Surface sediment hydrocarbons as indicators of subsurface hydrocarbons: Field calibration of existing and new surface geochemistry methods in the

Marco Polo area, Gulf of Mexico

Michael A. Abrams and Nicola F. Dahdah

AUTHORS Michael A. Abrams  Exploration and Production Technology Apache Corporation, Houston, Texas; Michael.Abrams@apachecorp.com Michael A. Abrams is currently the manager of geochemistry for Apache Corporation. Before working with Apache, Michael was senior research scientist in the University of Utahs Energy and Geoscience Institute and senior research geochemist in Exxon Production Research Company. Michaels research interests include surface geochemistry, petroleum systems evaluation, and migration pathway analysis. Michael received his Ph.D. from the Imperial College London, a B.S. degree from George Washington University, and an M.S. degree from the University of Southern California. Nicola F. Dahdah  Energy and Geoscience Institute University of Utah Salt Lake City, Utah; ndahdah@egi.utah.edu Nick Dahdah currently manages the organic geochemistry laboratory at EGI and has been a research scientist with the Institute since 1992, specializing in oil and source rock characterization. He previously worked as a well site geologist for the Natural Resources Authority in Jordan. He received a B.S. degree in geology from Southeast Missouri State University and an M.A. degree from the University of South Carolina.

ABSTRACT Multiple methods are currently used to collect, prepare, extract, and analyze near-surface migrated hydrocarbons from marine sediments to evaluate subsurface petroleum generation and entrapment. Few have been rigorously tested to evaluate their effectiveness. A Gulf of Mexico field calibration survey over the Marco Polo field was undertaken as part of an industry-funded research project to better understand previously published and unpublished seabed geochemical results and determine which gas and liquid hydrocarbon extraction methods best characterize migrated hydrocarbons in near-surface sediments. The Marco Polo calibration data set demonstrates the importance of targeted coring and sampling depth. To improve the detection of seabed migrated thermogenic hydrocarbons, core samples should be collected along major migration pathways (cross-stratal leakage features) identified by conventional deep seismic and high-resolution sea floor imaging. Not all targeted cores hit the designated feature, and thus, collecting replicates along key migration features is critical. Collecting sediment samples below the near-surface transition zone known as the zone of maximum disturbance is also important to

ACKNOWLEDGEMENTS We thank the Surface Geochemistry Calibration (SGC) research project industry supporters and Energy and Geoscience Institute at the University of Utah. Ger van Graas (Statoil), Dennis Miller (Petrobras), Harry Dembicki (Anadarko), Neil Frewin (Shell), Andy Bishop (Shell), Brad Huizinga (ConocoPhillips), Angelo Riva (ENI), and Peter Eisenach (Wintershall) have all been extremely helpful during the various phases of the multiyear industry-funded research project. We thank Anadarko Petroleum for allowing the SGC research project to collect samples at the Marco Polo field and access to key seismic and geochemical information. We thank Harry Dembicki who arranged permission for the Marco Polo location site, chose and monitored the core locations, and participated in the

Copyright 2011. The American Association of Petroleum Geologists. All rights reserved. Manuscript received August 13, 2010; provisional acceptance November 22, 2010; revised manuscript received January 24, 2011; final acceptance March 21, 2011. DOI:10.1306/03211110130

AAPG Bulletin, v. 95, no. 11 (November 2011), pp. 1907 1935

1907

cruise. We thank W. L. Gore and Associates and Taxon Biosciences, which provided staff and laboratory analysis at no cost. We thank Fugro and the Seis Surveyor crew as well as the shipboard research staff Harry Dembicki (Anadarko), Matt Ashby (Taxon), Shuanglin Li (Qingdoa Institute of Marine Geology), Rowland Rincon (Peregrine Ventures), and Chris Reny (Peregrine Ventures). The figures were drafted by Jeffrey Massara with Apache Corporation. Reviews by Harry Dembicki, Barry Katz, and an unnamed reviewer were very helpful. The AAPG Editor thanks the following for their work on this paper: Harry Dembicki Jr., Barry J. Katz, and an anonymous reviewer.

avoid possible alteration effects and interference by recent organic matter. Geochemical analysis should include a full range of hydrocarbon types: light hydrocarbon gases (C1C5), gasoline range (C5C10+), and high-molecular-weight (HMW) hydrocarbons (C15+). The interstitial sediment gas data should be plotted on a total hydrocarbon gas (S C1C5) versus wet gas fraction (S C2C5/S C1C5) chart to identify background, fractionated, and anomalous populations. Compound-specific isotopic analysis on selected anomalous samples is critical to correctly identify migrated subsurface gases from near-surface generated microbial gases. Microdesorption bound gases did not provide gas compositions or compound-specific isotope ratios similar to the Marco Polo reservoir gases, and thus, the bound gas extraction is not recommended. A gasoline range analysis provides a new range of hydrocarbons rarely examined in surface geochemical studies that assist in identifying thermogenic hydrocarbons. Extraction gas chromatography and total scanning fluorescence (TSF) maximum fluorescence intensity provided information on the presence of thermogenic HMW hydrocarbons but did not work as well with the lowlevel microseepage samples. The TSF fluorogram signature was similar for both seep and regional reference (background) samples and did not help to identify migrated thermogenic hydrocarbons. The Marco Polo calibration study provides a framework to better understand how best to collect (targeted deep cores) and extract migrated hydrocarbons from near-surface marine sediments and to evaluate the results.

INTRODUCTION Multiple methods are currently applied to collect, prepare, extract, and analyze near-surface migrated hydrocarbons from marine sediments to evaluate subsurface petroleum generation (Horvitz, 1985; Brooks and Carey, 1986; Abrams et al., 2001; Abrams, 2005; Logan et al., 2009; and Abrams and Dahdah, 2010). Many of the sediment hydrocarbon extraction procedures currently used by the industry are based on sampling and laboratory protocols initially designed for well cuttings and have not always been rigorously tested to evaluate their effectiveness with unconsolidated marine sediments. An extensive series of literature and data reviews, laboratory tests, and field studies have been conducted as part of an industryfunded Surface Geochemistry Calibration (SGC) research project conducted by the University of Utahs Energy and Geoscience
1908 Surface Sediment Hydrocarbons as Indicators of Subsurface Hydrocarbons

Figure 1. The Marco Polo field is approximately 175 mi (281 km) south of New Orleans, Louisiana, in blocks 563, 607, and 608 Green Canyon Gulf of Mexico in approximately 4000 ft (1219 m) of water.

Institute. The multiphase SGC research project was organized to better understand previous seabed geochemical results both published and unpublished and determine which sediment hydrocarbon (gas and liquid) extraction methods best characterize migrated near-surface sediment hydrocarbons (Abrams, 2002). The SGC Gulf of Mexico Marco Polo field calibration survey was designed to field test specific analytical procedures examined in the laboratory studies as well as several emerging and existing technologies. The Gulf of Mexico Marco Polo field was chosen because it is an area of known petroleum leakage based on previous seismic and geochemical surveys (Chaouche et al., 2004; Dembicki and Samuels, 2007), reservoir geochemical data available (Abrams and Dembicki, 2006), and highquality shallow seismic imaging data acquired (Dembicki and Samuels, 2007). The near-surface sediment geochemical methods examined in the Marco Polo field calibration survey can be subdivided into three categories: light hydrocarbon gas (C1C5), gasoline-range hy-

drocarbons (C5C10+), and high-molecular-weight (HMW) hydrocarbons (C15+). The light hydrocarbons were examined using two different sediment gas extraction methods: interstitial (conventional can headspace and modified headspace method called disrupter analysis) and adsorbed-bound (microdesorption analysis). The gasoline-range hydrocarbons were examined by two different analytical procedures, disrupter headspace solid-phase microextraction (HSPME) and Gore Module. The HMW hydrocarbons were examined using solvent extraction followed by whole-extract gas chromatography (GC) and total scanning fluorescence (TSF). The purpose of this article is to provide an overview of the Marco Polo field SGC survey results for different seepage types and to better understand how the different methods characterize the seeping hydrocarbons. This article provides guidance on best practices for seabed geochemical surveys based on both previously published laboratory experiments and the Marco Polo field calibration survey results.
Abrams and Dahdah 1909

Table 1. Core Description with Target Classification and Depth Information Seep Feature (based on seismic feature, previous survey) Outside Marco Polo minibasin Outside seep feature Outside seep feature Edge potential seepage Inside area of seepage Replicate Core 5 Previous survey oil stained Replicate Core 7 Replicate Core 7 Inside area of seepage Inside area of seepage Outside seep feature Inside area of seepageedge Previous survey oil stained with hydrate Edge potential seepage Outside seep feature Outside seep feature Near seeping fault along mud volcano On mud volcano Flank mud volcano On mud volcano Flank mud volcano Flank mud volcano Flank mud volcano Outside north edge mud volcano Outside north edge mud volcano Outside seep feature Outside seep feature Outside seep feature Outside seep feature Outside seep feature Outside seep feature Outside Marco Polo minibasin Core Length (m) 3.65 3.90 4.77 3.72 4.96 4.19 4.17 4.23 4.04 2.46 4.29 5.33 3.79 0.31 4.02 4.42 3.40 3.67 3.85 3.42 0.70 1.76 0.50 3.78 5.33 3.66 3.31 3.73 3.63 3.70 2.89 3.14 2.79 Depth Subsamples A (cm) 156 181 268 163 287 210 208 214 195 37 220 324 170 NA 193 233 131 158 176 133 NA NA NA 169 323 157 122 164 154 161 80 105 70 B (cm) 239 264 351 246 370 293 291 297 278 120 303 407 253 NA 276 316 214 241 259 216 0 60 NA 252 406 240 205 197 237 244 163 188 153 C (cm) 322 347 434 329 453 376 374 380 361 203 396 490 336 0 359 399 297 324 342 299 33 143 10 335 489 323 288 280 320 328 246 271 236

