly used radioisotope tracer (excess

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210Pb, 210Pbxs)

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sedimentation following DWH.

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210Pb

to characterize the spatial expression of increased flocculent

is a naturally occurring radioisotope that has been used to study

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sediment dynamics and sedimentary accumulation for records on the order of 100

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years (half life of 22.1 years)(Holmes, 2001).

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been used in the nGoM and elsewhere to determine particle scavenging in the water

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column (Baskaran and Santschi, 2002), identify sediment depositional fluxes and

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transport pathways (Muhammed et al., 2008), and constrain areas of high organic

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matter deposition (Gordon and Goñi, 2004, Yeager et al., 2004, Sampere et al.,

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2011). Brooks et al. (2015) characterized the mass accumulation rates of flocculent

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material following DWH using 210Pbxs and 234Thxs geochronologies at certain sites

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primarily in the northeastern Gulf of Mexico. This study seeks to build on the work

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of Brooks et al., (2015) by using a broader collection of cores throughout the nGoM

210Pbxs

inventories and fluxes have

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and 210Pbxs fluxes to characterize the extent of increased oiled-flocculent material

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following DWH.

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Methods

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Sediment cores were collected at 32 sites from 2010-2013 throughout the

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nGoM (Figure 1, Table 1) using an Ocean Instruments MC-800 multicoring system,

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which collects eight cores (diameter: 10 cm, length: up to 70 cm) simultaneously,

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one of which was used from each site for short-lived radioisotope analysis. Cores

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were refrigerated (~4O C) and sub-sampled by extrusion at 2 mm intervals for the

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upper 100 mm and 5 mm intervals for the remainder of each core using a calibrated,

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threaded-rod extrusion device (Schwing et al., 2016B). Once extruded, samples

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were weighed to provide the wet mass, freeze-dried and weighed again to

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determine the dry mass.

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Short-lived radioisotope measurements and geochronological model

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calculations follow those presented in Brooks et al. (2015). Brooks et al. (2015)

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presented several lines of evidence (biological, sedimentological, microbial,

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radiocarbon, organic geochemical, etc.) that bioturbation was not present in the

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surface of the cores collected following the DWH. Samples were analyzed by gamma

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spectrometry on Canberra HPGe (High-Purity Germanium) Coaxial Planar Photon

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Detectors for total 210Pb (46.5Kev), 214Pb (295 Kev and 351 Kev), and 214Bi (609Kev)

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activities. Data were corrected for counting time and detector efficiency, as well as

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for the fraction of the total radioisotope measured yielding activity in dpm g-1

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(disintegrations per minute per gram).

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Detector efficiencies (limit of detection) were all 1 dpm cm-2 yr-1, >1.5 dpm

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cm-2 yr-1, >3.0 dpm cm-2 yr-1) from the pre-DWH to the post-DWH period using a

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combination of coordinates identified from the ODV, DIVA grid and the Google Earth

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Pro polygon tool. The >1.5 dpm cm-2 yr-1 and >3.0 dpm cm-2 yr-1 intervals were

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based on consistent (1.5 dpm cm-2 yr-1) intervals from 0-4.5 dpm cm-2 yr-1. The 4.5

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dpm cm-2 yr-1 value represents the largest measured differential pre-to-post-DWH

flux were constructed using Ocean Data View (ODV). Polygons were created

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210Pbxs

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polygon was also constructed from the coordinates of the sampling sites with

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increased pre-to-post-DWH 210Pbxs flux to produce the most conservative estimate

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of spatial coverage, without including DIVA gridding extrapolation.

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Results

flux at site DWH01 near the DWH wellhead. A least distance-spanning

210Pbxs

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flux increased in every core from the 1900-1949 to the 1950-2009

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period (0.11-1.32 dpm cm-2 yr-1, Table 1).

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from the 1950-2009 to the 2010-2013 period (0.06-4.46 dpm cm-2 yr-1, Table 1). 210Pbxs

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210Pbxs

flux also increased in every core

flux decreased with distance from the DWH wellhead along three

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transects (northeast, southeast, southwest) during the 2010-2013 period (Figure 3).

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There was no decrease in 210Pbxs flux with distance from the DWH wellhead along

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the same transects during the 1950-2009 period. The 210Pbxs flux during the 1900-1949 and 1950-2009 periods generally

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increased with water depth and higher fluxes generally followed bathymetric

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features such as the DeSoto Canyon to the east and the Mississippi Valley to the west

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(Figure 4, Table 2).

