Report of Findings Related to California Department of Fish and Wildlife, Office of Spill Prevention and Response 2012 Avila Tank Farm Tide Pool Sampling
Melissa Boggs and Sonia Torres February 11, 2014
Table of Contents I. Introduction ...... 3 II. Background ...... 3 III. Objectives ...... 4 IV. Field Sample Collection Procedures ...... 5 IV.a. May 2012 Field Sampling………………………………………………………………………………………………………..….……5 IV.a.1. May 2012 Sample Locations……………………..…………………………………………………………….………..………….5 IV.a.2. May 2012 Field Sampling Team…………………………………………………………………………….…………………..….5 IV.a.3. May 2012 Field Sampling Methods………………………………………………………………….……………………………6 IV.b. June 2012 Field Sampling…………………………………………………………………………………………………………………7 IV.b.1. June 2012 Sample Locations ...... 7 IV.b.2. June 2012 Field Sampling Team ...... 8 IV.b.3. June 2012 Field Sampling Methods ...... 8 IV.b.4. June 2012 Mussel Tissue Sampling ...... 8 IV.b.5. June 2012 Sediment Sampling ...... 9 IV.b.6. June 2012 Water Sampling ...... 9 IV.b.7. June 2012 Decontamination Procedures ...... 9 V. June 2012 Quality Assurance/Quality Control (QA/QC) ...... 9 V.a. June 2012 Sample Transport and Storage ...... 10 VI. Lab Analytical Methods ...... 10 VI.a. BTEX Analysis ...... 10 VI.b. PAH Analysis ...... 10 VI.c. TPH Analysis ...... 11 VI.d. Petroleum Hydrocarbon Confirmation and Fingerprint Comparison ...... 11 VII. Laboratory Results ...... 11 VIII. Discussion……………………………………………………………………………………………………………………………………….12 IX. References ...... 14 Figures and Photos………………………………………………………………………………………………………………………………..15 Table 1 Summary of Samples Collected by CDFW-OSPR…………………………………………………………………………28 TOC continued on next page
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Table 2 Summary of Lab Results from CDFW-OSPR Samples Collected May 8 and May 11, 2012 ….………29 Table 3 Summary Mussel Lab PAH Results From CDFW-OSPR June 8, 2012 Sampling Event.…………………30 Table 4 Summary of Sediment Sample PAH Results from CDFW-OSPR June 8, 2012 Sampling Event…….31 Table 5 Summary of Sediment Sample TPH Results from CDFW-OSPR June 8, 2012 Sampling …..……….…32 Table 6 Summary of VOC Sample Results from CDFW-OSPR June 8, 2012 Sampling Event….…………………33 Appendix 1 Laboratory Results and Chain of Custody Forms…………………………………………………………….…..34 Appendix 2 R. Donohoe ATF Mussel Data Preliminary Toxicity Assessment, February 10, 2014……………86 Appendix 3 S. Klasing, OEHHA Fish Closure Evaluation, October 17, 2012…………………………………..…………95 Appendix 4 Field Notes, Sketch from June 2012 Sample Event……………………………………………………….…..101 Appendix 5 Avila Tank Farm Initial Mussel Sampling and Analysis Plan, June 5 2012……….………………….107 Appendix 6 CalEMA Spill Report 12-2772…………………………………………………………………………………………….116
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I. Introduction This document presents the results of the California Department of Fish and Wildlife, Office of Spill Prevention and Response (CDFW-OSPR) media sampling and chemical analysis related to the Avila Tank Farm (ATF) facility assessment. The investigation was conducted to initiate evaluation of potential natural resource injuries related to the ATF Cliff Seeps, specifically sheen that was first discovered May 8, 2012 (CalEMA spill report # 12-2772, Appendix 6) in the tide pools at the east end of Avila Beach, California, San Luis Obispo County (Figure 1). The area of concern (AOC) is in the intertidal zone below the Former Union Oil ATF facility (Figure 2), specifically adjacent to the toe of the cliff south of Former Tank No. 201104. This report summarizes field sampling methods and analytical chemistry data from samples collected by CDFW- OSPR in both May and June, 2012; but primarily focuses on the sampling event in June which was conducted according to a sampling and analysis plan (CDFW-OSPR, 2012; Appendix 5).
II. Background On May 8, 2012 a reconnaissance survey was conducted in the AOC by CDFW-OSPR, Chevron Environmental Management Company (CEMC), Padre Associates, Inc. (CEMC consultants), and California Regional Water Quality Control Board, Central Coast Region (RWQCB) staff. This survey was conducted for the purpose of identifying new cliff seep sample site locations related to the on-going ATF facility assessment of contamination from former oil storage and refining operations at the site since 1997. (Avocet Environmental, 2013). CEMC assumed the environmental assessment responsibilities of the ATF facility in 2005. In 1997 the facility was formally decommissioned. Operations at the site resulted in petroleum contaminated soil and groundwater which are being assessed in preparation for remediation. The on-going site assessment at the ATF facility has determined there is high concentrations (> 1,000 mg/kg) of total petroleum hydrocarbons (TPH) in shallow soils that have migrated to the groundwater resulting in high TPH water concentrations (> 1,000 µg/L) within the Obispo formation (Avocet Environmental, 2013).
While surveying the AOC on May 8, 2012, silver sheen in an area approximately 10 feet by 30 feet, was observed in the tide pools at the base of the cliff (photos 1-3). Additionally, an intermittent petroleum hydrocarbon odor was detected. The AOC where sheen was observed in the tide pools is adjacent to Padre Associates intertidal zone sample location IZ-3 (Padre, 2012a). This tide pool area is only accessible at low tide. Dominant species in this area include algae (nori, Turkish towel, scouring pad, iridescent), giant green anemones, common acorn barnacles, lined shore crabs, limpets, California mussels, and sea stars. Additionally, this area is designated critical habitat for endangered black abalone. In this area, typically sand accumulates in the ATF CDFW-OSPR Report of Findings Related to 2012 Tide Pool Sampling Page 3
summer months and the tide pools are covered with sand and during the winter the tide pools become exposed as the sand is eroded by the high energy surf and storms.
Samples were collected on May 8, 2012 by Padre Associates and CDFW-OSPR staff. CDFW-OSPR collected two sheen samples, using fiberglass strips, for petroleum hydrocarbon analysis. Padre staff collected 3 water samples for volatile organic compounds (VOCs), including fuel oxygenates, TPH, polycyclic aromatic hydrocarbons (PAHs), and lead analyses. After the May 8 observations, CDFW-OSPR staff collected additional sediment, water and sheen samples on May 11 (Table 1, Summary of Samples Collected).
Analysis of the May 8, 2012 water samples collected by CEMC consultants indicated the presence of VOCs, including benzene, toluene, ethylbenzene, and xylenes (BTEX), PAH, and TPH (Padre, 2012b). Some of the water samples from the AOC had fuel constituents in similar proportions to those observed in groundwater samples from monitoring wells B-230 and B-231 on the ATF facility. CDFW-OSPR sediment sample results from May 11, 2012 showed the tide pool sediment contained typical weathered biomarkers found in petroleum hydrocarbons. The sheen sample from the cliff face contained low levels of weathered aliphatic hydrocarbons but concentrations were too low to characterize further; and petroleum hydrocarbons were not confirmed in the tide pool sheen samples (Table 2, Summary of Lab Results from May Sampling and Appendix 1).
After reviewing the initial lab results from May 8 and 11, 2012 (Table 2 and Appendix 1), CDFW-OSPR determined additional sampling was warranted, developed a sampling plan (Appendix 5), and then collected additional samples on June 8, 2012, primarily focusing on mussel sample collection.
In the absence of contrary evidence, CEMC is considering the release from former Tank No. 201104 from the ATF facility as the source of the fuel-related contaminants detected in the intertidal area (Holder and Lambert, 2013).
III. Objectives Media samples were collected on May 8 and 11, 2012 with the objective of determining presence or absence of hydrocarbons and fingerprinting the petroleum mixture in an attempt to determine the source of the sheen.