Core No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33

Target Type Regional reference Near seep zone Near seep zone Near seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Near seep zone Within seep zone Within seep zone Near seep zone Near seep zone Near seep zone Within seep zone Within seep zone Near seep zone Within seep zone Within seep zone Within seep zone Within seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Regional reference

FIELD OPERATIONS Study Area The Marco Polo field is approximately 175 mi (281 km) south of New Orleans, Louisiana, in blocks 563, 607, and 608 Green Canyon Gulf of Mexico in approximately 4000 ft (1219 m) of water (Figure 1). The Marco Polo field is located in a salt-bounded minibasin with petroleum production from supra1910

salt Miocene reservoir sands (Chaouche et al., 2004). Geochemical analysis of reservoir fluids by Anadarko Petroleum indicates that the medium-gravity oil originated from a marine type II organic matter type consistent with generation from the subsalt upper Jurassic source rocks (see Chaouche et al., 2004, for details). Areas of fluid movement from the reservoir to near surface had been identified on the western side of the field area (Green Canyon Block 607) by the presence of mud mounds (volcanoes),

Surface Sediment Hydrocarbons as Indicators of Subsurface Hydrocarbons

Figure 2. The Marco Polo calibration cruise core locations on the surface terrain map, Gulf of Mexico, Green Canyon Block 607.

pockmarks (seabed craters), shallow acoustic blanking, and bright amplitudes (Dembicki and Samuels, 2007, 2008). Core Selection and Collection Thirty-three cores were collected based on 23 targets and one location far from known seepage (Table 1). The core locations are displayed on a digital terrain map generated from high-resolution multibeam bathymetry (Dembicki and Samuels, 2007) (Figure 2). Two types of features were targeted: within seep zone, sample location within major seepage zone based on high-resolution acoustic data; and near seep zone, sample location near feature with major seepage based on high-resolution acoustic

data. A regional reference (local background reference) location was selected outside the minibasin for a baseline sample of recent sediment organic matter. More details on the core locations and targeted seismic features can be found in Dembicki and Samuels (2007, 2008). Initial positioning of the vessel was done using shipboard global positioning system to match the location of features identified with autonomous underwater vehicle (AUV) data. The onboard Chirp subbottom profiler records were then compared with the AUV subbottom profiler records to confirm the targeted feature.The core samples were collected aboard the Fugro Seis Survey using a modified Kullenberg piston coring device (trough corer trap system) with a 6-m core barrel and a
Abrams and Dahdah 1911

Table 2. Marco Polo Surface Geochemistry Calibration Can Headspace and Disrupter Interstitial Sediment Gas Data Can Headspace Core No. EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI 01 01 01 02 02 02 03 03 03 04 04 04 05 05 05 06 06 06 07 07 07 08 08 08 09 09 09 10 10 10 11 11 11 12 12 12 13 13 13 14 15 15 15 16 16 Core Section A B C A B C A B C A B C A B C A B C A B C A B C A B C A B C A B C A B C A B C C A B C A B Core Target Classification Regional reference Regional reference Regional reference Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Near seep zone Near seep zone Near seep zone Within seep zone Within seep zone Within seep zone Within seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Methane (ppm) 6 7 8 11 19 16 11 22 13 8 59 12 21 10 22 10 10 16 31 42 112 168 206 14,262 32 53 166 43,083 120,570 147,738 191 2736 79,531 407 9206 48,260 74,639 39,127 41,999 5052 106,017 187,246 64,710 7 2387 Sum Wet Gases (ppm) 1 1 2 2 4 2 1 3 2 1 2 2 3 2 1 1 1 2 3 3 5 3 9 61 3 4 4 1177 7978 6384 6 25 121 7 2421 149 224 553 123 89 1309 552 403 1 5 Wet Gas Fraction 0.14 0.10 0.18 0.14 0.16 0.12 0.11 0.10 0.13 0.12 0.03 0.12 0.11 0.17 0.05 0.11 0.08 0.10 0.08 0.06 0.04 0.02 0.04 0.00 0.07 0.06 0.02 0.03 0.06 0.04 0.03 0.01 0.00 0.02 0.21 0.00 0.00 0.01 0.00 0.02 0.01 0.00 0.01 0.10 0.00 Methane (ppm) 9 16 11 15 30 35 11 22 21 12 19 25 21 17 40 18 21 25 45 111 273 206 831 23,710 92 126 249 71,454 136,500 181,780 268 4364 202,040 179 21,398 105,618 110,879 490,720 87,892 4179 161,053 234,324 211,839 3497 223,696 Disrupter Headspace Sum Wet Gases (ppm) 2 5 4 3 6 4 3 4 4 2 3 3 4 5 2 3 4 3 2 2 6 3 14 66 2 3 4 991 3843 5212 6 27 220 5 59 205 299 4331 172 58 2176 526 1199 22 206 Wet Gas Fraction 0.17 0.23 0.27 0.18 0.16 0.09 0.22 0.16 0.14 0.12 0.14 0.11 0.17 0.23 0.06 0.15 0.15 0.10 0.05 0.02 0.02 0.02 0.02 0.00 0.02 0.02 0.01 0.01 0.03 0.03 0.02 0.01 0.00 0.03 0.00 0.00 0.00 0.01 0.00 0.01 0.01 0.00 0.01 0.01 0.00

1912

Surface Sediment Hydrocarbons as Indicators of Subsurface Hydrocarbons

Table 2. Continued Can Headspace Core No. EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI 16 17 17 17 18 18 18 19 19 19 20 20 20 21 21 22 22 23 24 24 24 25 25 25 26 26 26 27 27 27 28 28 28 29 29 29 30 30 30 31 31 31 32 32 32 Core Section C A B C A B C A B C A B C B C B C C A B C A B C A B C A B C A B C A B C A B C A B C A B C Core Target Classification Near seep zone Near seep zone Near seep zone Near seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Near seep zone Near seep zone Near seep zone Within seep zone Within seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Methane (ppm) 185 16 20 15 22 26 29 81 310 11,750 180 4125 111,873 102,222 105,464 85,849 68,002 49,834 145 193 1076 294 9800 24,673 10 13 20 19 5 46 112 480 68,185 22 56 91 7 9 13 14 17 21 25 22 37 Sum Wet Gases (ppm) 2 1 3 2 3 5 7 3 8 78 4 31 110 10,581 16,270 463 69 504 7 3 15 3 19 21 1 2 2 2 1 3 2 7 75 2 2 2 1 3 9 8 4 8 3 2 3 Wet Gas Fraction 0.01 0.04 0.14 0.11 0.12 0.16 0.19 0.03 0.02 0.01 0.02 0.01 0.00 0.09 0.13 0.01 0.00 0.01 0.04 0.01 0.01 0.01 0.00 0.00 0.12 0.15 0.07 0.10 0.22 0.06 0.01 0.01 0.00 0.08 0.03 0.02 0.14 0.25 0.40 0.35 0.18 0.28 0.10 0.07 0.07 Methane (ppm) 234,874 11 15 17 25 31 16 113 427 24,238 384 13,253 206,623 149,638 147,362 153,412 133,143 164,486 222 325 2259 381 45,563 51,987 11 10 16 6 19 22 166 968 87,801 31 88 183 70 17 11 81 12 18 8 25 19 Disrupter Headspace Sum Wet Gases (ppm) 202 2 4 4 5 5 6 3 10 116 8 58 167 7484 11,699 395 156 2163 5 8 46 7 52 48 4 4 6 3 4 4 4 17 78 2 4 4 5 4 4 8 6 9 3 3 5 Wet Gas Fraction 0.00 0.18 0.20 0.20 0.17 0.14 0.27 0.02 0.02 0.00 0.02 0.00 0.00 0.05 0.07 0.00 0.00 0.01 0.02 0.02 0.02 0.02 0.00 0.00 0.27 0.30 0.28 0.29 0.19 0.16 0.02 0.02 0.00 0.07 0.04 0.02 0.06 0.19 0.25 0.09 0.32 0.33 0.30 0.11 0.21 1913

Abrams and Dahdah

Table 2. Continued Can Headspace Core No. EGI 33 EGI 33 EGI 33 Core Section A B C Core Target Classification Regional reference Regional reference Regional reference Methane (ppm) 14 25 34 Sum Wet Gases (ppm) 2 1 1 Wet Gas Fraction 0.14 0.04 0.03 Methane (ppm) 19 13 139 Disrupter Headspace Sum Wet Gases (ppm) 6 2 5 Wet Gas Fraction 0.23 0.14 0.04

6.7-cm internal diameter. The deep-water piston corer was launched and retrieved using a rotating A-frame high-speed hydroelectric dual winch. The 33 cores range in length from 0.5 to 5.3 m (1.6 17.4 ft) with an average recovery of 3.5 m (11.5 ft) (Table 1). Three core sections were collected from each sediment core: top (0.52.0 m [1.66.6 ft]), middle (2.03.0 m [6.69.8 ft]), and bottom (3.05.0 m [9.816.4 ft]). Each core section was subdivided in the shipboard laboratory and processed using the analytical protocols provided by the participating laboratories or established in the SGC laboratory studies: a 5-cm subsection placed in Gore Module sample container with a sorber; replicate 10-cm sample splits placed in a disrupter container (500-mL plastic container with a screw on sealing cap, built-in septum, and internal blades; see Abrams and Dahdah, 2010, for

details) and a metal can for interstitial gas analysis; 3-cm sample placed in a plastic bag for microdesorption analysis; and replicate 10-cm sample splits were wrapped in aluminum foil for solvent extraction.