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In total, five polygons were constructed, three in the western portion of the

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study area and two in the eastern portion (Table 3). In the western portion of the

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study area, an area of 32,350 km2 had a differential 210Pbxs flux greater than 1.5 dpm

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cm-2 yr-1, an area of 16,972 km2 had a differential 210Pbxs flux greater than 3 dpm cm-

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2 yr-1,

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210Pbxs

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3). In the eastern portion of the study area, an area of 3,075 km2 had a differential

and an area between sampling stations (minimum span) with differential flux greater than 1.5 dpm cm-2 yr-1 had an area of 11,273 km2 (Figure 5, Table

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210Pbxs

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with differential 210Pbxs flux greater than 1.0 dpm cm-2 yr-1 (minimum span) had an

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area of 1,532 km2 (Figure 5, Table 3).

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Discussion

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flux greater than 1 dpm cm-2 yr-1, and an area between sampling stations

The range of total 210Pbxs inventories from this study was slightly higher

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overall than those previously published. Yeager et al., (2004) reported a range in

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total 210Pbxs inventories of 21.0-208.8 dpm cm-2 from six sites throughout the nGoM

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and the 210Pbxs inventories from this study ranged from 34.0-275.1 dpm cm-2 (Table

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1). Two of the sampling sites (S36, 1849 m water depth; MT3, 985 m water depth)

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presented by Yeager et al., (2004) were near (21 km and 40 km, respectively) two of

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the sites sampled in this study (DSH10, MV02). The total 210Pbxs inventories at

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DSH10 and MV02 were 155.0 (± 0.06 dpm cm-2) and 275.1 (± 0.03 dpm cm-2), while

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the total 210Pbxs inventories at S36 and MT3 were 108.6 (± 0.12 dpm cm-2) and 208.8

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(± 0.07 dpm cm-2) respectively. Yeager et al. (2004) used an alpha spectrometry

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method while this study used a gamma spectrometry method. The errors associated

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with the different analytical methods are negligible compared to the variability

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between sites that both Yeager et al. (2004)(21-208 dpm cm-2) and this manuscript

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(34-275 dpm cm-2) document throughout the gulf. The overall agreement between

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records over the entire nGoM region is evidence that these datasets are comparable.

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Again, these comparisons are only used in this manuscript to demonstrate that our

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data are reasonable with regards to previously published literature in the region,

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which is quite limited. It is arguable that the overall increase in 210Pbxs inventories

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from Yeager et al., (2004) to this study could have been caused by the increased

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210Pbxs

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flux associated with MOSSFA during and following DWH. Prior to 2010, 210Pbxs flux primarily increased with water depth (Figure 4,

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Table 2) suggesting that bathymetric features acted as a control of 210Pbxs flux prior

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to 2010.

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regions from 1900-1949 and primarily in the Desoto Canyon from 1950-2009

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(Figure 4). As expected, a deeper water column provided greater 210Pbxs activity for

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particle scavenging and bathymetric lows may have provided focusing mechanisms

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for advective transport.

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210Pbxs

flux was focused in the DeSoto Canyon and Mississippi Valley

The fact that there is not a significant increase in 210Pbxs flux over the entire

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region from the 1900-1950 to 1950-2009, whereas there is a significant increase

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from 1950-2009 to 2010-2013, argues that the increased signal is not from natural

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variability (e.g. Mississippi River) and was in fact caused by DWH, MOSSFA. The

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pearson correlation (Table 2) further supports that prior to DWH, 210Pbxs flux was

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primarily determined by water depth. After 2010, the sinking of marine oil snow

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primarily controlled the distribution of 210Pbxs flux. The decrease in 210Pbxs flux with

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distance from the DWH wellhead is consistent with MOSSFA centered on the DWH

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wellhead (Figure 3, Table 2). This decrease in 210Pbxs flux with distance from the

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wellhead was not apparent in the 1950-2009 time period, which further supports a

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change in depositional pattern during and after DWH.

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The spatial extent of MOSSFA, determined by differential 210Pbxs flux between

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the 1950-2009 period and the 2010-2013 period was primarily focused in two

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areas: 1) in the western portion of the study area on an east-northeast to west-

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southwest axis, stretching 230 km to the southwest and 140 km to the northeast of

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the DWH wellhead, and 2) in the eastern portion of the study area on a 70 km

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northeast to southwest axis near the DeSoto Canyon (Figure 5).