The objectives of the June 8, 2012 sampling efforts were to: 1) collect data that might be used to assess potential biological injuries from sheen observed in the intertidal
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zone; 2) to some degree determine the extent of the contamination; and 3) to aid in identifying the source of the contamination.
The June 8, 2012 sampling primarily focused on the collection of resident mussels (Mytilus californianus). However, on-site conditions on the day of sampling also allowed for collection of sediment and water samples.
IV. Field Sample Collection Procedures All samples were collected as described below. Table 1 summarizes the samples CDFW-OSPR collected related to this assessment. The June field sampling was conducted according to the Sampling and Analysis Plan in Appendix 5.
IVa. May 2012 Sampling No sampling plan was prepared for the May 2012 sample collection events due to the unforeseen occurrence of the contamination and the immediate need to evaluate the AOC under a tidal regime that afforded access to the area. May 8 and 11, 2012 samples were collected and analyzed by methods described below.
IV.a.1. May 2012 Sample Locations On May 8, 2012, two sheen samples (IZ-3-MB1 and IZ-3-MB2) were collected from the two tide pools where a light silver sheen was observed and where a light petroleum odor was detected. Sample locations were documented by taking photos, and obtaining coordinates using a GPS unit, and in field notes/sketches. The sample locations were selected based on the presence of the sheen and odor (Table 1, Photos 1 and 2).
On May 11, 2012, a sheen sample was collected from the tide pool (IZ-3-MB6; Table 1), from near the same location as on May 8, 2012. A sheen sample (IZ-2-MB4; Table 1) was also collected from the cliff face where a light silver sheen was observed on the rock, adjacent to the sampled tide pool. A sediment sample (IZ-3-MB3; Table 1) was collected from the same tide pool as where the sheen sample was collected. One “source” groundwater sample was collected from the ATF facility monitoring well B-230 on the ATF facility above the tide pools (see Figure 2). GPS coordinates were not collected at the tide pool during the May 11 sampling but it was the same general location as IZ-3-MB1 collected on May 8.
IV.a.2. May 2012 Field Sampling Teams The May 8, 2012 sampling team consisted of Melissa Boggs (CDFW-OSPR), Dan Niles (RWQCB), and staff from Padre Associates. The May 11, 2012 sampling team consisted of Melissa Boggs, Rick Williams (CEMC), Cesar Santacana and Peter Anderson (U.S. Coast Guard).
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IV.a.3. May 2012 Field Sampling Methods On May 8, two sheen samples were collected from two tide pools where sheen was present using fiberglass cloth strips. Each sheen sample was collected by using one 12” fiberglass strip and passing the fiberglass strip through the sheen with a gloved hand, then placing the fiberglass strip into a 250-mL certified pre-cleaned glass jar with a TeflonTM-lined lid provided by the CDFW-OSPR Petroleum Chemistry Lab (PCL). Nitrile gloves were worn when collecting/handling samples. A new pair of gloves was worn at each sample site to prevent cross-contamination. Care was taken to not step into the tide pool containing the sheen.
On May 11, a sediment sample (IZ-3-MB-3) was collected from the tide pool using a gloved hand and scooping up surface sediment with a pre-cleaned scoop and filling a certified pre-cleaned 250 ml clear sampling jar with a TeflonTM-lined lid. The sheen sample collected from the cliff face (IZ-3-MB-4) was collected by rubbing one 12” fiberglass strip along the cliff face where water was seeping out of the cliff and then placing the fiberglass strip into a 250 ml clear sampling jar with a TeflonTM-lined lid, using a gloved hand. The sheen sample from the tide pool (sample number MB-6) was collected by using one 12” fiberglass strip and passing the fiberglass strip through the sheen in the tide pool with a gloved hand, then placing the fiberglass strip into a clean sample jar. Care was taken to not step into the tide pool where samples were collected from. The “source” sample (IZ-MB-7) was collected by filling a certified pre-cleaned one liter amber sampling jar with a TeflonTM-lined lid with known contaminated groundwater from monitoring well B-230 with the assistance of staff from Padre Associates as they were conducting their regular groundwater monitoring efforts at the ATF facility. Monitoring well B-230 is located in an area of the ATF facility, near Former Tank No. 201104, near the cliff face, where lighter-end petroleum hydrocarbon- impacted groundwater similar to gasoline is present. Groundwater elevation in monitoring well B-230 was -1.37 feet below mean sea level (MSL) at the time of sampling. The well was purged utilizing a low-flow or micro-purge technique (Padre, 2012c). No sheen was observed in the water sample at the time of sampling. This sample was considered the "source" sample for CDFW-OSPR fingerprinting purposes.
May 8, 2012 samples were brought back to the CDFW-OSPR vehicle where they were stored in a cooler (without ice since this was an un-planned sampling event), transported to CDFW-OSPR San Luis Obispo office approximately 1.5 hours after the sample was collected, and then stored in a sample refrigerator at 4C under appropriate chain of custody. The samples were transported via hand delivery to the CDFW-OSPR PCL (Rancho Cordova, CA) on May 10 in an ice chest.
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May 11, 2012 samples were brought back to the CDFW-OSPR vehicle where they were stored in a cooler with ice, transported to CDFW-OSPR San Luis Obispo office, and then stored in a sample refrigerator under appropriate chain of custody until hand delivered to the CDFW-OSPR PCL on May 18 in an ice chest.
IV.b. June 2012 Field Sampling The June 8 field sampling was conducted according to the Sampling and Analysis Plan in Appendix 5, with the exceptions noted below. Field notes can be found in Appendix 4. The tide pools were filled in with sand on June 8 so no sheen was observed, and as such, no sheen samples were collected.
IV.b.1. June 2012 Sample Locations On June 8 samples were collected from the eastern end of Avila Beach beneath the ATF facility in the AOC where sheen had been observed previously, in the same general area as samples collected in May 2012 (near Padre Associates IZ-3 sample location, Figure 2). Mussel samples were also collected June 6 from a reference location at Montana de Oro State Park. The reference site location is one that is regularly sampled as part of the Mussel Watch Program (http://www.waterboards.ca.gov/water_issues/programs/swamp/mussel_watch.shtml).
Within the AOC mussel sample plots or strata were delineated in the field using pin flags (Figures 3-6). Strata length and width for each of the three strata in the AOC were measured and noted on field data sheets, photos were taken, and coordinates of the strata corners were obtained using a field GPS with waypoints noted on the field data sheets (Table 1 and Appendix 4). The three strata or plots in the AOC were delineated as follows: strata 1 was closest to the toe of the cliff where odors had been detected and sheen observed (near sample numbers MB1, MB2, MB3, and MB6 [near Padre Associates sample #IZ-3]), strata 2 was located seaward of strata 1, and strata 3 was located east of strata1 and 2 (Figure 3).
Sediment and interstitial water samples were collected from two holes dug in strata1 and one hole dug in strata 2 (Figures 4 and 5). Coordinates of the holes were obtained using a field GPS with waypoints noted on the field data sheets (Table 1 and Appendix 4).
When CDFW-OSPR GIS staff plotted the coordinates of the sample locations/strata configurations the locations were off when compared to the photos, possibly due to a degraded GPS signal due to proximity of the rocky cliff so Figures 3-6 and photos 4, 5, 7, and 9 and field notes/sketches in Appendix 4 document the strata configurations.
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IV.b.2. June 2012 Field Sampling Team The June 8, 2012 sampling team consisted of CDFW-OSPR staff Melissa Boggs, Mitchell Goode, and Sonia Torres. Staff from Padre Associates were also present to observe. On June 6, CDFW-OSPR staff person Gary Ichikawa (and CDFW assistants) collected the mussel sample from the reference site at Montana de Oro (at the same time they were collecting samples for the Diablo Canyon Nuclear Power Plant monitoring program).