ANALYTICAL PROCEDURES Sediment Gas Analysis The conventional can headspace method is a nonmechanical procedure that uses high-speed shaking to release vapor-phase interstitial sediment gases into the can headspace (Bernard, 1978). A 500-mL metal can is filled with 170 mL of sediment, 160 mL of 3.5% NaCl in H2O solution, and the remaining headspace is flushed with N2 gas. The sample can

Figure 3. The three major groups for Marco Polo can headspace and disrupter light hydrocarbon data using the classification scheme from Abrams (2005); background with total gas concentrations less than 10,000 ppm and low wet gas fraction (<0.05), fractionated with total gas concentrations less than 100 ppm and elevated wet gas fraction (>0.05), anomalous with total gas concentrations greater than 10,000 ppm and wet gas fraction less than 0.1 (<10%).

1914

Surface Sediment Hydrocarbons as Indicators of Subsurface Hydrocarbons

with mud and processed water is stored frozen. The can is thawed for 24 hr before analysis, heated to 40C for 4 hr, and shaken vigorously using a conventional paint shaker. The headspace gas is collected by syringe and injected in the gas chromatograph for compositional analysis. See Bernard (1978) for more details. The disrupter sediment gas extraction method was designed as part of the SGC laboratory studies to capture interstitial gases not easily released by vigorous shaking (Abrams and Dahdah, 2010). The disrupter method uses a 165-mL sediment sample that is placed in a 500-mL disrupter chamber with 165 mL of saturated salt brine solution and remaining volume air headspace. The disrupter chamber has a fixed internal blade that breaks apart the sediment, releasing interstitial gases without crushing (Abrams and Dahdah, 2010). The disrupter with sample is frozen on the vessel, then shipped and stored frozen until analysis. The disrupter is thawed to room temperature 24 hr before analysis and shaken for 5 min using a high-speed unidirectional paint can shaker. A 0.2-mL disrupter headspace sample is collected by a syringe through the disrupter cap septum at room temperature and injected into the GC inlet. See Abrams and Dahdah (2010) for more details. The bound gases are believed to be attached to organic and/or mineral surfaces, entrapped in structured water, or entrapped in authigenic carbonate inclusions and thus require a more rigorous procedure to remove (Horvitz, 1985; Bjoroy and Ferriday, 2002; Whiticar, 2002). The microdesorption bound sediment gas extraction method (Whiticar, 2002) uses a 300- to 400-mL bulk sediment sample that has been stored frozen in a plastic bag. A fixed weight of wet sediment sample (13 g) is placed in a reaction vessel, sealed, and evacuated. A small amount of saline water is added, and the sedimentwater slurry is mixed using a vortex ultrasonic mixer. The interstitial gases are removed by vacuum. Phosphoric acid is added under reduced pressure where the sorbed gas is released to the vessel headspace. Potassium hydroxide is added before GC to reduce carbonate-generated carbon dioxide. The pressure is increased and sample aliquots of gas are collected for GC analysis. See Whiticar (2002) for details.

Gasoline-Range (C5C10+) Hydrocarbon Analysis Two methods were used in the Marco Polo field calibration survey to evaluate sediment gasolinerange hydrocarbons, the Gore Module and disrupter HSPME. The Gore method evaluates a full range of hydrocarbons from C2 to C20+ using a specially engineered hydrophobic adsorbent encased in a microporous expanded Gore Module polytetrafluoroethylene membrane (Anderson, 2006). The Gore Module is placed in a special glass container with a designated volume of sediment and analyzed via thermal desorption coupled with mass spectrometry (MS). See the W. L. Gore and Associates Web page for additional details. (www.gore.com) The HSPME headspace sample is collected after the disrupter headspace gas analysis. A 1-cm fused silica fiber coated with 100-mm-thick polydimethylsiloxane is inserted into the headspace for a 20-min extraction, then manually injected into the GC inlet for desorption. The SPME fiber is left in the GC inlet for 5 min. See Abrams et al. (2009) for details. High-Molecular-Weight Hydrocarbon Analysis A dried sediment sample is ground to a uniform size and an aliquot by weight is extracted using hexane in an automated extraction apparatus (Dionex ASE 200 Accelerated Solvent Extractor). Extracts are concentrated to a final volume of 8 mL using Zymark TurboVap II. The final extracts are submitted for hydrocarbon analysis by GC flame ionization detection (FID) and TSF. See Brooks et al. (1983) for additional information.

RESULTS AND DISCUSSION Sediment Gas Analysis Interstitial Gas Evaluation The can headspace and disrupter data are summarized in Table 2 and plotted on a total hydrocarbon gas (S C1C5) versus wet gas fraction (S C2C5/S C1C5) plot (Figure 3). Both interstitial sediment gas
Abrams and Dahdah 1915

extraction methods provide similar results. Three major groups exist for both interstitial sediment gas data sets using the classification scheme from Abrams (2005): background with total gas concentrations less than 10,000 ppm and low wet gas fraction (<0.05); fractionated with total gas concentrations less than 100 ppm and elevated wet gas fraction (>0.05); and anomalous with total gas concentrations greater than 10,000 ppm and wet gas fraction less than 0.1 (10%). The cutoffs are based on an examination of a worldwide surface geochemistry database (Abrams, 2005). Examination of the three sediment gas groups relative to the pre-survey core targets (within seep zone, near seep zone, and regional reference) reveals interesting observations. The regional reference core samples fall within the background and fractionated samples. The fractionated group was defined in Abrams (2005) to represent very low concentration samples (<100 ppm) with differential volatile loss (methane loss greater than the wet gases) that results in wet gas enrichment. This is a common feature noted in most interstitial sediment gas seabed surveys (Abrams, 2005) and SGC laboratory experiments (Abrams et al., 2009). The within-seep-zone and near-seep-zone targeted cores fall within all three groups: background, fractionated, and anomalous. Note the relatively large number of cores collected from within seep zone and near seep zone based on AUV acoustic data that contain very low total interstitial hydrocarbon gas (<10,000 ppm). Several reasons exist why near-surface sediment cores collected within a seep feature contain low levels of total interstitial sediment hydrocarbon gas. First, the core samples were collected within the transition zone known as the zone of maximum disturbance (ZMD) (Abrams, 1992). Samples collected within the ZMD may be altered by microbial processes or pore water flushing (Abrams, 1996) unless the seepage volume and rate overwhelm the alteration processes (Abrams, 2005). A plot of core sampling depth versus total disrupter headspace interstitial hydrocarbon gas indicates that the ZMD is approximately 2.0 m (6.6 ft) based on the near-seep-zone samples with elevated total gases (>10,000 ppm) relative to sample depth (Figure 4). Note that the ZMD will vary
1916

Figure 4. The plot of core sampling depth versus total disrupter headspace interstitial hydrocarbon gas indicates the zone of maximum disturbance (ZMD) is approximately 2.0 m (6.6 ft). The within-seep-zone samples have elevated total gas concentrations within and below the ZMD, whereas the near-seepzone samples have elevated total gas concentrations only below the ZMD.

for each petroleum seepage system (Abrams, 1996, 2005). The second and more fundamental issue is collecting cores within the chosen targeted feature. Sampling a relatively small target in 4000 ft (1219.2 m) of water with a gravity corer is very difficult. Many of the cores collected within the Marco Polo survey did not sample the targeted feature based on the geochemistry results. Abrams (1992) demonstrated the importance of sampling depth and hitting the target by collecting core samples from an anchored drill ship using shallow drilling technology on and off a known hydrocarbon seeping fault. The drill ship survey showed that the migrated thermogenic signal was quickly lost from deep sediment cores collected 15 to 25 m (4992 ft) away from the migration pathway (leaky fault). The Marco Polo calibration data set reinforces the

Surface Sediment Hydrocarbons as Indicators of Subsurface Hydrocarbons

Figure 5. The disrupter interstitial sediment gas composition (wet gas fraction and C1/C2 ratiomethane/ethane) is different from the Marco Polo Field reservoir gases.