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In the area to the west, spatial estimates of MOSSFA ranged from 11,273-

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32,350 km2 using differential 210Pbxs flux. Estimates of the spatial extent of

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sedimentary petroleum deposition, based on sedimentary radiocarbon, flocculent

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sedimentary hopane concentration, flux rates of petroleum compounds, and

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petroleum compounds in flocculent sediments ranged from 1,300-24,000 km2

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(Chanton et al., 2015; Valentine et al., 2014; NRDA, 2015; Stout et al., 2015; Stout

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and German, 2015; Passow and Ziervogel, 2016). Chanton et al., (2015) identified

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an area of 8,400 km2 primarily to the southwest of the DWH wellhead that was

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impacted by sedimentary petroleum deposition. Valentine et al., (2014) utilized

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hopane concentrations in sedimentary flocculent material to constrain an area of

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3,200 km2 centered on the DWH wellhead. However, the objective of these studies

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was to identify areas with increased petroleum deposition using petroleum

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indicators, while the aim of this study was to constrain the total spatial extent of

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increased flux of flocculent material from the water column. So, it was expected that

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210Pbxs

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previous petroleum indicator estimates. Ultimately, the most conservative estimate

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(11,273 km2), which was based on the minimum span between sampling sites, was

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most consistent with previous studies that identified the spatial extent of various

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sedimentary petroleum indicators.

flux would provide a larger estimate of the spatial extent of MOSSFA than the

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For the eastern extent of this study, spatial estimates of MOSSFA ranged from

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1,532-3,075 km2 using differential 210Pbxs flux. Again, the most conservative

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estimate (1,532 km2), based on the minimum span between sampling sites was most

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consistent with previous studies that identified the spatial extent of sedimentary

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petroleum indicators (~2,000 km2) near the DeSoto Canyon (Romero et al., 2015;

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Passow and Ziervogel, 2016). The ~2000 km2 estimate was generated by using GIS

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to calculate the area of polygons between impacted sites (Passow, pers. comm.).

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Based on synthetic aperture radar (SAR) data, the maximum daily extent of

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surface petroleum coverage was 39,600 km2 (NRDA, 2015). The highest estimates

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(35,425 km2) of the spatial extent of MOSSFA from this study (3,075 km2 >1 dpm

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cm-2 yr-1 to the east and 32,350 km2 >1.5 dpm cm-2 yr-1 to the west) were less than,

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but on the same order as the spatial extent of daily surface petroleum coverage, and

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agreed with findings that MOSSFA affected broad sections of the continental slope

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and shelf where surface oil occurred (NRDA, 2015; Stout and German, 2015). The

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eastern and western areas of higher 210Pbxs fluxes identified in this study were also

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within the extent of the cumulative surface petroleum coverage (87 days, 112,115

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km2, NRDA, 2015) (Figure 5).

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Another important consideration was the agreement of the spatial extent of

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increased 210Pbxs flux with observed MOSSFA impacts to the benthos in the nGoM

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following the DWH event. Following the DWH event, a 4-10 fold increase in

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sedimentary mass accumulation rates and a 2-3 fold increase in polycyclic aromatic

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hydrocarbons was documented in the DeSoto Canyon region (Brooks et al., 2015;

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Romero et al., 2015). The total organic carbon (TOC) accumulation rates at DSH08

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and PCB06 increased from 6.3-12.6 gcm-2yr-1 on average prior to the DWH to 91-

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136 gcm-2yr-1 during 2010 (Romero et al., 2015, Schwing et al., 2015). Respiration

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of the increased organic carbon flux caused intensifying reducing conditions until

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2013 (Hastings et al., 2016). Schwing et al. (2015, 2016A) documented an 80-93%

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decrease in benthic foraminiferal density and a 30-40% decrease in benthic

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foraminiferal diversity directly related to increased PAH concentrations and

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intensification of reducing conditions at sites in the DeSoto Canyon region (e.g.

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DSH08) from 2010-2011. The differential pre-to-post-DWH 210Pbxs flux at DSH08

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was 2.42 dpm cm-2 yr-1. In the western portion of the study area, Montagna et al.