IV.b.3. June 2012 Field Sampling Methods Nitrile gloves were worn when collecting/handling samples and using sampling equipment. A new pair of gloves was worn at each sample site to prevent cross- contamination. Care was taken to try not to step into the area where the water and sediment samples were collected from and mussels were not stepped on. Sample collection equipment was decontaminated in the field, utilizing procedures outlined in the Sampling and Analysis Plan (Appendix 5). In the field, samples were stored in a cooler with wet ice for subsequent transport to the CDFW office, and then to the lab under appropriate chain of custody.
IV.b.4. June 2012 Mussel Tissue Sampling A composite sample of 25-40 mussels (depending on mussel size) was collected from rocks from each of the three strata within the AOC. One composite sample of 25-40 mussels was also collected from Montana de Oro, the reference site.
Intact mussels (closed and sealed shells) were collected by prying mussels off rocks with stainless steel dive knives at the AOC and reference site at Montana de Oro. Nitrile gloves were worn when handling samples and sampling equipment and were changed in between sample sites. The stainless steel dive knives were decontaminated between sample sites (see section IV.b.7 below).
Each composite mussel sample was wrapped in aluminum foil pre-rinsed with methanol, dull side to the shells, and placed in two ZiplockTM plastic bags. A label for each composite sample was inserted between the first and second bags. In the field, samples were stored in an ice chest with wet ice prior to transport to a secured freezer in CDFW-OSPR San Luis Obispo office where each sample bag was sealed with evidence tape. The samples were then shipped to the lab under chain of custody.
The reference mussel sample collected June 6, 2012 from Montana de Oro was collected in the same manner as noted above but was kept under the possession of CDFW-OSPR staff person Gary Ichikawa who stored the sample and shipped it to the lab under separate chain of custody. ATF CDFW-OSPR Report of Findings Related to 2012 Tide Pool Sampling Page 8
IV.b.5. June 2012 Sediment Sampling Discrete sediment grab samples were collected on the beach in the intertidal zone by digging a hole with a shovel to the depth of groundwater (approximately 1 foot) and scooping up sand from the bottom of the hole with a plastic scoop and placing sediment in a 250 mL pre-cleaned certified sample jar. Sediment samples were collected from the same sample sites or strata where the mussels were collected from, from two holes in strata 1 and one hole in strata 2. Coordinates of the holes were obtained using a field GPS with waypoints noted on the field data sheets (Table 1 and Appendix 4). The tide came in such that a sediment sample from strata 3 could not be collected. Sample numbers were written on each sample jar, jars were stored in an ice chest with wet ice in the field prior to transport to a secured sample refrigerator in CDFW-OSPR San Luis Obispo office. The samples were then shipped to the lab under chain of custody.
IV.b.6. June 2012 Water Sampling Water samples were collected from the interstitial/groundwater in holes dug in strata 1 and strata 2 by filling three volatile organic analysis (VOA) vials per each hole. The VOA vials were filled by submerging capped vials, opening under water to fill, re-capping under water, then inverting to make sure there was no head space/bubbles. Sample numbers were written on each sample jar, jars were stored in an ice chest with wet ice in the field prior to transport to a secured sample refrigerator in CDFW-OSPR San Luis Obispo office. The samples were then shipped to the lab under chain of custody.
IV.b.7. June 2012 Decontamination Procedures Sampling equipment was decontaminated between samples using Alconox/distilled water mixture using a brush, between sample locations. Rinsate was collected in a 5- gallon bucket. Nitrile gloves were changed following sample collection at each location and a new pair of gloves was worn prior to sampling at subsequent locations.
V. June 2012 Quality Assurance/Quality Control (QA/QC) A rinsate blank sample was collected of distilled water that had been used to rinse sampling equipment after the prescribed decontamination procedures had been completed. The rinsate blank was prepared by collecting a sample of the final distilled water rinse from the decontaminated shovel that was used to dig the pits for the sediment and interstitial water samples collected. One rinsate blank was collected in a certified, pre-cleaned 1 L amber bottle, filled to the top, and labeled as a rinsate (equipment) blank. The rinsate sample was stored in an ice chest with wet ice in the field prior to transport to a secured sample refrigerator in CDFW-OSPR office. The sample was then shipped with the rest of the samples to the lab under chain of custody.
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V.a. June 2012 Sample Transport and Storage From the field, the samples collected from Avila Beach on June 8 were transported in a cooler with wet ice to the CDFW-OSPR office in San Luis Obispo where the mussel samples were kept frozen and the water and sediment samples were kept refrigerated at 4°C in a tamper proof manner (sealed with evidence tape) until transported on ice to the lab for processing. The samples were shipped in a cooler via FedEx priority overnight on June 11 to the CDFW-WPCL under chain of custody.
The reference mussel sample collected June 6 from Montana de Oro was kept under the possession of CDFW-OSPR staff person Gary Ichikawa who stored the sample and shipped it via OnTrac overnight to the CDFW-WPCL on June 7 under separate chain of custody.
A standard CDFW-OSPR chain of custody form accompanied all samples transported to the lab (Appendix 1).
VI. Lab Analytical Methods Samples were analyzed by the CDFW-OSPR WPCL, CDFW-OSPR PCL, and a contract lab. The WPCL is a certified State environmental testing laboratory pursuant to the provisions of the California Environmental Laboratory Improvement Act of 1988. The contract lab, California Laboratory Services, is also a state certified lab. Mussel tissue samples were analyzed for PAHs. Sediment and water samples were analyzed for PAHs, TPH, BTEX, and petroleum fingerprint analysis. Petroleum fingerprinting was also conducted on the “source” sample from groundwater monitoring well B-230 from the ATF (Table 1).
VI.a. BTEX Analysis For water samples collected using VOA vials, BTEX was analyzed by EPA Method 8260-modified-GC/MS/SIM by a contract lab, California Laboratory Services (http://www.epa.gov/osw/hazard/testmethods/sw846/pdfs/8260b.pdf).
VI.b. PAH Analysis For mussel, water (including “source” sample), and sediment samples, PAHs and alkylated PAHs were analyzed by the CDFW WPCL using EPA Method 8270-modified- GC/MS/SIM (http://www.epa.gov/epawaste/hazard/testmethods/sw846/pdfs/8270d.pdf).
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VI.c. TPH Analysis For sediment and water samples TPH analysis was completed by the CDFW WPCL using EPA Method 8015 modified, GC/FID, extended range (http://www.epa.gov/osw/hazard/testmethods/sw846/pdfs/8015c.pdf).
VI.d. Petroleum Hydrocarbon Confirmation and Fingerprint Comparison Sediment, water, and sheen were analyzed for petroleum hydrocarbon confirmation and fingerprint comparisons to each other and compared to the “source sample” (collected May 11, 2012, M. Boggs, MB7), using CDFW Petroleum Chemistry Lab (PCL) Method PH51, ASTM Method D - 5739, Modified.
VII. Laboratory Results VII.a. Laboratory results from May 2012 sampling event Results from May 8, 2012 sampling event: Petroleum hydrocarbons were not confirmed in either of the two sheen samples (IZ-3-MB1 and IZ-3-MB2). See Table 2 for a summary of the analytical results for samples collected in May and Appendix 1 for complete lab results.
Results from the May 11, 2012 sampling event: The tide pool sediment sample (MB-3) contained typical weathered biomarkers found in petroleum hydrocarbons, including hopanes and steranes, but concentrations were too low to compare or characterize further. Sheen sample MB-4, fiberglass strip rubbed on cliff face, contained weathered aliphatic hydrocarbons in the C26 to C36 range. Petroleum hydrocarbons were not confirmed in the sheen sample (MB-6) from the tide pool. The “source” water sample (MB-7) contained weathered petroleum hydrocarbons in the C9 to C15 range. See Table 2 for summary of lab results and Appendix 1 for complete lab results.
VII.b. Laboratory results from June 2012 sampling event Mussel tissue samples were analyzed for 47 parent and alkylated PAHs; 26 PAHs were detected (Table 3 and Appendix 1). Mussel tissue from the Montana de Oro reference site had a higher total PAH concentration than any of the three mussel samples from the AOC at Avila. However, the three Avila mussel samples had consistently higher concentrations of some parent PAHs (phenanthrene, naphthalene, anthracene, fluoranthene, pyrene, chrysene), compared to the reference site.