Figure 6. The methane and ethane d13Cn values for disrupter extracted interstitial gases are similar to the 12,200 ft (3719 m) reservoir production gases, except propane (C3) (does not include sample 23C).

importance of good seismic data to define the seep feature and a core collection protocol with the ability to hit the targeted feature at 2+ m below the water-sediment interface. The disrupter interstitial sediment gas composition (wet gas fraction and C1/C2 ratio) and Marco Polo field reservoir gases are different (Figure 5). Similar observations were made by Abrams and Dembicki (2006). The differences between reservoir and near-surface sediment gas compositions are most likely related to near-surface affects (phase fractionation and microbial alteration) as well as mixing with shallow microbial gases. Therefore, caution should be used when interpreting near-surface

sediment gas compositions using interpretation charts designed for reservoir gases (Abrams, 2005). Compound-specific carbon isotopic analysis (methane, ethane, and propane) of selected highconcentration macroseepage (anomalous) can headspace and disrupter extracted interstitial gases provide similar results except for core number 23C (Table 3). The disrupter d13C1 for sample 23C is 9 lighter, indicating in-situ microbial gas generation. The methane and ethane d13Cn values for the disrupter-extracted interstitial gases are similar to the 12,200-ft reservoir production gases, except propane (Figure 6). The disrupter and can headspace-extracted hydrocarbon gases have propane isotopic values heavier (d13C3, 15.3 to

Table 3. Marco Polo Surface Geochemistry Calibration Interstitial Sediment Gas (Can Headspace and Disrupter) Compound-Specific Carbon and Methane Hydrogen Isotopic Data Core No. 10B 10C 21B 21C 23C Method Laboratory Disrupter Can headspace Disrupter Can headspace Disrupter Can headspace Disrupter Can headspace Disrupter Can headspace d13C1 () 56.8 55.6 54.8 52.6 56.2 53.9 55.1 54.5 64.8 55.7 d13C2 () 35.9 36.2 36.4 36.8 36.5 36.5 36.4 35.3 41.1 38.7 d13C3 () 25.8 29.2 29.3 30.4 15.3 16.3 17.0 17.0 18.6 19.4 Abrams and Dahdah dDC1 () 203 193 207 203 199 196 203 202 196 178 1917

Table 4. Marco Polo Surface Geochemistry Calibration Microdesorption Sediment Gas Data Depth Section A B C A B C A B C A B C A B C A B C A B C A B C A B C A B C A B C A B C A B C C A B C A B C A Core Target Classification Regional reference Regional Reference Regional Reference Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Near seep zone Near seep zone Near seep zone Within seep zone Within seep zone Within seep zone Within seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Total Gas (nmol/g) 253 278 303 287 309 220 248 196 388 201 218 251 240 475 272 216 240 244 263 345 418 241 257 513 274 194 430 717 772 992 384 314 768 246 807 991 863 634 771 121 545 995 640 409 757 899 89 Wet Gas Fraction 0.07 0.08 0.09 0.07 0.07 0.09 0.07 0.07 0.12 0.07 0.07 0.07 0.08 0.10 0.09 0.07 0.07 0.09 0.07 0.10 0.11 0.06 0.07 0.11 0.06 0.07 0.07 0.68 0.12 0.09 0.06 0.04 0.06 0.09 0.12 0.09 0.02 0.05 0.06 0.10 0.12 0.03 0.05 0.06 0.04 0.03 0.07 Carbon Isotopes C1 56.0 52.3 48.7 54.6 51.1 48.9 52.0 53.7 45.5 54.7 50.2 51.2 53.7 45.9 49.5 53.3 50.1 49.1 50.2 47.8 49.7 53.5 62.0 49.0 56.8 52.8 53.0 52.7 56.2 55.1 58.7 62.7 57.0 51.3 48.3 58.7 55.2 52.9 48.7 63.0 56.4 56.1 59.6 58.3 62.6 58.9 49.2 C2 32.3 32.0 33.2 32.4 31.9 32.7 32.7 32.6 34.3 32.4 32.4 32.8 32.3 34.3 33.9 33.1 32.2 33.9 32.4 34.5 34.5 32.7 31.9 34.8 32.2 32.6 32.6 29.9 33.5 33.8 32.9 33.0 34.8 32.9 34.6 35.2 33.5 33.2 34.6 31.1 34.6 35.3 34.6 32.7 35.3 36.2 32.6 C3 32.5 30.8 31.5 31.1 30.5 30.7 31.4 31.0 31.8 31.6 30.5 31.3 31.0 31.5 31.8 30.6 31.1 31.4 30.5 32.4 32.7 30.4 29.4 30.4 31.0 30.2 30.1 7.7 23.4 26.7 31.8 26.5 29.1 28.5 28.3 18.1 24.2 30.6 15.6 21.7 27.4 29.3 29.5 29.5 iC4 34.0 33.0 31.0 33.0 33.0 32.0 31.3 NC4 31.0 31.0 31.0 30.0 30.0 30.0 30.0 31.0 29.9 30.0 30.0 31.0 30.0 29.8 30.0 31.0 29.0 30.0 28.0 30.4 31.0 31.0 29.1 31.0 30.3 29.8 28.3 22.1 29.8 30.6 30.4 30.2 29.0 28.4 30.7 30.1 23.0 27.7 29.6 29.6 30.1 29.6

Sample ID EGI 01 EGI 01 EGI 01 EGI 02 EGI 02 EGI 02 EGI 03 EGI 03 EGI 03 EGI 04 EGI 04 EGI 04 EGI 05 EGI 05 EGI 05 EGI 06 EGI 06 EGI 06 EGI 07 EGI 07 EGI 07 EGI 08 EGI 08 EGI 08 EGI 09 EGI 09 EGI 09 EGI 10 EGI 10 EGI 10 EGI 11 EGI 11 EGI 11 EGI 12 EGI 12 EGI 12 EGI 13 EGI 13 EGI 13 EGI 14 EGI 15 EGI 15 EGI 15 EGI 16 EGI 16 EGI 16 EGI 17 1918

C1 (nmol/g) 236 256 277 267 286 200 232 182 342 187 203 233 221 427 247 201 223 221 243 312 372 227 240 457 258 181 400 227 678 902 362 300 725 223 706 898 847 602 727 109 479 965 609 385 730 872 83

31.2 32.0

32.0 33.0 31.0 32.2

31.6

33.0 31.5 32.4 32.3 32.2 32.0 32.8 31.5 32.1 31.8 27.8 30.0 28.3 30.7 31.9 34.1 31.6 32.2

Surface Sediment Hydrocarbons as Indicators of Subsurface Hydrocarbons

Table 4. Continued Depth Section B C A B C A B C A B C B C B C C A B C A B C A B C A B C A B C A B C A B C A B C A B C A B C Core Target Classification Near seep zone Near seep zone Within seep zone within seep zone within seep zone within seep zone within seep zone within seep zone near seep zone near seep zone Near seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Regional reference Regional reference Regional reference Total Gas (nmol/g) 312 279 311 391 325 311 316 410 287 373 844 835 1736 937 1020 234 150 227 701 233 285 759 296 305 204 91 262 283 179 252 414 256 223 213 301 244 237 77 270 206 67 338 244 74 263 249 Wet Gas Fraction 0.06 0.07 0.06 0.07 0.07 0.06 0.07 0.07 0.06 0.07 0.03 0.48 0.66 0.08 0.03 0.08 0.08 0.10 0.12 0.08 0.08 0.10 0.05 0.07 0.09 0.08 0.07 0.07 0.03 0.06 0.04 0.05 0.05 0.06 0.05 0.07 0.07 0.09 0.05 0.06 0.09 0.06 0.07 0.11 0.06 0.07 Carbon Isotopes C1 55.6 51.4 57.5 48.0 53.7 55.4 53.1 53.0 59.8 50.6 59.8 46.5 54.2 52.0 58.0 55.5 54.8 51.2 44.2 54.3 57.7 52.9 58.3 49.3 49.6 51.4 54.6 51.5 62.7 56.2 64.4 59.2 58.2 57.3 59.2 46.6 53.8 42.5 58.4 55.5 44.6 58.5 53.3 42.0 57.9 52.8 C2 33.3 33.0 32.5 32.4 33.4 32.5 33.0 33.8 32.5 31.8 33.0 33.9 34.3 37.0 35.6 33.7 34.0 33.3 34.6 33.1 33.9 35.0 32.6 32.3 32.6 32.9 32.7 32.6 31.9 33.6 34.1 32.3 33.5 32.4 32.3 32.5 32.3 31.9 33.0 32.5 31.7 33.4 32.9 31.0 32.5 31.6 C3 30.9 31.2 31.3 30.6 32.0 32.2 30.9 31.3 31.9 28.7 28.5 28.2 14.8 26.5 27.5 28.9 30.6 25.5 32.1 30.3 31.8 32.0 32.1 31.8 31.4 29.3 31.0 31.0 28.8 31.5 31.0 30.8 31.8 30.3 30.5 31.6 29.7 32.9 29.9 30.9 30.2 33.0 iC4 NC4 30.8 29.9 30.7 28.9 32.1 30.3 29.3 28.7 30.5 28.8 29.7 26.7 27.3 27.7 26.5 29.1 29.3 30.2 27.9 30.7 30.2 31.9 29.6 32.4 30.6 31.2 30.9

