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PERFORMANCE-BASED WORK STATEMENT
I. GENERAL INFORMATION
A.
Introduction: Work will involve chemical analyses of sediments to identify polycyclic aromatic hydrocarbons, total petroleum hydrocarbons, and metals.
B. Background: The 2010 Deepwater Horizon (DWH) oil spill was an unprecedented event. Approximately 3.2 million barrels of oil were released into the deep ocean over nearly three months. The plume of oil moved throughout the water column, formed surface slicks that cumulatively covered an area the size of Virginia, and washed oil onto at least 1,300 miles of shoreline habitats. More than 770 square miles of deep benthic habitat surrounding the Deepwater Horizon wellhead and four-square miles of the Pinnacles mesophotic reef complex, located at the edge of the continental shelf, were injured by the oil spill.
As part of the deep benthic habitats, sediment environments were impacted by the DWH oil spill, with an estimated 4-31% of oil remaining trapped in the deep sea. The footprint of the DWH spill on soft-sediment communities in the norther Gulf of Mexico (GOM) estimated 263 km2 were affected by the spill, with macrofaunal abundance and diversity patterns driven by total hydrocarbons, PAHs, and barium concentrations. Severe impacts were found in an area of 58 km2 that also included reduced diversity and abundances of macrofauna. Similar to soft-sediment habitats, near-coral associated macrofauna communities were impacted, with high variance of density, diversity, and community structure associated with elevated hydrocarbon concentrations. Meiofaunal communities were also impacted by the DWH spill, with high densities and nematode: copepod ratios but low diversity a function of sediment TPH, PAH, and barium concentrations.
Recovery of deep sediment communities have been estimated to take decades or longer and documenting this recovery will be important for understanding the response of deep habitats to disturbance events like the DWH oil spill. Examining the sediment communities in soft-sediment and coral-associated habitats (work conducted at USGS WARC) combined with detailed geochemical analyses including hydrocarbons and trace metals (scope defined below) will allow for documentation of important baseline information to inform recovery trajectories. They will also improve our understanding of the spatial distribution of communities across the northern GOM and the influence of both natural and anthropogenic influences and changes.
C.
Definitions/Applicable Documents:
Reuscher MG, Baguley JG, Montagna PA (2020) The expanded footprint of the Deepwater
Horizon oil spill in the Gulf of Mexico deep-sea benthos. PLoS ONE 15(6): e0235167. https://doi.org/10.1371/journal.pone.0235167 Demopoulos, A. W., Bourque, J. R., Cordes, E., & Stamler, K. M. (2016). Impacts of the Deepwater Horizon oil spill on deep-sea coral-associated sediment communities. Marine Ecology Progress Series, 561, 51-68.
ANALYTICAL QUALITY ASSURANCE PLAN MISSISSIPPI CANYON 252 (DEEPWATER HORIZON) NATURAL RESOURCE DAMAGE ASSESSMENT Version 4.0 Prepared for:
U.S. Department of Commerce National Oceanic and Atmospheric Administration, https://pub-data.diver.orr.noaa.gov/field-files/MC%20252%20Analytical%20QAP%20V4%200%20FINAL.pdf D.
Scope:
The USGS, NOAA, and partners must determine current baseline information on sediment communities and their geochemical environment to inform the Mesophotic and Deep Benthic Communities Habitat Assessment and Evaluation project as part of the Natural Resource Damage Assessment Open Ocean TIG. Analysis of sediment hydrocarbons, including total hydrocarbons and PAHs, and trace metals are a major factor in determining the long-term impacts from the DWH oil spill and critical to understanding overall recovery trajectories. Our objectives are to:
(1) Quantitatively assess deep GOM sediments for total hydrocarbons, PAHs, and metals
These results will be used to quantitatively assess deep GOM sediments for macrofauna, meiofauna, and microbial communities; assess sediment communities in relation to sediment geochemistry parameters; and compare new results with previous studies to determine the status and recovery trajectory of deep GOM sediment communities.
II. WORK REQUIREMENTS
A.
Technical Requirements.
1.