All three sediment samples contained heavily weathered petroleum hydrocarbons, in
the range C18 – C34, and all three were consistent with a common source (Table 5 and Appendix 1). The sediment samples were also compared to the source water sample and were found to not be consistent. Sediment samples were analyzed for 47 parent
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and alkylated PAHs and 21 of those compounds were detected (Table 4 and Appendix 1).
The three interstitial water samples were analyzed for BTEX. Ethylbenzene and total xylene concentrations were12 µg/L and 62 µg/L, respectively, in one sample from strata 1 but were not detected in the second sample from strata 1. Interstitial water from strata 2 contained benzene and total xylene at 2.5 µg/L and 1.9 µg/L, respectively (Table 6 and Appendix 1).
The rinsate blank water sample contained trace concentrations of naphthalene and naphthalenes, C1 (Appendix 1); but because the mussel tissue and sediment concentrations were at least five times greater than the concentrations in the rinsate blank, the contribution from the rinsate would not be considered significant (U.S. EPA, 2008).
VIII. Discussion Sampling and fingerprinting to date has not provided verification of the source of the intermittent sheen and odor in the tide pool beneath the ATF facility. However, lines of evidence indicate the release is coming from the former Tank No. 201104 from the ATF facility (Holder and Lambert, 2013).
When comparing mussel tissue sum PAH concentrations from the June 8, 2012 sampling, the reference location at Montana de Oro had the highest concentration. When comparing the 3 mussel samples collected from Avila, the sample from strata 3 (sample number MB10) adjacent to the cliff and east of strata 1 had the highest total PAH concentration detected and the second highest total PAH concentration was detected in strata 1 (sample number MB8), also adjacent to the cliff. The mussel sample from Avila with the lowest sum PAH concentration was from strata 2 (sample number MB9), the sample furthest from the cliff and furthest seaward.
Mussel tissue PAH concentrations from the three strata were compared to several mussel tissue effect concentrations. This evaluation was completed by CDFW-OSPR Staff Toxicologist Regina Donohoe (see Appendix 2 for summary memo). Tissue PAH concentrations were compared to benchmarks developed to predict mortality, acute toxicity and chronic toxicity, using the generic target lipid model. It was determined that no toxicity was predicted by this model. Feeding activity benchmarks for specific PAHs were used as surrogates for low molecular weight and high molecular weight PAHs but there were no exceedances. Tissue PAH levels also did not exceed the scope for growth benchmarks. PAH levels also did not exceed those shown to cause 50% lysosomal destabilization. Dr. Donohoe also compared the mussel data from the AOC
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from Avila to state-wide Mussel Watch data and concluded mussels from Avila were consistent with the Mussel Watch data with PAH levels in the low contaminant range. CDFW-OSPR also requested the California Environmental Protection Agency, Office of Environmental Health Hazard Assessment (OEHHA) to perform a non-emergency fisheries closure evaluation for mussels collected from Avila Beach. OEHHA evaluated human health risks based on concentrations of carcinogenic PAHs detected in the mussels collected June 8, 2012 (see Appendix 3 for summary memo). Based on the June 2012 results, OEHHA concluded the risk for consumption of mussels from Avila Beach was not of sufficient magnitude to warrant a fisheries closure. The Benzo[a]pyrene [BaP] equivalent concentrations in mussels from Avila Beach were approximately two orders of magnitude below the Public Health Protective Concentration developed for the Cosco Busan and Dubai Star oil spills (44 parts per billion BaPE, wet weight) and were considered not to pose a significant human health risk (Klasing, 2012).
Regarding the sediment sample results, all three sediment samples contained detectable levels of heavily weathered petroleum hydrocarbons, and the three were consistent with a common source; but they were not consistent when compared to the groundwater source sample. According to personal communications with CDFW Chemist Jim McCall, the “source” groundwater sample appeared to be a refined product more closely resembling gasoline with a low, narrow carbon range and no biomarker signal (i.e., no hopanes or steranes detected) and the sediment samples from the tide pools contained heavily weathered crude with a wider carbon range and a low biomarker signal. While the connection between a low, narrow carbon (refined product) source to a broad carbon range, heavily weathered crude signature in the sediment is unclear, different environmental conditions/properties in the tide pools versus the groundwater monitoring well (i.e., amount of UV light, oxygen levels, salinity, temperature, biodegradation, etc…) could in part account for some of the differences. Per Jim McCall, fingerprinting light end petroleum products is difficult because of the lack of weathering resistant compounds and biomarkers in such mixtures (McCall, 2012).
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IX. References Avocet Environmental, Inc., 2013, Site Conceptual Model, dated April 12, 2013. Holder and Lambert, 2013, Notification Plan for the Intertidal Area, Avila Tank Farm, June 5, 2013.
McCall, 2012, Personal Communications, August 7, 2012.
Padre Associates, Inc., 2012a. Revised Intertidal Zone Observation Monitoring Plan, Former Unocal Avila Terminal, June 29, 2012.
Padre Associates, Inc., 2012b. Report of Findings Intertidal zone Assessment Activities Area South of Former Tank No. 201104 Former Unocal Avila Terminal, December 2012.
Padre Associates, Inc., 2012c. Report of Findings First Semi-Annual 2012 Groundwater, Cliff Springs, and Intertidal Zone Monitoring Event, Former Unocal Avila Terminal, July 2012.
U.S. Environmental Protection Agency. 2008. National Functional Guidelines for Superfund Organic Methods Data Review.
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Figures
Figure 1. General Location of Avila Beach and Montana de Oro (Reference Site)
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Figure 2. Intertidal Area of Concern Beneath Avila Tank Farm Facility
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Figure 3. Approximate Configuration of the 3 Strata Where Mussel, Sediment, and Water Samples Were Collected
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Figure 4. Approximate Configuration of Strata 1 Mussel, Sediment, and Water Sample Location
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Figure 5. Approximate Configuration of Strata 2 Mussel, Sediment, and Water Sample Location
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Figure 6. Approximate Configuration of Strata 3, Mussel Sample Location
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Photos 1 and 2, May 8, 2012, Close-up of Sheen in Tide pool
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Photo 3, May 8, 2012 Overview of Area of Concern (note tide pools were exposed, not covered with sand).