Sample ID EGI 17 EGI 17 EGI 18 EGI 18 EGI 18 EGI 19 EGI 19 EGI 19 EGI 20 EGI 20 EGI 20 EGI 21 EGI 21 EGI 22 EGI 22 EGI 23 EGI 24 EGI 24 EGI 24 EGI 25 EGI 25 EGI 25 EGI 26 EGI 26 EGI 26 EGI 27 EGI 27 EGI 27 EGI 28 EGI 28 EGI 28 EGI 29 EGI 29 EGI 29 EGI 30 EGI 30 EGI 30 EGI 31 EGI 31 EGI 31 EGI 32 EGI 32 EGI 32 EGI 33 EGI 33 EGI 33

C1 (nmol/g) 293 259 293 362 302 293 294 381 270 346 822 436 591 862 993 215 138 205 619 215 262 684 280 284 185 83 245 262 174 237 398 243 210 199 287 227 220 70 256 194 61 318 228 66 246 233

33.2 31.4 32.5 31.5

32.1 33.6 31.7 31.8 30.3 30.8 30.6 32.4 32.1 33.4 32.2

32.9 33.9

28.5

32.1

30.1 29.7 30.0 33.0 30.5 30.9 30.5 30.5 29.1 29.4 1919

Abrams and Dahdah

extracted sediment gases show higher gas wetness than the reservoir gases (Figure 7). The bound gases compound-specific isotopic ratios do not match the reservoir gases (Figure 8). The sediment-bound methane and ethane isotopes are as much as 7 heavier than the Marco Polo Field reservoir gases. This is not an uncommon observation for sediment-bound gases removed by acid extraction from both washed and closedvessel adsorbed-hydrocarbon analysis (Abrams and Dahdah, 2010).
Figure 7. The bound gases display different trends from the interstitial gases. No bimodal distribution and total microdesorption hydrocarbon gas displays significant variability from the low- and high-concentration samples. Most have wet gas fractions less than 0.12 (<12%) with three notable exceptions: 0.48, 0.66, and 0.68. Most display higher gas wetness than the reservoir gases.

Gasoline-Range Hydrocarbon Analysis The gasoline-range petroleum hydrocarbons comprise molecules with 5 to 12 carbon atoms (C5 C12) arranged in linear, branched, and cyclic aliphatic structures along with monoaromatic hydrocarbons, such as benzene, toluene, and o-, m-, and p-xylenes. This group of hydrocarbons is normally derived from thermogenic processes associated with a mature generating source rock unlike methane and ethane (C1 and C2) that could be derived from either thermogenic or microbial processes (Whiticar, 1999). The gasoline-range hydrocarbons are volatile and migrate within key oil migration avenues to the sediment surface and should be an

29.3) relative to the reservoir gases (d 13C 3, 27.8 to 31.1) (Table 3; Figure 6). This is most likely related to near-surface microbial alteration of propane. The preferential attack of propane was noted by James and Burns (1984) in reservoir gases, and microbial fractionation of near-surface gases is not uncommon for seabed sediment gases (Abrams, 1989). Microdesorption (Bound) Gases The microdesorption bound gas data (Table 4) are plotted on the same total hydrocarbon gas (S C1 C4) versus wet gas fraction (S C2C4/S C1C4) evaluation plot using the same core designations (Figure 7). Note that the microdesorption sediment gases are reported in nanomoles per gram by weight, whereas the disrupter headspace gas is reported in parts per million by volume. The bound gases display a very different trend than the interstitial gases. No bimodal distribution is present and total microdesorption hydrocarbon gas displays significant variability from low- and high-concentration samples (Figure 7). Most of the samples have wet gas fractions less than 0.12 (<12%), with three notable exceptions: 0.48, 0.66, and 0.68 (4868%). Most of the microdesorption
1920

Figure 8. Most Marco Polo sediment-bound gases do not match the reservoir gas isotopic values. Bound gases are up to 7 heavier than the Marco Polo Field reservoir gases.

Surface Sediment Hydrocarbons as Indicators of Subsurface Hydrocarbons

important target for most surface geochemical surveys (Abrams et al., 2009). To date, few surface geochemical surveys attempt to evaluate the gasoline-range hydrocarbons in near-surface marine sediments. Conventional headspace light hydrocarbon analysis is not an effective method to evaluate the C6 to C12 hydrocarbons because of higher boiling points and low vapor pressures relative to the hydrocarbons gases (C1C5) (Abrams and Dahdah, 2010).

Headspace Solid-Phase Microextraction The HSPME data are reported as the area sum of a single carbon number (SCN) within the main boiling point range detected using the SPME fiber. The unresolved complex mixture (UCM) is included in the area of each SCN (Abrams et al., 2009) (Table 5). A plot of the disrupter total hydrocarbon interstitial gas (S C1C5) versus HSPME SCN (Figure 9) displays moderate correlation between sediment interstitial gas and the concentration of gasoline-range hydrocarbons. The regional reference HSPME gas chromatograms contain very low overall signal responses (<10 total GC area) that are dominated by SPME fiber peaks (Figure 10A) (Abrams et al., 2009). In contrast, the high-concentration within-seep-zone HSPME gas chromatograms have an elevated overall signal response increasing with depth, significant resolvable compounds, depleted light end, and elevated baseline hump or UCM (Figure 10B). Compound distributions for the within-seepzone chromatograms are very different to an unaltered reservoir oil whole-oil chromatogram. The HSPME within-seep-zone chromatograms contain very low n-alkanes (C5, C6, C7, and C8), aromatics (benzene, toluene, and xylenes), cycloalkanes (cyclopentane and cyclohexane), and cycloalkanes with one methyl group (methyl-cyclopentane and methyl-cyclohexane) but elevated isoalkanes and cycloalkanes with more than one methyl group. This unique compound distribution is commonly found in biodegraded oils (George et al., 2002), indicating that the macroseepage seabed gasolinerange hydrocarbons are rapidly and heavily altered (Abrams et al., 2009).

Gore Module The Gore Module examines as much as 150 volatile compounds using cluster analysis and linear discriminate classification for defining petroleum and background character end members (Anderson, 2006). Three end-member groupings were defined by the Gore statistical evaluation: high aliphatic, medium aliphatic, and background (Table 5; Figure 11AC). The Gore high aliphatic group contains the higher concentration (based on headspace gas and HSPME data) within-seep-zone samples, with two exceptions (Table 5). The key compounds that characterize this end member group include 2-methylbutane, 3-methylpentane, methylcyclohexane, cyclohexane, 1-octene, cyclopentane, c1314 dimethylcyclohexane, and ethylcyclohexane (Figure 11A). The Gore medium aliphatic group contains a mix of the within-seep-zone and near-seep-zone samples (Table 5). The key compounds that characterize this end member group include carbon disulfide, 2,4-dimethylpentane, 2,5-dimethylhexane, pristane, ethane, and cyclooctane (Figure 11B). The Gore background group contains the regional reference samples as well as the lowconcentration within-seep-zone and near-seep-zone samples (Table 5). The key compounds that characterize this end member group include carbon disulfide, propene, ethane, octanal, decanal, propane, 1-butene, butane, and tetradecane (Figure 11C). A plot of Gore Module total reported hydrocarbons versus total disrupter HSPME SCN indicates that both gasoline-range sediment extraction methods provide similar results (Figure 12). Both methods provide strong gasoline-range signals within the interstitial sediment gas high-concentration within-seep-zone and near-seep-zone samples and minimal signal in the regional reference and interstitial sediment gas low-concentration within-seepzone and near-seep-zone targeted cores. The Gore Module thermal desorption MS analysis provides greater compound specific information than could be achieved with the HSPME GC-FID approach. This could prove to be important to characterize seep origin (source facies, level of maturity, and/or seep to oil correlation). In addition, the desorption
Abrams and Dahdah 1921

Table 5. Marco Polo Surface Geochemistry Calibration Headspace Solid-Phase Microextraction and Gore Module Gasoline Plus Data with Statistical Grouping Classifications Core No. EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI 01 01 01 02 02 02 03 03 03 04 04 04 05 05 05 06 06 06 07 07 07 08 08 08 09 09 09 10 10 10 11 11 11 12 12 12 13 13 13 14 15 15 15 16 16 16 Core Section A B C A B C A B C A B C A B C A B C A B C A B C A B C A B C A B C A B C A B C C A B C A B C Core Target Classification Regional reference Regional reference Regional reference Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Near seep zone Near seep zone Near seep zone Within seep zone Within seep zone Within seep zone Within seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Core Depth 156 239 322 181 264 347 268 351 434 163 246 329 287 370 453 210 293 376 208 291 374 214 287 380 194 278 361 37 120 203 220 303 396 324 407 490 170 253 336 10 193 276 359 233 316 399 Gore Grouping Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Medium Aliphatic Background Background Background High aliphatic High aliphatic High aliphatic Medium Aliphatic Background Medium aliphatic Background Background Medium aliphatic High aliphatic High aliphatic High aliphatic Medium aliphatic High aliphatic High aliphatic High aliphatic Background Medium aliphatic Medium aliphatic Total Gore Hydrocarbons 142 303 243 131 174 148 131 205 216 146 159 370 214 278 134 173 193 160 129 134 185 124 179 1558 150 154 155 6212 132,986 153,739 443 331 1106 159 202 856 24,625 59,660 47,206 516 34,715 42,592 23,301 150 1390 517 Total Disrupter C1C5 15 21 11 18 36 39 14 26 25 14 22 28 26 22 42 21 25 28 48 113 279 209 845 23,775 94 129 253 72,445 140,343 186,992 274 4391 202,259 184 21,456 105,824 111,178 495,051 88,064 4237 163,229 234,851 213,038 3519 223,903 235,076 Total SPME SCNUCM 158 181 76 493 129 189 70 299 175 119 73 154 82 271 153 86 74 163 252 146 119 83 1467 2334 178 188 171 4588 4859 34,294 116 547 2426 92 116 151 9948 9155 6387 1807 9502 12,214 16,784 510 921 508