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(2013) found that macrofaunal diversity was impacted throughout an area of 148

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km2 centered around the DWH wellhead. The DWH01 site, less that 1km from the

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DWH wellhead, differential pre-to-post-DWH 210Pbxs flux was 4.46 dpm cm-2 yr-1.

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Baguley et al. (2015) also found that meiofaunal diversity was impacted over an

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area of 406 km2 in two distinct regions; surrounding the DWH wellhead and the

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Mississippi Valley. The Mississippi Valley area of impact described by Baguley et al.

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(2015) encompasses the MV02 and SW01 sites from this study. The differential pre-

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to-post-DWH 210Pbxs flux was 1.57 dpm cm-2 yr-1 at SW01 and 3.83 dpm cm-2 yr-1 at

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MV02. Increased 210Pbxs flux was documented at each of the sites in the DeSoto

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canyon, near the DWH wellhead, and in the Mississippi Valley regions where there

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were corresponding impacts to benthic biological diversity and density. The spatial

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agreement between these three records of benthic biological impact and increased

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210Pbxs

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supporting the use of 210Pbxs flux as a tracer for MOSSFA.

flux measurements provided another corroborative line of evidence

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Overall, the use of 210Pbxs flux was successfully utilized as a tracer for DWH-

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related MOSSFA. Two primary depositional areas were identified with a total

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spatial extent ranging from 12,805-35,425 km2. The primary advantage of using

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210Pbxs

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was the ability to constrain the total spatial extent of increased mass flux of

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flocculent material from the water column, beyond simply the petroleum fraction.

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Further work is needed, using sedimentary collections beyond 2013, to assess the

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effects of advective transport and to identify the ultimate depocenters of MOSSFA

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material.

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Acknowledgements

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This research was made possible in part by a grant from the Gulf of Mexico Research

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Initiative, C-IMAGE, DEEP-C and in part by the British Petroleum/Florida Institute of

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Oceanography (BP/FIO)-Gulf Oil Spill Prevention, Response, and Recovery Grants

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Program. The authors also thank the crew of the R/V Weatherbird II for their

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assistance during the field program. Data are publicly available through the Gulf of

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Mexico Research Initiative Information & Data Cooperative (GRIIDC) at:

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http://data.gulfresearchinitiative.org/data/R4.x267.000:0016 (doi:

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10.7266/N73N21FW).

flux as a complimentary tool in addition to sedimentary petroleum tracers

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Hussain N.; Kim G.; Church T.M.; Carey W. A simplified technique for gammaspectrometric analysis of 210Pb in sediment samples. Appl. Radiat. Isot., 1996, 47: 473–477. Kitto, M.E. Determination of photon self-absorption corrections for soil samples, Appl. Radiat. Isot., 1991, 42, 835-839. Montagna P.A.; Baguley J.G.; Cooksey C.; Hartwell I.; Hyde L.J.; Hyland, J.L.; Kalke R.D.; Kracker, L.M.; Reuscher, M.; Rhodes, A.C.E. Deep-Sea Benthic Footprint of the Deepwater Horizon Blowout. PLoS ONE, 2013, 8(8): e70540. doi:10.1371/journal.pone.0070540 Muhammad, Z.; Bentley, S.J.; Febo, L.A.; Droxler, A.W.; Dickens, G.R.; Peterson, L.C. and Opdyke, B.N. Excess 210Pb inventories and fluxes along the continental slope and basins of the Gulf of Papua, J. Geophys. Res., 2008, 113, F01S17, doi:10.1029/2006JF000676. Draft Programmatic Environmental Impact Statement; Natural Resource Damage Assessment, National Ocean Service, National Oceanic and Atmospheric Administration, 2015; http://www.Gulfspillrestoration.noaa.gov/wpcontent/uploads/Chapter-4_Injury-to-Natural-Resources.pdf. Passow, U. and K. Ziervogel. Marine snow sedimented oil released during the Deepwater Horizon spill. Oceanography, 2016, 29(3):118–125, http://dx.doi.org/10.5670/oceanog.2016.76. Passow, U.; Ziervogel, K.; Aper, V.; Diercks, A. Marine snow formation in the aftermath of the Deepwater Horizon oil spill in the Gulf of Mexico. Environ. Res. Lett., 2012, 7, 035301. Romero, I.C.; Schwing, P.T.; Brooks, G.R.; Larson, R.A.; Hastings, D.W.; Ellis G.; Goddard, E.A.; Hollander, D.J. Hydrocarbons in Deep Sea Sediments Following the 2010 Deepwater Horizon Blowout in the Northeast Gulf of Mexico. PLoS ONE, 2015, 10(5): e0128371. doi: 10.1371/journal.pone.0128371