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Photo 4, June 8, 2012 Sampling Event, General Area
Photo 5, June 8, 2012 Sampling Event, General Area, Strata 1
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Photo 6, June 8, 2012 Sampling Event, Mussel Sample Collected from, Strata 1
Photo 7, June 8, 2012 Sampling Event, Collecting Mussels from Strata 2
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Photo 8, June 8, 2012 Sampling Event, Mussel Sample from Strata 2
Photo 9, June 8, 2012 Sampling Event, Mussel Sample from Strata 3
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Photo 10, June 8, 2012 Sampling Event, Mussel Sample from Strata 3
Photo 11, June 8, 2012 Sampling Event, Collecting Sediment Sample from Strata 1
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Photo 12, June 8, 2012 Sampling Event, Filling VOA Vials for VOC Analysis, Sample from Strata 1
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Table 1 Summary of Samples Collected by CDFW-OSPR Date Sample Number Media Analysis Sample Location Coordinates of Samples Sample Sampled Requested Taken 5/8/12 IZ3-MB1 Sheen (fiberglass) TPH confirmation & Beneath ATF, tide pool N35.17609 W120.72667 petroleum fingerprint 5/8/12 IZ3-MB2 Sheen (fiberglass) TPH confirmation & Beneath ATF, tide pool N35.17616 W120.72660 petroleum fingerprint 5/11/12 MB3 Sediment TPH confirmation & Beneath ATF, tide pool None taken petroleum fingerprint 5/11/12 MB4 Sheen (fiberglass) TPH confirmation & Beneath ATF, cliff face None taken petroleum fingerprint 5/11/12 MB6 Sheen (fiberglass) TPH confirmation & Beneath ATF, tide pool None taken petroleum fingerprint 5/11/12 MB7 Water TPH confirmation & Monitoring Well B230 (“source” None taken petroleum fingerprint sample from ATF Facility) 6/6/12 Station Code #430 Mussel Tissue PAHs Montana de Oro (reference site) N35.28046 W120.88889 (lab # L-255-12-01) 6/8/12 ATF-MB11 Sediment TPH, petroleum Strata 1 (pit 1), beneath ATF, tide N35.17608 W120.72672 fingerprint, PAHs pool 6/8/12 ATF-MB14 Sediment TPH, petroleum Strata 1 (pit 2), beneath ATF, tide N35.17602 W120.72684 fingerprint, PAHs pool 6/8/12 ATF-MB16 Sediment TPH, petroleum Strata 2 (pit 3), beneath ATF, tide pool N35.17599 W120.72660 fingerprint, PAHs 6/8/12 ATF-MB12a,b,c Interstitial water VOA Strata 1 (pit 1) N35.17608 W120.72672 6/8/12 ATF-MB13a,b,c Interstitial water VOA Strata 1 (pit 2) N35.17602 W120.72684 6/8/12 ATF-MB15a,b,c Interstitial water VOA Strata 2 (pit 3) N35.17599 W120.72660 6/8/12 ATF-MB8 Mussel Tissue PAHs Strata 1, beneath ATF, tide pool N35.17606 W120.72654 N35.17610 W120.72651 N35.1603 W120.72662 N35.17607 W120.72637 6/8/12 ATF-MB9 Mussel Tissue PAHs Strata 2, beneath ATF, tide pool N35.17607 W120.72657 N35.17605 W120.72662 N35.17600 W120.72664 N35.17602 W120.72660 6/8/12 ATF-MB10 Mussel Tissue PAHs Strata 3, beneath ATF, tide pool N35.17607 W120.72654 N35.17603 W120.72653 N35.17597 W120.72657 N35.17596 W120.72660 6/8/12 ATF-MB17 Rinsate, blank PAHs None taken
ATF CDFW-OSPR Report of Findings Page 28 Related to 2012 Tide Pool Sampling 0
Table 2 Summary of Lab Results from CDFW-OSPR Samples Collected May 8 and May 11, 2012
Date of Sample Media/sample Collection Results Sample ID # Device/Sample Location Collection 5/8/12 IZ-3 – MB1 Sheen from tide pool surface Non detect for petroleum water hydrocarbon confirmation Fiberglass strip Next to sample site IZ-3 5/8/12 IZ-3 – MB2 Sheen from tide pool surface Non detect for petroleum water Fiberglass strip hydrocarbon confirmation Next to sample site IZ-3 5/11/12 MB3 Sediment Petroleum hydrocarbons were from tide pool confirmed but in trace amounts. Next to sample site IZ-3 Concentrations were too low to further characterize. 5/11/12 MB4 Fiberglass strip wiped on cliff Weathered aliphatic hydrocarbons face in the C26-C36 range detected Next to sample site IZ-3 5/11/12 MB5 Water (containing algae or Sample held bacteria?) From pool at toe of cliff near sample site IZ-3 5/11/12 MB6 Sheen from tide pool surface Non detect for petroleum water hydrocarbon confirmation Fiberglass strip Next to sample site IZ-3 5/11/12 MB7 Water Weathered petroleum Liter jar hydrocarbons were confirmed in Suspected “source” from GW the C9 to C15 range monitoring well B230 from Tank Farm
ATF CDFW-OSPR Report of Findings Related to 2012 Tide Pool Sampling 29
Table 3 Summary Mussel Lab PAH Results From CDFW-OSPR June 8, 2012 Sampling Event
ATF CDFW-OSPR Report of Findings Related to 2012 Tide Pool Sampling Page 30
Table 4 Summary of Sediment Sample PAH Results from CDFW-OSPR June 8, 2012 Sampling Event
ATF CDFW-OSPR Report of Findings Related to 2012 Tide Pool Sampling Page 31
Table 5 Summary of Sediment Sample TPH Results from CDFW-OSPR June 8, 2012 Sampling Event
SAMPLE # TPH-FULL RANGE (µg/g)* CONCENTRATION DETECTED Strata 1, pit #1 53 L-260-12-2 Strata 1; pit #2 46 L-260-12-5 Strata 2; pit #3 63 L-260-12-9
Samples L-260-12-2, L-260-12-5 and L-260-12-9 were extracted with dichloromethane and analyzed for total petroleum hydrocarbons-full [TPH-F] by GC/MS.
* Sample concentrations reported on a dry weight basis. BRL=below reporting limit. Surrogate used: OTP @ 62 ug/mL Spike Solution: Prudhoe Bay Crude Oil @ 1,100 ug/mL 1 Description taken from corrected CoC from M. Boggs, dated 06/15/12.
ATF CDFW-OSPR Report of Findings Related to 2012 Tide Pool Sampling Page 32
Table 6 Summary of VOC Sample Results from CDFW-OSPR June 8, 2012 Sampling Event
SAMPLE # BENZENE TOLUENE ETHYLBENZENE XYLENES µg/L µg/L µg/L (TOTAL) µg/L Strata 1, pit #1 ATFMB12a,b,c ND ND ND ND Strata 1; pit #2 ATFMB13a,b,c ND ND 12 62 Strata 2; pit #3 ATFMB15a,b,c 2.5 ND ND 1.9
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Laboratory Results and Chain of Custody Forms
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Appendix 2
Regina Donohoe, Draft Avila Tank Farm Mussel Data Preliminary Toxicity Assessment, dated February 10, 2014
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Table 1. Comparison of Avila Tank Farm Mussel PAH Concentrations to Mussel Tissue Effect Concentrations Reference Endpoint Effect Level ATF* ∑PAH Tissue Hazard Concn. ( ATF CDFW-OSPR Report of Findings Page 87 Related to 2012 Tide Pool Sampling Reference Endpoint Effect Level ATF* ∑PAH Tissue Hazard Concn. ( Tissue Damage Hwang et al., 50% lysosomal 9.3 nmol/g dw or ATF-1 = 1.1 nmol/g HQ < 1 2008 destabilization in 2,100 ng/g dw dw oysters Sum PAHs = 219 ng/g (n=24) dw ATF-2 = 0.9 nmol/g dw = 175 ng/g dw ATF-3 = 1.0 nmol/g dw = 195 ng/g dw REF = 1.6 nmol/g dw = 302 ng/g dw (Sum of Total PAHs) Mussel Watch Baseline Data Kimbrough et Low Range of 63 – 1187 ng/g ATF-1 = 219 ng/g al., 2008 Total PAH dw dw Concentrations in Sum PAHs ATF-2 = 175 ng/g 1986-2005 Mussel (n=38) dw Watch Data ATF-3 = 195 ng/g dw REF = 302 ng/g dw (Sum of Total PAHs) *ATF-1; Avila Tank Farm Strata 1: ATF-2; Avila Tank Farm Strata 2: ATF-3 = Avila Tank Farm Strata 3; REF = Montana De Oro; Reporting Limit ( R.L) used for analytes below reporting limit.; Sum of total polycyclic aromatic hydrocarbons ( ∑PAH), n=47 ATF CDFW-OSPR Report of Findings Page 88 Related to 2012 Tide Pool Sampling Summary • Tissue PAH concentrations were converted to umol/g lipid (assuming 3.4% lipid; U.S. Army Corps of Engineers BSAF Database) or umol/g wet weight units and were compared to benchmarks developed to predict mortality, acute toxicity and chronic toxicity, using the generic target lipid model. No toxicity was predicted by this model. • Feeding activity benchmarks for specific PAHs were used as surrogates for low molecular weight and high molecular weight PAHs but there were no exceedances. • Tissue PAH levels did not exceed scope for growth benchmarks. • Levels did not exceed those shown to cause 50% lysosomal destabilization. • Levels within “low” contaminant range of mussel tissue data from Mussel Watch Program. References DiToro, D. M. , McGrath, J. A., and Hansen, D. J. 2000. Technical basis for narcotic chemicals and polycyclic aromatic hydrocarbon criteria. I. Water and tissue. Environmental Toxicology and Chemistry 19: 1951-1970. Donkin, P., Widdows, J., Evans, S. V., Worrall, C. M., and Carr, M. 1989. Quantitative structure- activity relationships for the effect of hydrophobic organic cehmcials on the rate of feeding by mussels (Mytilus edulis). Aquatic Toxicology 14: 277-294. Eertman, R. H. M., Groenink, C., Sandee, B., and Hummel, H. 1995. Response of the blue mussel, Mytilus edulis, following exposure to PAHs or contaminated sediments. Marine Environmental Research 39: 169-173. Hwang, H., Wade, T. L., and Sericano, J. L. 2008. Residue-response relationship between PAH body burdens and lysosomal membrane destabilization in eastern oysters (Crassostrea virginica) and toxicokinetics of PAHs. Journal of Environmental Science and Health 43: 1373-1380. Kimbrough, K. L., W. E. Johnson, G. G. Lauenstein, J. D. Christensen and D. A. Apeti. 