1922

Surface Sediment Hydrocarbons as Indicators of Subsurface Hydrocarbons

Table 5. Continued Core No. EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI 17 17 17 18 18 18 19 19 19 20 20 20 21 21 22 22 23 24 24 24 25 25 25 26 26 26 27 27 27 28 28 28 29 29 29 30 30 30 31 31 31 32 32 32 33 33 33 Core Section A B C A B C A B C A B C B C B C C A B C A B C A B C A B C A B C A B C A B C A B C A B C A B C Core Target Classification Near seep zone Near seep zone Near seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Near seep zone Near seep zone Near seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Regional reference Regional reference Regional reference Core Depth 131 214 297 158 241 324 176 259 342 133 216 299 10 33 60 143 10 169 252 335 323 406 489 157 240 323 122 205 288 164 197 280 154 237 320 161 244 328 80 163 246 105 188 271 70 153 236 Gore Grouping Background Background Background Background Background Background Background Background Medium aliphatic Medium aliphatic Background High aliphatic High aliphatic High aliphatic High aliphatic High aliphatic High aliphatic Background Background Background Background Background Medium aliphatic Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Background Total Gore Hydrocarbons 133 318 215 244 201 256 145 111 1757 2332 115 882 19,134 226,976 26,428 6983 79,866 147 247 277 124 201 482 269 291 200 206 116 175 102 210 281 130 120 112 184 193 144 255 351 313 151 162 235 195 180 246 Total Disrupter C1C5 13 18 22 29 36 22 116 437 24,355 392 13,312 206,790 157,122 159,061 153,807 133,299 166,649 227 333 2305 389 45,616 52,034 15 15 22 9 9 26 170 985 87,879 34 92 187 75 21 15 88 18 27 12 28 24 15 25 144 Abrams and Dahdah Total SPME SCNUCM 97 153 107 124 100 97 145 105 13,076 235 179 1875 14,087 21,952 11,747 6689 16,515 215 177 342 188 126 165 152 263 107 105 105 82 147 235 689 143 64 74 136 86 264 102 142 111 158 97 290 148 102 131 1923

Figure 9. The headspace solid-phase microextraction (HSPME) data reported as sum of single carbon number (SCN) within the detection range of SPME fiber. The unresolved complex mixture is included in the area of each SCN. A plot of disrupter total hydrocarbon interstitial gas (S C1C5) versus HSPME SCN displays a moderate correlation between sediment interstitial gas and concentration of gasoline-range hydrocarbons with notable exceptions.

MS analysis can detect much lower concentrations than other seabed geochemical analysis methods. However, it could not discriminate the lowconcentration within-seep-zone and near-seep-zone samples any better than the disrupter headspace gas or HSPME gasoline-range analysis. The 8, 11, 16, 19, and 25 within-seep-zone and near-seep-zone core shallow subsamples were classified by Gore in the background group, whereas the deeper subsamples fall in the medium aliphatic group. This observation reinforces the importance of sampling depth and placing the corer directly on the targeted feature.

High-Molecular-Weight Hydrocarbon Analysis Extract GC: The sediment extract GC evaluation includes the chromatogram signature, total UCM, and total n-alkanes. Table 6 contains extract GC total UCM and total n-alkanes for the Marco Polo calibration samples. Samples with UCM values less than 25 mg/g are considered to be background, whereas samples with UCM greater than 100 mg/g
1924

are associated with migrated hydrocarbon seepage (Cole et al., 2001; Abrams, 2005). Six of the 15 cores collected at the within-seep-zone targets did not have elevated UCM (>100 mg/g), indicating that the samples may not have hit the targeted feature (Table 6). One near-seep-zone sample contains elevated UCM (Table 6). Sediments containing migrated thermogenic HMW hydrocarbons typically have GC-FID chromatograms characterized by a large unresolved complex mixture (UCM) with some discernible C15 C32 n-alkanes and isoprenoids peaks, depending on the severity of microbial alteration (Figure 13A) (Brooks and Carey, 1986). All but one of the withinseep-zone samples have extremely high UCM values (>1000 mg/g) and a sum of total alkanes less than 1. This is a common observation with sediment extract chromatograms and is related to the severe near-surface bacterial alteration that has destroyed most of the resolvable normal alkane compounds very quickly. Sediments containing mainly the recent organic matter (ROM) signature with some migrated thermogenic signal will contain lower UCM and overprint of odd n-alkanes greater than C23 (Figure 13B) (Brooks and Carey, 1986). Extract TSF: The sediment extract TSF evaluation includes examination of the fluorogram signature and maximum fluorescence intensity (MFI). Samples with significant seepage require dilution before TSF analysis. The MFI values are adjusted by multiplying the measured MFI by the dilution factor to obtain a corrected MFI (Brooks et al., 1983). The extract TSF MFI ranges from 30,140 to 73,260,000 MFI units (Table 6) for the SGC phase III GOM calibration samples. Most of the samples collected in the within-seep-zone targets contain highextract TSF MFI values (100,000 MFI units) (Cole et al., 2001; Abrams, 2005). Several near-seep-zone samples as well as one shallow regional-reference sample also have extract TSF MFI greater than 100,000 units. An extract GC total UCM versus TSF MFI plot demonstrates a relatively strong correlation between the two HMW screening tools (Figure 14), but examination of the TSF fluorogram signatures indicate a potential problem with the extract TSF

Surface Sediment Hydrocarbons as Indicators of Subsurface Hydrocarbons

method (Figure 15). The fluorogram signatures for a regional-reference sample with low-interstitial sediment gas, UCM, and TSF MFI; and within-seepzone sample with highly elevated interstitial sediment gas, UCM, and TSF MFI should have very different shapes and locations of the maximum excitation wavelength (MFI Max Ex) and maximum emission wavelength (MFI Max EM), yet they are similar (Figure 15A, B). This indicates that the fluorogram shape, MFI Max Ex, and MFI Max EM may not assist in the identification of thermogenic seepage in marine sediments.

KEY OBSERVATIONS Sediment Gases The can headspace and disrupter extraction methods provide similar interstitial sediment gas data, indicating that the disrupter plastic container with screw cap and sealing gasket, built-in septum, and blades to break up the sediment did not provide significantly better results than the conventional can headspace method. Both methods provide highly variable gas compositions compared with the Marco Polo reservoir gases. Very few of the high-concentration within-seep-zone samples have sediment gas compositions similar to the Marco Polo reservoir gases. In contrast, the can headspace and disrupter interstitial sediment gas compoundspecific isotopes are similar to the Marco Polo reservoir gases, except for the propane carbon isotope value. The propane isotopic values are much heavier most likely because of preferential microbial alteration (James and Burns, 1984; Abrams, 1989, 2005). The bound gas extraction method did not provide gas compositions or compoundspecific isotopes similar to the Marco Polo reservoir gases. This could be related to the bound gas removal process, which may fractionate the sediment gas sample (Abrams and Dahdah, 2010). Proper identification of anomalous versus background interstitial (free) sediment gas is required to separate background samples that may seem to be thermogenic because of phase fractionation. Phase fractionation (preferential loss of methane relative

to ethane plus gases) results in background lowconcentration sediment gases having elevated wet gas fractions. The fractionated samples are commonly confused with migrated thermogenic hydrocarbons (Abrams, 2005) because of the higher relative wet gas component. Only the high-concentration samples are likely to be derived from migrated thermogenic gas. Compound-specific isotopic measurements are critical to confirm the thermogenic origin, assuming that isotopically distinctive changes are present. Many samples collected at within-seep-zone or near-seep-zone targets identified by conventional and high-resolution surface seismic data have only low concentrations (background) of interstitial gas. We believe that these samples did not hit the intended target or were collected within the ZMD.

Gasoline-Range Sediment Hydrocarbons Both the HSPME and Gore Module extraction methods provide strong gasoline-range seepage signals for the high-concentration within-seep-zone and near-seep-zone samples and minimal to no signal in the regional reference and low-concentration within-seep-zone and near-seep-zone samples. The Gore Module thermal extraction combined with MS provides much greater compositional detail than the HSPME GC-FID method. The HSPME chromatograms show evidence for significant near-surface microbial alteration. The lack of an unaltered oil, even in zones of high flux macroseepage, leads us to believe that the rate of alteration is rapid. It is our belief that despite microbial alteration, gasoline-range hydrocarbons provide key information for a boiling point range not examined in most offshore surveys, and this type of data is very important to help identify subsurface hydrocarbon generation (Abrams et al., 2009). High-Molecular-Weight Sediment Hydrocarbons The within-seep-zone samples with elevated HMW hydrocarbons (macroseepage) have extremely high UCM values and a distinctive GC signature. The regional reference samples have much lower UCM
Abrams and Dahdah 1925

Figure 10. (A) The headspace solid-phase microextraction (HSPME) data for regional reference core. (B) The HSPME data for the within-seep-zone core.

with a different and distinctive GC signature. When concentrations of migrated HMW hydrocarbon are low relative to the in-situ ROM material, the identification of migrated thermogenic hydrocarbons is difficult. Reworked or transported hydro1926

carbons can be confused with locally migrated hydrocarbons (Abrams, 2005). Reworking and transported hydrocarbons have been identified within the Marco Polo Green Canyon area (Cole et al., 2001; Dembicki, 2010).