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Sampere, T. P.; Bianchi, T. S. & Allison, M. A. Historical changes in terrestrially derived organic carbon inputs to Louisiana continental margin sediments over the past 150 years. J. Geophys. Res., 2011, 116(G1), G01016. http://doi.org/10.1029/2010JG001420

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Schwing, P.T.; O’Malley, B.J.; Romero, I.C.; Martínez-Colón, M.; Hastings, D.W.; Glabach, M.A.; Hladky, E.M.; Greco, A., Hollander, D.J. Characterizing the variability of benthic foraminifera in the northeastern Gulf of Mexico following the Deepwater Horizon event (2010-2012). Environ. Sci. & Poll. Res., 2016A, DOI 10.1007/s11356016-7996-z.

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Schwing, P.T., Romero, I.C., Larson, R.A., O'Malley, B.J., Fridrik, E.E., Goddard, E.A., Brooks, G.R., Hastings, D.W., Rosenheim, B.E., Hollander, D.J., Grant, G., Mulhollan, J. Sediment Core Extrusion Method at Millimeter Resolution Using a Calibrated, Threaded-rod. J. Vis. Exp., 2016B (114), e54363, doi:10.3791/54363. Schwing, P.T.; Romero, I.C.; Brooks, G.R.; Hastings, D.W.; Larson, R.A.; Hollander, D.J. A Decline in Deep-Sea Benthic Foraminifera Following the Deepwater Horizon Event in the Northeastern Gulf of Mexico. PLoS ONE, 2015, 10(3): e0120565. doi:10.1371/journal.pone.0120565. Stout, A.S. and German, C.R. Characterization and Flux of Marine Oil Snow into the Visca Knoll (Lophelia Reef) Area due to the Deepwater Horizon Oil Spill. US Department of the Interior, Deepwater Horizon Response & Restoration, Administrative Record, 2015, 34, http://pub-dwhdatadiver.orr.noaa. gov/dwh-ardocuments/946/DWH-AR0039084.pdf. Stout, A.S.; Rouhani, S.; Liu, B. and Oehrig, J. Spatial Extent (“Footprint”) and Volume of Macondo Oil Found on the Deep-Sea Floor Following the Deepwater Horizon Oil Spill. US Department of the Interior, Deepwater Horizon Response & Restoration, Administrative Record, 2015, DWH-AR0260244, 29, http://pubdwhdatadiver.orr.noaa.gov/ dwh-ar-documents/946/DWH-AR0260244.pdf. Valentine, D. L.; Fisher, G. B.; Bagby, S. C.; Nelson, R. K.; Reddy, C. M. & Sylva, S. P. Fallout plume of submerged oil from Deepwater Horizon, PNAS, 2014, 1–6. doi:10.1073/pnas.1414873111 Yeager, K.M.; Santschi, P.H.; Rowe, G.T. Sediment accumulation and radionuclide 239,240

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inventories ( Pu, Pb and Th) in the northern Gulf of Mexico, as influenced by organic matter and macro- faunal density. Mar. Chem. 2004, 91: 1–14.

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Ziervogel, K.; Mckay, L.; Rhodes, B.; Osburn, C. L.; Dickson-Brown, J.; Arnosti, C.; Teske, A. Microbial activities and dissolved organic matter dynamics in oilcontaminated surface seawater from the Deepwater Horizon oil spill site. PLoS One, 2012, 7(4), e34816.

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Figure Captions Figure 1: Coring site locations in the northern Gulf of Mexico. (For reference: DWH01 is less than 1 km from the Deepwater Horizon wellhead).