2008. An Assessment of Two Decades of Contaminant Monitoring in the Nation’s Coastal Zone. Silver Spring, MD. NOAA Technical Memorandum NOS NCCOS 74. 105 pp. O'Connor, T. P. 2002. National distribution of chemical concentrations in mussels and oysters in the USA. Marine Environmental Research 53: 117-143. Payne, J. R., Driskell, W. B., Barron, M. G., and Lees, D. C. Assessing Transport and Exposure Pathways and Potential Petroleum Toxicity to Marine Resources in Port Valdez, Alaska. 2001. Anchorage, Alaska, Prince William Sound Regional Citizen's Advisory Council. Reineke, V., Rullkotter, J., Smith, E. L., and Rowland, S. J. 2006. Toxicity and compositional analysis of aromatic hydrocarbon fractions of two pairs of undegraded and biodegraded crude oils fromt he Santa Maria (California) and Vienna basins. Organic Geochemistry 37: 1885-1899. U.S. Army Corps of Engineers. Biota Sediment Accumulation Factor (BSAF) and Lipid Database. http:/el/erdc.usace.army.mil/bsafnew/LipidWeb2b.dbw. Accessed July 2012. ATF CDFW-OSPR Report of Findings Page 89 Related to 2012 Tide Pool Sampling U.S. EPA. 2003. Procedures for the Derivation of Equilibrium Partitioning Sediment Benchmarks (ESBs) for the Protection of Benthic Organisms: PAH Mixtures. EPA-600-R-02-013. Office of Research and Development. Washington, D.C. ATF CDFW-OSPR Report of Findings Page 90 Related to 2012 Tide Pool Sampling ATF CDFW-OSPR Report of Findings Page 91 Related to 2012 Tide Pool Sampling ATF CDFW-OSPR Report of Findings Page 92 Related to 2012 Tide Pool Sampling Figure 1 - PAH Profile Page 93 50.00 45.00 40.00 35.00 30.00 25.00 20.00 Tissue Conc. (ng/g dw) (ng/g Conc. Tissue 15.00 10.00 ATF-1 5.00 ATF-2 < R.L. ATF-3 0.00 REF Pyrene Biphenyl Perylene Fluorene Chrysene Anthracene Naphthalene Fluoranthene Phenanthrene Acenaphthene Fluorenes, C1 - C1 Fluorenes, - C2 Fluorenes, - C3 Fluorenes, Chrysenes, C1 - Chrysenes, C2 - Chrysenes, C3 - Benzo(a)pyrene Benzo(e)pyrene Acenaphthylene Dibenzothiophene Methylfluorene, 1- Benz(a)anthracene Naphthalenes, C1 - Naphthalenes, C2 - Naphthalenes, C3 - Naphthalenes, C4 - Benzo(g,h,i)perylene Benzo(k)fluoranthene Benzo(b)fluoranthene Dibenz(a,h)anthracene Methylnaphthalene, 2- Methylnaphthalene, 1- Methylfluoranthene, 2- Indeno(1,2,3-c,d)pyrene Dibenzothiophenes, C1 - C1 Dibenzothiophenes, - C2 Dibenzothiophenes, - C3 Dibenzothiophenes, Methylphenanthrene, 1- Dimethylnaphthalene, 2,6- Fluoranthene/Pyrenes, C1 - Fluoranthene/Pyrenes, Dimethylphenanthrene, 3,6- Methyldibenzothiophene, 4- Trimethylnaphthalene, 2,3,5- Phenanthrene/Anthracene, C1 - Phenanthrene/Anthracene, C2 - Phenanthrene/Anthracene, C3 - Phenanthrene/Anthracene, C4 - Phenanthrene/Anthracene, ATF CDFW-OSPR Report of Findings ATF Related to 2012 Tide Pool Sampling ATF CDFW-OSPR Report of Findings Page 94 Related to 2012 Tide Pool Sampling Appendix 3 Susan Klasing, Office of Environmental Health Hazard Assessment, Memorandum, Non-Emergency Fisheries Closure Evaluation, Avila Beach, dated October 17, 2012 ATF CDFW-OSPR Report of Findings Page 95 Related to 2012 Tide Pool Sampling ATF CDFW-OSPR Report of Findings Page 96 Related to 2012 Tide Pool Sampling ATF CDFW-OSPR Report of Findings Page 97 Related to 2012 Tide Pool Sampling ATF CDFW-OSPR Report of Findings Page 98 Related to 2012 Tide Pool Sampling ATF CDFW-OSPR Report of Findings Page 99 Related to 2012 Tide Pool Sampling ATF CDFW-OSPR Report of Findings Page 100 Related to 2012 Tide Pool Sampling Appendix 4 Field notes/sketches from June 2012 Sampling Event ATF CDFW-OSPR Report of Findings Page 101 Related to 2012 Tide Pool Sampling ATF CDFW-OSPR Report of Findings Page 102 Related to 2012 Tide Pool Sampling ATF CDFW-OSPR Report of Findings Page 103 Related to 2012 Tide Pool Sampling ATF CDFW-OSPR Report of Findings Page 104 Related to 2012 Tide Pool Sampling ATF CDFW-OSPR Report of Findings Page 105 Related to 2012 Tide Pool Sampling AVILA TANK FARM SAMPLE LOCATIONS Way Point # Date Coordinates 018 08-MAY-12 15:16 N35.17609 W120.72667 019 08-MAY-12 15:18 N35.7616 W120.72660 020 10-MAY-12 15:37 N35.17595 W120.72661 021 24-MAY-12 16:51 N35.16505 W120.69252 022 30-MAY-12 18:11 N35.17488 W120.62249 023 30-MAY-12 18:13 N35.17415 W120.62166 024 30-MAY-12 19:13 N35.17364 W120.62129 025 08-JUN-12 15:31 N35.17606 W120.72654 026 08-JUN-12 15:34 N35.17610 W120.72651 027 08-JUN-12 15:36 N35.1603 W120.72662 028 08-JUN-12 15:36 N35.17607 W120.72637 029 08-JUN-12 15:55 N35.17607 W120.72657 030 08-JUN-12 15:56 N35.17605 W120.72662 031 08-JUN-12 15:57 N35.17600 W120.72664 032 08-JUN-12 15:57 N35.17602 W120.72660 033 08-JUN-12 16:08 N35.17607 W120.72654 034 08-JUN-12 16:08 N35.17603 W120.72653 035 08-JUN-12 16:08 N35.17597 W120.72657 036 08-JUN-12 16:08 N35.17596 W120.72660 037 08-JUN-12 16:35 N35.17608 W120.72672 038 08-JUN-12 16:47 N35.17602 W120.72684 039 08-JUN-12 16:55 N35.17599 W120.72660 ATF CDFW-OSPR Report of Findings Page 106 Related to 2012 Tide Pool Sampling Appendix 5 June 2012 Sampling Plan ATF CDFW-OSPR Report of Findings Page 107 Related to 2012 Tide Pool Sampling AVILA TANK FARM INITIAL MUSSEL SAMPLING AND ANALYSIS PLAN June 5, 2012 Prepared by: Melissa Boggs California Department of Fish and Game Office of Spill Prevention and Response ATF CDFW-OSPR Report of Findings Page 108 Related to 2012 Tide Pool Sampling 1.0 Scope, Application, and Background The purpose of this Sampling and Analysis Plan (SAP) is to provide a written record of the sampling and analysis procedures in support of the natural resource injury assessment and to help inform us if further response actions are warranted related to the Avila Tank Farm Cliff Seeps Incident (CalEMA # 12-2772) located near Avila Beach, California, San Luis Obispo County (Figure 1). Specifically the area of concern (AOC) is in the intertidal zone below the Former Unocal (now Chevron) Avila Tank Farm. Figure 1. Google Earth Image of Avila Beach Area of Concern and general location of reference site at Montana de Oro. On May 8, 2012 a survey was conducted in the AOC by Department of Fish and Game, Office of Spill Prevention and Response (DFG-OSPR) staff, Padre (Chevron consultants), Chevron Environmental Management Company (CEMC) staff, and the California Regional Water Quality Control Board, Central Coast Region (RWQCB). Initially this May 8 survey was conducted for the purpose of identifying new sample site locations and collecting samples related to the on-going Tank Farm assessment. While surveying the AOC silver sheen was observed in tidepools at the base of the cliff and an intermittent petroleum hydrocarbon odor was detected (PID reading of 3.0 parts per million by volume (ppmv). The AOC where sheen was observed in the tidepools is adjacent to Chevron intertidal zone