Surface Sediment Hydrocarbons as Indicators of Subsurface Hydrocarbons

Figure 10. Continued.

The Marco Polo extract TSF data indicate that MFI measurements provide information on the presence of anomalous hydrocarbons, but TSF fluorogram shapes do not change with target type or other geochemical measurements (interstitial

gas, gasoline-range hydrocarbons, or extract UCM). Edwards and Crawford (1999) demonstrated that a linear relationship between oil concentration and total fluorescence intensity can only be obtained between 0.10 and 10 ppm oil. Within this range,
Abrams and Dahdah 1927

Figure 11. Three end-member groupings defined by the Gore Module data for the Marco Polo calibration data set: (AC) high aliphatic, medium aliphatic, and background.

fluorescence intensity is proportional to concentration, but outside this range, TSF fluorescence intensity (MFI) and shape can vary because of the dilution factor (hydrocarbon concentration). Other factors that affect TSF fluorescence intensity (MFI) and shape include absorbance (compounds in ex1928

tract that can absorb either excitation or emitted light), quenching (energy can be transferred nonradiatively to coexisting molecules instead of being emitted as fluorescence), and secondary alteration (water washing, biodegradation, evaporative fractionation, and weathering).

Surface Sediment Hydrocarbons as Indicators of Subsurface Hydrocarbons

Figure 11. Continued.

CONCLUSIONS The Marco Polo SGC and previous SGC laboratory studies provide a strong empirical data set to evaluate surface geochemical methods used by industry for marine surface geochemical surveys. The Marco Polo SGC calibration data set demonstrates the importance of targeted coring and sampling depth. To improve the detection of seabed migrated thermogenic hydrocarbon seepage, core samples should be collected along major migration pathways (cross-stratal leakage features) identified by conventional deep seismic and highresolution sea floor imaging technology. Not all targeted cores will hit the designated feature, and thus, collecting replicates along key migration features is recommended. Collecting sediment samples below the ZMD is also important to reduce the transition zone alteration interference.

Figure 12. A plot of the Gore Module total reported hydrocarbons versus total disrupter headspace solid-phase microextraction (HSPME) single carbon number (SCN) indicates that both gasolinerange sediment extraction methods provide similar results: strong gasoline-range signals within the interstitial sediment gas highconcentration within-seep-zone and near-seep-zone samples and minimal signal in the regional reference and interstitial sediment gas low-concentration within-seep-zone and near-seep-zone targeted cores. Abrams and Dahdah 1929

Table 6. Marco Polo Surface Geochemistry Calibration Extract Gas Chromatography and Total Scanning Fluorescence Data Extract GC Core ID EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI 01 01 01 02 02 02 03 03 03 04 04 04 05 05 05 06 06 06 07 07 07 08 08 08 09 09 09 10 10 10 11 11 11 12 12 12 13 13 13 14 15 15 15 16 16 16 17 Depth (cm) 156 239 322 181 264 347 268 351 434 163 246 329 287 370 453 210 293 376 208 291 374 214 287 380 194 278 361 37 120 203 220 303 396 324 407 490 170 253 336 10 193 276 359 233 316 399 131 Core Target Regional reference Regional reference Regional reference Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Near seep zone Near seep zone Near seep zone Within seep zone Within seep zone Within seep zone Within seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone nAlkanes 875 486 1841 1414 1209 1618 1037 1562 3044 1110 1233 1255 881 1953 1071 1120 833 2259 1216 996 2034 1260 0 0 1026 1269 1236 0 0 1508 0 0 2302 989 3869 2880 0 0 0 0 0 0 0 1098 935 1793 696 UCM (mg/g) 11 6 12 19 9 11 10 18 19 17 32 9 8 12 10 9 8 12 10 8 14 16 6359 3971 16 13 81 664 1070 20 322 941 63 17 26 17 2497 1130 224 3700 3660 3393 5254 20 10 19 16 UCM > n-C23 (mg/g) 7 5 8 16 8 9 9 16 13 13 21 7 6 8 8 7 6 9 8 7 11 12 4876 2815 11 9 55 399 598 15 264 469 28 14 22 14 1648 712 126 2456 2344 2265 3400 14 8 12 12 Extract TSF MFI 60,920 51,430 56,480 89,960 43,670 34,140 94,720 30,215 68,370 57,310 57,770 49,170 26,205 127,420 54,600 54,440 46,760 107,660 47,810 51,410 119,600 53,760 42,712,000 26,892,000 55,900 50,920 716,400 4,288,000 6,926,000 4,558,000 90,100 2,171,500 563,000 49,420 230,600 201,650 20,516,000 7,032,000 2,382,000 36,080,000 27,768,000 27,560,000 46,752,000 57,700 71,900 121,320 195,600

1930

Surface Sediment Hydrocarbons as Indicators of Subsurface Hydrocarbons

Table 6. Continued Extract GC Core ID EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI EGI 17 17 18 18 18 19 19 19 20 20 20 21 21 22 22 23 24 24 24 25 25 25 26 26 26 27 27 27 28 28 28 29 29 29 30 30 30 31 31 31 32 32 32 33 33 33 Depth (cm) 214 297 158 241 324 176 259 342 133 216 299 10 33 60 143 10 169 252 335 323 406 489 157 240 323 122 205 288 164 197 280 154 237 320 161 244 328 80 163 246 105 188 271 70 153 236 Core Target Near seep zone Near seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Near seep zone Near seep zone Near seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Within seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Near seep zone Regional reference Regional reference Regional reference nAlkanes 1194 988 1314 1293 979 1419 1661 3375 1364 2213 1240 0 0 54,864 0 0 1425 2048 3008 1382 2621 3720 1370 1397 827 958 1553 1133 1096 1140 1016 1243 1245 1157 1385 1446 1016 460 1211 1408 436 1367 1607 424 1467 1101 UCM (mg/g) 15 12 18 16 7 22 115 207 19 258 13 3537 7423 6754 2678 1983 11 10 32 15 12 27 24 13 6 19 16 11 14 16 9 19 15 12 24 15 10 8 17 11 9 20 13 18 22 14 UCM > n-C23 (mg/g) 10 9 13 14 7 17 100 139 14 228 10 3016 4789 4452 1745 1523 9 8 18 14 10 23 18 11 4 14 13 9 9 14 7 13 13 9 16 11 8 7 11 9 8 14 10 15 16 11 Abrams and Dahdah Extract TSF MFI 99,680 76,980 78,780 249,300 22,530 98,420 1,147,600 2,335,000 63,100 2,759,500 24,380 35,512,000 73,260,000 67,845,000 22,896,000 18,772,000 78,700 98,360 122,820 76,370 15,965 368,800 72,980 39,515 53,680 118,260 85,520 77,400 66,580 150,510 74,580 117,300 57,530 82,760 84,160 60,170 34,250 58,780 58,970 26,695 30,040 32,670 54,070 269,800 84,220 65,470 1931

Figure 13. The Marco Polo Surface Geochemistry Calibration (SGC) extract gas chromatograms. (A) Upper: within seep zone. (B) Lower: regional reference.

Geochemical analysis should include a full range of hydrocarbon types; light hydrocarbon gases (C1 C5), gasoline range (C5C10+), and HMW hydrocarbons (C15+).
1932

The two interstitial sediment gas extraction methods, can headspace and disrupter, provide similar results in both laboratory (Abrams and Dahdah, 2010) and field calibration studies. The

Surface Sediment Hydrocarbons as Indicators of Subsurface Hydrocarbons

interstitial sediment gas data should be plotted on a total hydrocarbon gas (S C1C5) versus wet gas fraction (S C2C5/S C1C5) chart to identify background, fractionated, and anomalous populations (Abrams, 2005). The Marco Polo survey anomalous interstitial sediment gases have variable gas compositions compared with the reservoir gases, thus, caution should be used when plotting seabed gases on conventional gas interpretation charts. The methane and ethane stable carbon isotopes from selected anomalous samples are similar to the Marco Polo reservoir gases. However, propane isotope values are much heavier, indicating that propane is more easily modified by in-situ microbial alteration. The microdesorption bound gases have gas compositions and compound-specific isotopes unlike the Marco Polo reservoir gases. The microdesorption sediment gases tend to have more wet gas fraction and highly variable methane carbon isotopes with heavier ethane carbon isotopes. The SGC laboratory studies indicate that prewashing to remove interstitial gases can have a major impact on bound gas results (Abrams and Dahdah, 2010). We do not recommend using bound gas extraction methods to evaluate subsurface hydrocarbons based on the Marco Polo and previous laboratory calibration studies reported in Abrams and Dahdah (2010).