Figure 2: Graphic depiction of the decay correction method and integration of 210Pbxs flux during each time period. The yellow bars represent the 210Pbxs activity corrected to the surface activity (time of collection) for each sample increment. The base figure of idealized supported and unsupported (excess) 210Pb was adapted from Holmes, 2001 and the inventories were calculated using the method described by Baskaran and Santschi, 2002. Figure 3: Plots of 210Pbxs flux with distance (left to right) from the DWH wellhead along three transects (A. southeast, B. northeast, and C. southwest) for the pre-DWH (1950-2009, light gray bars) and post-DWH (2010-2013, dark gray bars) time periods. Figure 4: DIVA gridded contour maps of 210Pbxs flux for 1900-1949 (A), 1950-2009 (B), and 2010-2013 (C). The star represents the location of the DWH wellhead. Figure 5: A DIVA gridded contour map of the differential (difference of post-DWH and pre-DWH values) 210Pbxs flux. Polygons were constructed to determine the spatial extent of differential 210Pbxs flux. The polygons surround differential 210Pbxs flux greater than 3 dpm cm-2 yr-1 (blue), 1.5 dpm cm-2 yr-1 (black) and a minimum span between coring sites (red) in the western extent of the study area and greater than 1 dpm cm-2 yr-1 (black) and minimum span between coring sites (red) in the eastern extent of the study area. The gray overlay is the cumulative total extent of surface petroleum coverage (ERMA, 2015). The star represents the location of the DWH wellhead.

505 506 507 508 509 510 511 512 513 514 515 516 517 518 519 520

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Tables Table 1: Core site names, collection date, location, water depth, distance from the Deepwater Horizon wellhead, 210Pbxs flux for each time period (1900-1949, 1950-2009, 2010-2013) and the total 210Pbxs inventory. 210Pb

-2

xs

-1

Flux (dpm cm yr )

Longitude

Water Depth (m)

Distance from DWH (km)

20102013

19502009

19001949

Total Pbxs Inventory -2 (dpm cm )

29.66

-86.33

108

222

0.77

0.26

0.06

42.45

29.41

-86.58

302

188

2.83

1.06

0.68

59.26

10-Nov

29.3

-86.68

400

177

0.95

0.37

0.23

68.28

10-Nov

29.17

-86.81

504

160

3.06

0.83

0.37

85.44

MC06

10-Nov

29.08

-86.91

600

148

2.02

0.58

0.2

59.57

MC07

10-Nov

29.39

-86.75

400

175

1.47

0.52

0.32

43.49

MC08

10-Nov

29.49

-86.87

404

168

2.03

1.03

0.28

79.29

MC09

10-Nov

29.22

-86.64

406

177

1.48

0.58

0.35

45.95

MC10

10-Nov

29.07

-86.56

399

183

1.18

0.46

0.26

65.20

DSH07

10-Dec

29.27

-87.76

399

83

2.87

1.29

0.26

112.64

PCB06

10-Dec

29.13

-87.26

1043

117

1.17

0.79

0.44

85.02

DSH08

11-Feb

29.12

-87.87

1143

63

3.4

0.98

0.34

118.49

DSH10

11-Feb

28.98

-87.89

1520

54

2.76

2.2

0.88

152.97

PCB08

11-Feb

28.9

-87.16

900

120

0.86

0.41

0.17

54.50

PCB09

11-Feb

28.86

-87.21

1000

116

1.54

0.92

0.37

69.50

PCB10

11-Feb

28.82

-87.27

1100

108

2.41

1.71

0.48

64.43

NT150

11-Jun

28.53

-85.2

150

312

0.75

0.35

0.06

36.70

NT200

11-Jun

28.4

-85.4

233

290

0.93

0.63

0.31

41.99

NT300

11-Jun

28.31

-85.57

306

277

1.56

0.66

0.34

40.55

NT400

11-Jun

28.23

-85.65

400

275

1.06

0.36

0.26

34.03

NT1200

11-Jun

27.97

-86.03

1200

246

1.81

1.26

0.76

61.58

ST1050

11-Jun

27.04

-85.09

1047

376

1.17

1.11

0.33

35.09

Date Collected (YY-MMM)

Latitude

MC01

10-Nov

MC03

10-Nov

MC04 MC05

Site Name

210

PCB11

11-Sep

28.8

-87.31

1200

103

3.13

1.01

0.31

70.88

NE01

11-Sep

28.79

-88.26

1300

13

3.51

0.86

0.53

93.41

DWH01

11-Sep

28.74

-88.39

1550

1

5.08

0.62

0.25

115.25

SW01

12-Apr

28.22

-89.07

1151

92

2.73

1.16

0.33

133.01

SW03

12-Apr

28.58

-88.8

1200

45

3.17

1.05

0.18

139.24

MV02

12-Aug

28.49

-89.78

550

140

4.3

0.47

0.37

275.11

SL5100

12-Oct

28.55

-85.37

186

296

1.55

0.6

0.22

40.66

SE02

12-Oct

28.36

-86.94

977

142

2.12

1.69

0.64

55.47

HC01

13-Aug

28.37

-90.52

45

212

1.13

0.31

0.09

47.92

HC03

13-Aug

28.22

-90.41

72

207

3.16

0.74

0.28

136.18

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527 528

Table 2: Pearson correlation table of 210Pbxs flux for each time-period with water depth and the inverse of the distance from the DWH wellhead. Note: P < 0.05 is significant. Time Period