sample location IZ-3 sampled on May 8, 2012. Sheen was observed in an area approximately 10 feet by 30 feet. Coordinates of one of the DFG-OSPR samples collected May 8 are N35.17609/W120.72667 (sample locations were close to each other). Due to the visible sheen and odor detected on May 8, Chevron agreed to analyze water ATF CDFW-OSPR Report of Findings Page 109 Related to 2012 Tide Pool Sampling samples for the presence of volatile organic compounds (VOCs) including fuel oxygenates and total petroleum hydrocarbons (TPH), polycyclic aromatic hydrocarbons (PAHs), and lead. Intertidal zone sample IZ -3 (where the sheen was visible on the surface of the water and odor was noted) contained detectable levels of fuel-related compounds, including benzene, lead scavenger 1,2-dichloroethane (EDC), and fuel oxygenate tertiary butyl alcohol (TBA) in water at concentrations of 34 micrograms per liter (µg/L), 2.7 µg/L, and 91 µg/L, respectively. Regarding PAH results, sample IZ-3 contained 1.4 µg/L napthalene in water. This sample also contained TPH (C4-C10) at 500 ug/L. Organic lead was not detected. DFG-OSPR also collected samples on May 8 (two sheen on water samples collected using fiberglass strips) and May 11(one sediment sample; one sheen on water sample collected using fiberglass strip; and one fiberglass strip rubbed on cliff face sample). Petroleum hydrocarbons were not detected in the DFG-OSPR samples collected May 8. Regarding the DFG-OSPR samples collected on May 11, trace concentrations of weathered biomarkers found in petroleum hydrocarbons were detected in the sediment sample; and weathered aliphatic hydrocarbons were detected in the fiberglass strip rubbed on cliff face sample. Additional assessment is warranted because: • Current analytical data indicates detectable levels of fuel-related compounds were present in water samples collected from the intertidal zone; • Sheen and odor have been detected in and around the tidepools on more than one occasion; • The magnitude and mechanism of the release is unknown; • DFG-OSPR has to take into account the possibility of issuing a fishery closure and mussels have been used in previous studies as an indicator species; and • The source has not been confirmed (although a number of lines of evidence lead to the source being contaminated groundwater from the Tank Farm). The sampling proposed in this plan is limited in scope, primarily to show presence/absence of contaminants; and depending on results, a more robust sampling effort may be warranted. 2.0 Project Organization and Department Responsibilities DFG-OSPR staff will be responsible for implementing the procedures summarized herein and DFG-OSPR staff will prepare a summary report. 3.0 Sampling Objectives The objectives of this sampling effort are to 1) collect data that may be used to assess potential biological injuries from sheen observed in the intertidal zone, 2) to some extent to determine the extent of the contamination, and 3) to aid in identifying the source of the contamination. This sampling will primarily focus on collection of resident mussels (Mytilus californianus). Depending on site conditions on the day of sampling, we may also collect sediment and/or water samples. Mussel tissue samples will be analyzed for PAHs and sediment and/or water samples will be analyzed for PAHs, total petroleum hydrocarbons (TPH) and benzene, toluene, ethylbenzene, and xylenes (BTEX). If possible, petroleum fingerprinting will also be ATF CDFW-OSPR Report of Findings Page 110 Related to 2012 Tide Pool Sampling conducted using a “source” sample from groundwater monitoring well B230 from the Avila Tank Farm (sample previously collected May 11, 2012). 4.0 Health and Safety Prior to starting work, the lead DFG-OSPR staff will conduct a safety brief. Potential hazards and preventive measures associated with this sampling include: • Hazards from rouge waves: Because sampling will only occur during low tide, use of personal floatation devices (PFDs) may not be necessary but team members will have them on scene. • Slip, trip, and fall hazards exist when walking on the rocks in the intertidal zone. Extra care and awareness is required. • Hazards from falling rocks from cliff: Because sampling is being conducted beneath a rocky cliff there is a potential for rocks to fall. Hard hats will be worn when working under/near the cliff. • Heat or cold stress: Appropriate layers of clothing will be worn. • Exposure to chemicals of concern: Gloves will be worn when collecting samples. 5.0 Sample Locations Samples will be collected from the eastern end of Avila Beach and from a reference location (mussel samples only) at Montana de Oro State Park in San Luis Obispo County (N35.28046/W120.88889), Figures 1 and 2. The reference site location is one that is regularly sampled as part of the DFG mussel watch program. Below the Avila Tank Far, the sample locations will be concentrated in the area where the sheen has been observed, near sample site IZ-3. Figure 2. Google Earth Image, close up of Area of Concern ATF CDFW-OSPR Report of Findings Page 111 Related to 2012 Tide Pool Sampling 6.0 GPS and Photo Documentation Sampling locations will be documented by taking photos, obtaining coordinates using a GPS unit, and in field notes. 7.0 Field Sampling Methods Nitrile gloves will always be worn when collecting/handling samples and using sampling equipment. A new pair of gloves will be worn at each sample site to prevent cross- contamination. In the field samples will be stored in a cooler with wet ice for subsequent transport to DFG-OSPR office under appropriate chain of custody. 7.1 Mussel Tissue Sampling Beneath the Avila Tank Farm, at each of three sample sites, a composite sample of 25-40 mussels (depending on size) will be collected. One composite sample of 25-40 mussels (depending on size) will also be collected from Montana de Oro, the reference site. Beneath the Avila Tank Farm, mussels from three locations will be collected from randomly selected strata on the rocks within the AOC. Strata length and width for each of the three locations will be measured and noted on the data sheet. It will be attempted to collect mussels from three sites in a gradient, one closest to the toe of the cliff where odors have been strongest and sheen observed (near sample site IZ-3), second site will be seaward of the first, and the third site will be to the east of the first and second locations. Intact mussels (closed and sealed shells) will be collected by prying mussels off rocks with stainless steel dive knives at the AOC and reference site at Montana de Oro. Nitrile gloves will be worn when handling samples and sampling equipment. Each composite mussel sample will be wrapped in aluminum foil pre-rinsed with methanol, dull side to the shells, and placed in two ZiplockTM plastic bags. A label for each composite sample will be inserted between the first and second bags. 7.2 Sediment Sampling Discrete sediment grab samples may be collected by digging a hole with a shovel to the depth of groundwater (approximately 1 foot) and scooping up sand from the bottom of the hole with a scoop or spoon and placed in a pre-cleaned certified sample jar. And/or if sand is present in tidepools where sheen is visible or was previously visible, sand will be scooped up with a scoop or spoon and placed in a certified pre-cleaned 250 mL sample jar. If sediment is present at/next to the locations where mussels are collected, sediment samples may be collected there and/or from a random location within the AOC. 7.3 Water Sampling If sheen is visible in the interstitial/groundwater in holes dug to collect sediment samples, a water sample may be collected by filling VOA vials by submerging, un-capping, filling, and re-capping under water. If sufficient volume is available, water samples will also be collected in 1 L amber glass jars by submerging, un-capping, filling, and re-capping under ATF CDFW-OSPR Report of Findings Page 112 Related to 2012 Tide Pool Sampling water. 