Figure 15. Fluorogram signatures for regional reference sample with low interstitial sediment gas, unresolved complex mixture (UCM), and total scanning fluorescence (TSF) maximum fluorescence intensity (MFI); and within-seep-zone sample with highly elevated interstitial sediment gas, UCM, and TSF MFI should not have similar shapes and locations of maximum excitation wavelength (MFI Max Ex) and maximum emission wavelength (Max EM). (A) Regional reference target EGI-1 (322 cm [127 in.]): MFI = 56,480 and DIL 1:10. (B) Within-seep-zone target EGI-22 (60 cm [24 in.]): MFI = 67,845,000 and DIL 1:4000.

Figure 14. The extract gas chromatography (GC) total unresolved complex mixture (UCM) versus total scanning fluorescence (TSF) maximum fluorescence intensity (MFI) plot demonstrates relatively strong correlation between two high-molecular-weight screening tools for Marco Polo extract GC and TSF data.

The gasoline-range analysis provides a new range of hydrocarbons rarely examined in surface geochemical studies. Both the HSPME and Gore Module methods used in the Marco Polo calibration studies provide strong gasoline-range seep signals having useful information in the macroseepage (high-flux) and microseepage (low-flux) seep sites. The Gore Module thermal extraction combined with MS provides more compositional detail than the HSPME GC-FID method, which may be helpful to evaluate the seep hydrocarbon source and maturity. Extraction GC and TSF analyses provide information on the presence of HMW hydrocarbons in the Marco Polo calibration survey. The GC chromatogram signature and total UCM tracked the migrated thermogenic hydrocarbon macroseepage but did not work as well with the low-level
Abrams and Dahdah 1933

microseepage samples. The TSF MFI data also directionally tracked migrated thermogenic hydrocarbon macroseepage and microseepage samples, but the fluorogram shape could not distinguish within-seep-zone and regional reference samples. We do not recommend extraction TSF to evaluate migrated HMW hydrocarbons in near-surface marine sediment seep surveys based on the above results. Follow-up studies by Dembicki (2010) with Anadarko examined extract saturate and aromatic fraction GC-MS to evaluate biomarker signature variability. Results of Dembicki (2010) demonstrate the importance of biomarker data to assist in detecting and interpreting low-concentration petroleum seepage (microseepage). Biomarker data provide a means to characterize the ROM contribution and in turn allow for the identification of thermogenic hydrocarbons when the seep oil concentration is low relative to ROM. The above conclusions are based on the Marco Polo calibration study as well as previous laboratory calibration studies (Abrams et al., 2009; Logan et al., 2009; Abrams and Dahdah, 2010). They provide a framework to better understand how best to collect and extract migrated hydrocarbons from shallow-marine sediments and evaluate the results. However, it is also very important to integrate sediment hydrocarbon results with basin geology to fully understand how surface geochemistry observations relate to subsurface generation and potential entrapment (Abrams, 2005). A fully integrated evaluation provides the best petroleum systems interpretation model.

REFERENCES CITED
Abrams, M. A., 1989, Interpretation of surface methane carbon isotopes extracted from surficial marine sediments for detection of subsurface hydrocarbons: Association Petroleum Geochemical Explorationist Bulletin, v. 5, p. 139166. Abrams, M. A., 1992, Geophysical and geochemical evidence for subsurface hydrocarbon leakage in the Bering Sea, Alaska: Marine and Petroleum Geology Bulletin, v. 9, p. 208221, doi:10.1016/0264-8172(92)90092-S. Abrams, M. A., 1996, Distribution of subsurface hydrocarbon seepage in near-surface marine sediments, in D.

Schumacher and M. A. Abrams, eds., Hydrocarbon migration and its near-surface effects: AAPG Memoir 66, p. 114. Abrams, M. A., 2002, Surface geochemical calibration research study: An example of research partnership between academia and industry (abs.), in New insights into petroleum geoscience research through collaboration between industry and academia, abstract volume: Geological Society (London). Abrams, M. A., 2005, Significance of hydrocarbon seepage relative to subsurface petroleum generation and entrapment: Marine and Petroleum Geology Bulletin, v. 22, no. 4, p. 457478, doi:10.1016/j.marpetgeo.2004.08.003. Abrams, M. A., and N. Dahdah, 2010, Surface sediment gases as indicators of subsurface hydrocarbons: Examining the record in laboratory and field studies: Marine and Petroleum Geology, v. 27, p. 273284, doi:10.1016/j .marpetgeo.2009.08.005. Abrams, M. A., and H. Dembicki, 2006, Variation in seabed geochemical signature relative to reservoir hydrocarbons (abs.): AAPG Search and Discovery article, http://www .searchanddiscovery.net/documents/2006/06088houston _abs/abstracts/abrams.htm (accessed July 7, 2011). Abrams, M. A., M. P. Segall, and S. G. Burtell, 2001, Best practices for detecting, identifying, and characterizing near-surface migration of hydrocarbons within marine sediments: Proceedings of the Offshore Technology Conference, Houston, Texas, OTC Paper 13039, 14 p. Abrams, M. A., N. Dahdah, and E. Francu, 2009, Development of methods to collect and analyze gasoline plus range (C5 to C12) hydrocarbons from seabed sediments as indicators of subsurface hydrocarbon generation and entrapment: Applied Geochemistry, v. 24, p. 19511970, doi:10.1016/j.apgeochem.2009.07.009. Anderson, H. S., 2006, Amplified geochemical imaging: An enhanced view to optimize outcomes: European Association of Geoscientists and Engineers First Break, v. 24, p. 7781. Bernard, B. D., 1978, Light hydrocarbons in marine sediments: Ph.D. thesis, Texas A&M University, College Station, Texas, 144 p. Bjoroy, M., and I. Ferriday, 2002, Surface geochemistry as an exploration tool: A comparison of results using different analytical techniques (abs.): AAPG Hedberg Conference, Vancouver, British Columbia, Canada, 2 p. Brooks, J. M., and B. D. Carey, 1986, Offshore surface geochemical exploration: Oil & Gas Journal, v. 84, p. 6672. Brooks, J. M., M. C. Kennicutt II, L. A. Bernard, G. J. Genoux, and B. D. Carey, 1983, Applications of total scanning fluorescence to exploration geochemistry: Proceedings of the Offshore Technology Conference, Houston, Texas, May 25, 1983, OTC Paper 4624, p. 393400 Chaouche, A., P. Gamwell, and J. Brooks, 2004, Surface geochemical evaluation of Green Canyon Block 608, Gulf of Mexico: A comparison of sea floor seeps and reservoir fluids (abs.): AAPG Annual Meeting, Dallas, Texas, April 1820, 2004. Cole, G., R. Requejo, J. DeVay, A. Yu, F. Peel, C. H. Taylor, J. Brooks, B. Bernard, J. Zumberge, and S. Brown, 2001, The deep-water GOM petroleum system: Insights from

1934

Surface Sediment Hydrocarbons as Indicators of Subsurface Hydrocarbons

piston coring, defining seepage, anomalies, and background: 21st Annual GCS-SEPM Research Conference, p. 315342. Dembicki, H., 2010, Recognizing and compensating for interference from recent organic matter and biodegradation during interpretation of biomarker data from sea floor hydrocarbon seeps: An example from the Marco Polo area seeps, Gulf of Mexico: Marine and Petroleum Geology, v. 27, p. 19361951, doi:10.1016/j.marpetgeo .2010.06.009. Dembicki Jr., H., and B. M. Samuels, 2007, Identification, characterization, and groundtruthing of deep-water thermogenic hydrocarbon macroseepage utilizing highresolution AUV geophysical data, Offshore Technology Conference, Houston, Texas, April 30 to May 3, 2007. OTC Paper 18556, 11 p. Dembicki Jr., H., and B. M. Samuels, 2008, Improving the detection and analysis of seafloor macro-seeps: An example from the Marco Polo Field, Gulf of Mexico: International Petroleum Research Conference, Kuala Lumpur, Malaysia, December 35, 2008, IPTC Paper 12124. Edwards, D., and N. Crawford, 1999, UVF fluorimetry: Australian Geological Survey Organization Research Report. George, S., C. J. Boreham, S. A. Minifie, and S. C. Teerman,

2002, The effect of minor to moderate biodegradation on C5 to C9 hydrocarbons in crude oils: Organic Geochemistry, v. 33, p. 12931317, doi:10.1016/S0146-6380 (02)00117-1. Horvitz, L., 1985, Geochemical exploration for petroleum: Science, v. 229, p. 812827. James, A. T., and B. J. Burns, 1984, Microbial alteration of subsurface natural gases accumulations: AAPG Bulletin, v. 68, p. 957960. Logan, G. A., M. A. Abrams, N. Dahdah, and E. Grosjean, 2009, Examining laboratory methods for evaluating migrated high-molecular-weight hydrocarbons in marine sediments as indicators of subsurface hydrocarbon generation and entrapment: Organic Geochemistry, v. 40, p. 365375, doi:10.1016/j.orggeochem.2008.11.009. Whiticar, M. J., 1999, Carbon and hydrogen isotope systematics of bacterial formation and oxidation of methane: Chemical Geology, v. 161, p. 291314, doi:10.1016 /S0009-2541(99)00092-3. Whiticar, M. J., 2002, Characterization and application of sorbed gas by microdesorption CF-IRMS: Near-surface hydrocarbon migration: Mechanisms and seepage rates: AAPG Hedberg Conference, Vancouver, British Columbia, Canada, April 710, 2002.

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