Specific work requirements and/or work products
a. Hydrocarbons analyses, including PAHs, saturated hydrocarbon and total extractable hydrocarbons. Sediment samples have been collected by USGS and will be shipped to the contractor.
i. PAHs including alkyl homologues by gas chromatography with low resolution mass spectrometry using selected ion monitoring (GC/MS-SIM). The analytical procedure is based on EPA Method 8270D with the GC and MS operating conditions optimized for separation and sensitivity of the target analytes. Target PAH included in ToxPAH50 shown in Table 1 along with the Target Method Detection Limit.
ii. Saturated hydrocarbons by gas chromatography with flame ionization detection (GC/FID) based on EPA Method 8015. See Table 2 for compound details and detection limits.
iii. Total Extractable Hydrocarbons (TEH) representing the total aromatic and aliphatic hydrocarbon content of sample extracts after silica gel clean-up and analysis by GC/FID. The result is reported based on integration of the FID signal over the entire hydrocarbon range from n-C9 to n-C44 and calibrated against the average alkane hydrocarbon response factor. See Table 2 for details and detection limits.
iv. Wet sediment samples range in size from 32-36 mL (1-cm vertical fractions) and 160-180 mL (5-cm vertical fractions) and all hydrocarbon analyses need to come from an individual sample. Total number of samples is not to exceed N=234 and payment only provided for number of samples analyzed.
Table 1. List of required individual compounds of PAHs with notes about acceptable coelutions. Target Method Detection Limit Range for Sediment/Soil = 0.1 – 0.5 ng/g dry weight.
| Reference for Compound 1 |
| chemname |
| chemcode |
| ToxPAH502 |
| Alklyated PAH - Table 1.1a AQAP |
| Naphthalene |
| NAPTHALENE |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C1-Naphthalenes |
| C1NAPHTHS |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C2-Naphthalenes |
| C2NAPHTHS |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C3-Naphthalenes |
| C3NAPHTHS |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C4-Naphthalenes |
| C4NAPHTHS |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Biphenyl |
| BIPHENYL |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Dibenzofuran |
| DIBNZFURAN |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Acenaphthylene |
| ACENAPTYLE |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Acenaphthene |
| ACENAPTHEN |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Fluorene |
| FLUORENE |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C1-Fluorenes |
| C1FLUORENS |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C2-Fluorenes |
| C2FLUORENS |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C3-Fluorenes |
| C3FLUORENS |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Anthracene |
| ANTHRACENE |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Phenanthrene |
| PHENANTHRN |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C1-Phenanthrenes/anthracenes |
| C1PHENANCS |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C2-Phenanthrenes/anthracenes |
| C2PHENANCS |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C3-Phenanthrenes/anthracenes |
| C3PHENANCS |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C4-Phenanthrenes/anthracenes |
| C4PHENANCS |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Dibenzothiophene |
| DIBNZTHIO |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C1-Dibenzothiophenes |
| C1DBZTHIOP |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C2-Dibenzothiophenes |
| C2DBZTHIOP |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C3-Dibenzothiophenes |
| C3DBZTHIOP |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C4-Dibenzothiophenes |
| C4DBZTHIOP |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Benzo(b)fluorene |
| BNZFL_23 |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Fluoranthene |
| FLUORANTHN |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Pyrene |
| PYRENE |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C1-Fluoranthenes/pyrenes |
| C1FLUORPYR |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C2-Fluoranthenes/pyrenes |
| C2FLUORPYR |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C3-Fluoranthenes/pyrenes |
| C3FLUORPYR |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C4-Fluoranthenes/pyrenes |
| C4FLUORPYR |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Naphthobenzothiophene |
| NTHPHNE |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C1-Naphthobenzothiophenes |
| C1NTHPHNE |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C2-Naphthobenzothiophenes |
| C2NTHPHNE |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C3-Naphthobenzothiophenes |
| C3NTHPHNE |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C4-Naphthobenzothiophenes |
| C4NTHPHNE |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Benzo(a)anthracene |
| BAA |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Chrysene + Triphenylene a |
| CHRY3PHYL |
| X |
| alternative isomeric reference - see footnotes |
| Chrysene a |
| CHRYSENE |
| Alklyated PAH - Table 1.1a AQAP |
| C1-Chrysenes |
| C1CHRYSENS |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C2-Chrysenes |
| C2CHRYSENS |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C3-Chrysenes |
| C3CHRYSENS |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| C4-Chrysenes |
| C4CHRYSENS |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Benzo(b)fluoranthene b |
| BBF |
| X |
| alternative isomeric reference - see footnotes |
| Benzo(b+j)fluoranthene b |
| BBJF |
| Alklyated PAH - Table 1.1a AQAP |
| Benzo(j+k)fluoranthene c |
| BJKF |
| X |
| alternative isomeric reference - see footnotes |
| Benzo(k)fluoranthene c |
| BKF |
| Alklyated PAH - Table 1.1a AQAP |
| Benzo(a)fluoranthene |
| BAF |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Benzo(e)pyrene |
| BEP |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Benzo(a)pyrene |
| BAP |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Indeno(1,2,3-c,d)pyrene |
| ICDP |
| X |
| alternative isomeric reference - see footnotes |
| Dibenzo(a,h+a,c)anthracene d |
| BANTH_AHAC |
| X |
| Alklyated PAH - Table 1.1a AQAP |
| Benzo(g,h,i)perylene |
| BGHIP |
| X |
Footnotes a "Chrysene" and "Chrysene + Triphenylene" represent the same PAH. Most references, and some laboratories working under different analytical conditions, refer only to evaluation of Chrysene; however, as samples were analyzed under the DWH AQAP, the analytical laboratories found that Triphenylene coelutes with the it's Chrysene isomer; therefore, the labs, for accuracy in reporting, changed reporting "Chrysene" to "Chrysene + Triphenylene".