7.4 Sheen Sampling When a surface sheen exists on the water surface, a sample will be collected by using 4- 12” cut strips of fiberglass strips, which are then placed in a 250-mL pre-cleaned and certified glass jar. The fiberglass strips will be passed through the sheen at approximately a 90-degree angle to the fiberglass strips. 8. Decontamination Procedures Sampling equipment will be decontaminated between samples using Alconox/distilled water mixture using a brush, between sample locations. Rinsate will be collected in a 5- gallon bucket. Nitrile gloves will be changed following sample collection at each location and a new pair of gloves will be worn prior to sampling at subsequent locations. 9. Quality Assurance/Quality Control (QA/QC) QA/QC samples will be collected following the discretion of the team leader, the level of contamination to be assessed, the medium being sampled, and any recommendations from the lab. A rinsate blank is a sample of distilled water that has been used to rinse sampling equipment after the prescribed decontamination procedures have been completed. A rinsate blank will be prepared by collecting a sample of the final distilled water rinse of decontaminated field sampling equipment. The rinsate blank will be collected in a certified, pre-cleaned 1 L amber bottle, filled to the top, and labeled as a rinsate (equipment) blank. 10. Sample Transport and Storage From the field, samples will be transported in the cooler with ice to the DFG-OSPR office in San Luis Obispo where mussel samples will be kept frozen and water and sediment samples will be kept refrigerated in a tamper proof manner (locked or sealed with evidence tape) until transported on ice to the lab for processing. A standard DFG-OSPR chain of custody form will accompany all samples that are brought to the lab. 11. Chemical Analysis to be Performed • Mussel tissues: PAHs • Sediment: PAHs, TPH, petroleum fingerprint • Water: PAHs, TPH, petroleum fingerprint • VOA: BTEX • Sheen: Petroleum fingerprint • “Source”: PAHs (groundwater monitoring well B230) 11.1 BTEX Analysis ATF CDFW-OSPR Report of Findings Page 113 Related to 2012 Tide Pool Sampling If water samples are collected using VOA vials, BTEX will be analyzed for by the DFG Water Pollution Control Laboratory (WPCL) using EPA Method 8260-modified- GC/MS/SIM. 11.2 PAH Analysis For mussel, water (including “source” sample previously collected May 11 from groundwater monitoring well B230), and sediment samples (if collected), PAHs and alkylated PAHs will be analyzed by the DFG WPCL using EPA Method 8270-modified- GC/MS/SIM (http://www.epa.gov/epawaste/hazard/testmethods/sw846/pdfs/8270d.pdf). 11.3 TPH Analysis If sediment and/or water samples are collected TPH will be analyzed by the DFG Water Pollution Control Laboratory using EPA Method 8015 modified, GC/FID, extended range. 11.4 Petroleum Hydrocarbon Confirmation and Fingerprint Comparison Sediment, water, and/or sheen analyzed for petroleum hydrocarbon confirmation and fingerprint comparison will be compared to “source sample” (previously collected May 11, 2012, M. Boggs, MB7 and identified as PCL Lab Number S-017-12-4), using DFG Petroleum Chemistry Lab Method PH51, ASTM Method D - 5739, Modified." 12. Data Quality Objectives (DQOs) ATF CDFW-OSPR Report of Findings Page 114 Related to 2012 Tide Pool Sampling Table 1. Data Quality Objectives Steps For Mussel Sample Collection. DQO DESCRIPTION DETAILS STEP STEP 1 State the PAHs of petrogenic origin have known toxicity to mussels (Mytilus sp.). Tissue sampling Problem is needed to determine whether there is (1) a potential exposure pathway between mussels and dissolved or particulate PAHs in the water column, (2) discern whether any potential PAH exposures are petrogenic in origin (i.e., from the release) versus pyrogenic in orgin (i.e., from combustion) and attributable to ambient sources, and (3) evaluate whether mussels may be exposed to toxic levels of PAHs in water, at both the AOC and at a reference location at Montana de Oro. STEP 2 Identify the 1. Are petrogenic PAHs detected in mussel samples collected from reference and Decisions assessment site locations? 2. If petrogenic PAHs are detected are they potentially attributable to the Avila Tank Farm site or ambient sources? Is there a spatial pattern in mussel PAH concentrations that is consistent with the degree of oiling observed in the sampled locations? 3. Are concentrations of petrogenic PAHs above or below thresholds known to generate toxicity to mussels or similar species? STEP 3 Identify Inputs to • Sample locations have been identified from the May 8, 2012 reconnaissance survey the Decisions • Individual pyrogenic and petrogenic PAHs will be identified and measured in each tissue sample following a modified (ultra trace) gas chromatograph/mass spectrometry selective ion monitoring method. • Patterns, including types of pyrogenic and petrogenic PAHs, will be compared between the reference and assessment sampling areas to see if the sampling locations can be differentiated by a PAH and steranes/triterpanes profile. • Analytical results from each tissue sample will be compared to a variety of PAH toxicity benchmarks to evaluate potential adverse effects to mussels. STEP 4 Define Study • Within the AOC, to the extent feasible, mussel tissue samples will be collected from the Boundaries intertidal zone in a gradient fashion. Figures 1 and 2 show the general vicinity of the mussel sampling locations STEP 5 Develop Decision • If the pattern/fingerprint of petrogenic PAH tissue concentrations is spatially correlated Rules with the area where sheen has been observed, there is evidence that the PAHs are attributable to the Avila Tank Farm and there is a potential pathway of exposure to mussels. • If tissue concentrations of petrogenic PAHs are greater than literature established toxicity thresholds, then there is evidence that tissue PAH concentrations may limit the survival of mussels and similar species in that habitat. STEP 6 Specify Tolerable • Analytical errors will be minimized through the use of measurement quality objectives Limits on Errors described in the laboratory QAPP. • Sample quantitation limits will be at least for each PAH. STEP 7 Optimize • All samples will be collected before or during one tidal cycle on June 8, 2012with the Sampling Design exception of the reference site mussel sample which will be collected on June 6, 2012). • Samples will be collected on a low tide. • Samples will be delivered to the laboratory for prompt extraction and analyses within the holding times. DQO = Data Quality Objective; QAPP Quality Assurance Project Plan ATF CDFW-OSPR Report of Findings Page 115 Related to 2012 Tide Pool Sampling Appendix 6, CalEMA Spill Report # 12-2772 ATF CDFW-OSPR Report of Findings Page 116 Related to 2012 Tide Pool Sampling Hazardous Materials Spill Report - 12-2772 http://w3.calema.ca.gov/operational/malhaz.nsf/f1841a103c1027348825... California Emergency Management Agency DATE: 05/09/2012 RECEIVED BY: CONTROL#: TIME: 1818 Cal EMA - 12-2772 NRC - 1011043 1.a. PERSON NOTIFYING Cal EMA: 1. NAME: 2. AGENCY: 3. PHONE#: 4. Ext: 5. PAG/CELL: Chevron 1.b. PERSON REPORTING SPILL (If different from above): 1. NAME: 2. AGENCY: 3. PHONE#: 4. Ext: 5. PAG/CELL: 2. SUBSTANCE TYPE: 2. a. SUBSTANCE: b.QTY:>= CONFIRMATION REQUEST: ********* Control No: 12-2772 ********* Created by: Warning Center on: 05/09/2012 06:18:03 PM Last Modified by: Warning Center on: 05/09/2012 06:27:58 PM ATF CDFW-OSPR Report of Findings Page 117 Related to 2012 Tide Pool Sampling 1 of 1 5/10/2012 12:32 PM