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Water Depth 2

Inverse Distance from DWH 2

r

R

p

r

R

p

2010+

0.47

0.22

0.01

0.67

0.45

2.73E-05

1950-2009

0.61

0.37

2.35E-04

0.36

0.13

0.04

1900-1950

0.50

0.25

2.20E-03

0.23

0.05

0.21

Table 3: The location of each polygon outline point and polygon area for the three polygons in the western (West) extent of the study area (>3 dpm cm-2 yr-1, >1.5 dpm cm-2 yr-1, and minimum span) and two polygons in the eastern (East) extent of the study area (>1 dpm cm-2 yr-1 and minimum span). Polygon and 2 Site Name Latitude Longitude Area (km )

West -2

>3 dpm cm yr

-1

16,972 29.46

-88.06

29.07

-88.18

28.51

-88.31

28.65

-89.03

28.06

-89.59

28.06

-90.36

29.09

-90.02

29.21

-89.77

29.03

-89.08

29.68

-87.42

28.31

-87.91

28.04

-88.97

28.06

-90.42

28.19

-90.64

28.37

-90.52

29.09

-90.49

29.10

-90.22

29.25

-89.82

29.00

-89.20

DSH07

29.27

-87.76

DSH10

28.98

-87.89

SW01

28.22

-89.07

SW03

28.58

-88.80

HC01

28.37

-90.52

HC03

28.22

-90.41

-2

>1.5 dpm cm yr

HC01

-1

32,350

Minimum Span

11,273

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East -2

>1 dpm cm yr

-1

3,075 29.60

-86.64

29.38

-86.34

28.87

-86.85

29.22

-87.12

Minimum Span

1,532

MC03

29.41

-86.58

MC10

29.07

-86.56

MC06

29.08

-86.91

MC07

29.39

-86.75

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TOC_Abstract Art 279x215mm (300 x 300 DPI)

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Figure 1: Coring site locations in the northern Gulf of Mexico. (For reference: DWH01 is less than 1 km from the Deepwater Horizon wellhead). 279x215mm (300 x 300 DPI)

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Figure 2: Graphic depiction of the decay correction method and integration of 210Pbxs flux during each time period. The yellow bars represent the 210Pbxs activity corrected to the surface activity (time of collection) for each sample increment. The base figure of idealized supported and unsupported (excess) 210Pb was adapted from Holmes, 2001 and the inventories were calculated using the method described by Baskaran and Santschi, 2002. 279x215mm (300 x 300 DPI)

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Figure 3: Plots of 210Pbxs flux with distance (left to right) from the DWH wellhead along three transects (A. southeast, B. northeast, and C. southwest) for the pre-DWH (1950-2009, light gray bars) and post-DWH (2010-2013, dark gray bars) time periods. 279x215mm (300 x 300 DPI)

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Figure 4: DIVA gridded contour maps of 210Pbxs flux for 1900-1949 (A), 1950-2009 (B), and 2010-2013 (C). The star represents the location of the DWH wellhead. 279x215mm (300 x 300 DPI)

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Figure 5: A DIVA gridded contour map of the differential (difference of post-DWH and pre-DWH values) 210Pbxs flux. Polygons were constructed to determine the spatial extent of differential 210Pbxs flux. The polygons surround differential 210Pbxs flux greater than 3 dpm cm-2 yr-1 (blue), 1.5 dpm cm-2 yr-1 (black) and a minimum span between coring sites (red) in the western extent of the study area and greater than 1 dpm cm-2 yr-1 (black) and minimum span between coring sites (red) in the eastern extent of the study area. The gray overlay is the cumulative total extent of surface petroleum coverage (ERMA, 2015). The star represents the location of the DWH wellhead. 279x215mm (300 x 300 DPI)

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