b "Benzo (b) fluoranthene" and "Benzo (b+j) fluoranthene" represent the same PAH. Most references, and some laboratories working under different analytical conditions, refer only to evaluation of Benzo (b) fluoranthene; however, as samples were analyzed under the DWH AQAP, some of the analytical laboratories found that the Benzo(j)fluoranthene isomer coelutes with the Benzo (b) fluoranthene isomer; therefore, some labs, for accuracy in reporting, changed reporting "Benzo (b) fluoranthene" to "Benzo (b+j) fluoranthene".
c "Benzo (j+k0) fluoranthene" and "Benzo (k) fluoranthene" represent the same PAH. Most references, and some laboratories working under different analytical conditions, refer only to evaluation of Benzo (k) fluoranthene; however, as samples were analyzed under the DWH AQAP, some of the analytical laboratories found that the Benzo (j) fluoranthene isomer coelutes with the Benzo (k) fluoranthene isomer; therefore, some labs, for accuracy in reporting, changed reporting "Benzo (k) fluoranthene" to "Benzo (j+k) fluoranthene".
d "Dibenzo (a,h) anthracene" and "Dibenzo (a,h+a,c) anthracene" represent the same PAH. Most references, and some laboratories working under different analytical conditions, refer only to evaluation of Dibenzo (a,h) anthracene; however, as samples were analyzed under the DWH AQAP, some of the analytical laboratories found that the Dibenzo (a,c) anthracene isomer coelutes with the Dibenzo (a,h) anthracene isomer; therefore, some labs, for accuracy in reporting, changed reporting "Dibenzo (a,h) anthracene" to "Dibenzo (a,h+a,c) anthracene".
REFERENCES
1 Analytical Quality Assurance Plan (AQAP), Mississippi Canyon 252 (Deepwater Horizon) Natural Resource Damage Assessment, Version 3.1, Prepared for NOAA by EcoChem, Inc. November 15, 2012
2 ToxPAH50 is a list of 50 PAHs which Stratus Consulting uses to evaluate the PAH content of samples (Memorandum, 12/7/12)
Table 2. Saturated Hydrocarbons (Alkanes/Isoprenoids Compounds) and Total Extractable Hydrocarbons.
| 1380 |
| 2,6,10 Trimethyldodecane |
| 1470 |
| 2,6,10 Trimethyltridecane |
Integration of the FID signal over the entire hydrocarbon range from n-C9 to n-C44 after silica gel cleanup.
Integration of the FID signal over the entire hydrocarbon range from n-C9 to n-C44 no silica gel cleanup.
Target Method Detection Limit
| Sediment (Alkanes) = |
| 0.01 μg/g dry weight |
| Sediment (TEH) = |
| 1 μg/g dry weight |
| Water (Alkanes) = |
| 0.8 µg/L |
Target Reporting Limit
| Oil (Alkanes) = |
| 200 mg/kg |
| Water (TEH/TEM) = |
| 200 µg/L |
TEH = Total Extractable Hydrocarbons with silica gel "clean-up" TEM = Total Extractable Matter with no extract "clean-up"
b. Metals analyses. Sediment samples have been collected by USGS and will be provided to the contractor.
i. Total metals in sediments and tissues by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS) and total mercury in sediments and tissues by cold vapor atomic absorption (CVAA) or cold vapor atomic fluorescence spectrometry (CVAFS). The analytical procedures are based on EPA SW-846 Methods 6010C, 6020A, 7470A, 7471A, 7471B, 7474, and 7742. The target analyte list and target reporting limits (RLs) for each matrix are included in Table 3.
ii. Sediments have been preprocessed as follows: Dried at 80°C and ground to a fine powder.
iii. Original wet sediment samples range in size from 32-36 mL (1-cm vertical fractions) and 160-180 mL (5-cm vertical fractions) and all hydrocarbon analyses need to come from an individual sample. Total number of samples is not to exceed N=234 and payment only provided for number of samples analyzed.
Table 3. List of target metal analytes and reporting limits.
Metals Target Analyte List
| Analyte |
| Method |
| Target Reporting Limits (RL) |
| Sediment (mg/Kg) dry weight |
| Tissues (mg/Kg) wet weight |
| Antimony |
| ICP/ICP-MS |
| 0.05 |
| NA |
| Barium |
| ICP/ICP-MS |
| 0.1 |
| 0.05 |
| Beryllium |
| ICP/ICP-MS |
| 0.05 |
| NA |
| Cadmium |
| ICP/ICP-MS |
| 0.05 |
| 0.02 |
| Calcium |
| ICP/ICP-MS |
| 100 |
| NA |
| Chromium |
| ICP/ICP-MS |
| 0.2 |
| 0.2 |
| Cobalt |
| ICP/ICP-MS |
| 0.05 |
| 0.05 |
| Copper |
| ICP/ICP-MS |
| 0.1 |
| 0.1 |
| Lead |
| ICP/ICP-MS |
| 0.05 |
| 0.02 |
| Magnesium |
| ICP/ICP-MS |
| 50 |
| NA |
| Manganese |
| ICP/ICP-MS |
| 0.2 |
| 0.2 |
| Mercury |
| CVAA/CVAFS |
| 0.01 |
| 0.01 |
| Nickel |
| ICP/ICP-MS |
| 0.5 |
| 0.5 |
| Potassium |
| ICP/ICP-MS |
| 100 |
| NA |
| Selenium |
| ICP/ICP-MS |
| 0.1 |
| 0.1 |
| Silver |
| ICP/ICP-MS |
| 0.05 |
| 0.05 |
| Strontium |
| ICP/ICP-MS |
| 2.00 |
| NA |
| Thallium |
| ICP/ICP-MS |
| 0.1 |
| NA |
| Vanadium |
| ICP/ICP-MS |
| 0.5 |
| 0.5 |
Method detection limits (MDL) should be at least 3 times lower than the target reporting limits.
c. Report of quantitative results of hydrocarbons and trace metals including quality assurance and quality control parameters.
2. Criteria for acceptance of Product or Service
a. All analyses must be consistent with the MC252 Analytical Quality Assurance Plan
b. Report includes quantitative measures of hydrocarbons and trace metals including quality assurance and quality control parameters.
B.
Deliverables.
1.
Characteristics for work product described in II.A.1., identified by name and quantity.
a. Quantitative measures of identified PAHs, saturated hydrocarbons, and total hydrocarbons in excel spreadsheet or other machine-readable format (e.g. .csv)
b. Quantitative measures of trace metals in excel spreadsheet or other machine-readable format (e.g. .csv).
c. Data should be in a format suitable for a data release or online data repository.
2.
Delivery dates for work/product to be completed and point of delivery.
a. Final product: 120 days from establishment of contract
b. Delivered to USGS Wetland and Aquatic Research Center, Gainesville, FL
III.
SUPPORTING INFORMATION
A.
Place of Performance. Contractor laboratory B.
Period of Performance: 120 days C.
Government Furnished Property (GFP): USGS will provide sediment samples for chemical analyses D.
Special Considerations.
1.
Key personnel qualifications: Contractor must have demonstrated ability to conduct the analyses required, as demonstrated by published reports of similar studies.
2. Data Rights, Safety, Environment: USGS Wetland and Aquatic Research Center will retain rights to the data resulting from these analyses and will follow established USGS protocols for releasing data when publishing results of this study.
3.
Security/Privacy issues: N/A