1 **FINAL REPORT IGAP Unmet Needs Project** 

**– Oil Spill Monitoring Capacity**  **- 8019**  **Tribe’s Name** Aleutian Pribilof I slands Association, Inc. **Environmental Contact Name**  **s** Bruce Wright and Karen Pletnikoff **Contact Phone Number** 907 - 222 - 4260 **Grant Name** Indian Environmental General Assistance Program (GAP) Unmet Needs Project

– Oil Spill Monitoring Capacity **Grant Number and Project Period**  G - 96001901 - 1 ; Project Period: October 1, 2005 - December 31, 2009 **EPA’s Project Officer Name and Address**  Tami Fordham, Tribal Coordinator U.S. Environmental Protection Agency Alaska Operations Office 222 West 7 th Avenue, #19 Anchorage, AK 99513 IN TRODUCTION The oil pollution monitoring project is funded b y the Environmental Protection Agency (EPA) and was established to develop oil monitoring protocol, increase local capacity, monitor subsistence areas, determine if there is low - level PAH contamination, identify potential sources of contamination, explore the establishment of regional monitoring partnerships and increase the capacity of tribal environmental staff to monitor for oil in the environment which could impact subsistence resources. The baseline hydrocarbon data will be useful for supporting the environmental impact statement for the exploratio n and development of oil and gas in the North A leutian Basin. This project develop ed a program for monitoring the marine environment for oil from spills and other pollution events including chronic releases of oil from the land, natural seeps in the ocean and spills and discharges from sea going vessels, perform monitoring of the water in Aleutian and Pribilof Island villages and to provide recommendations based on the findings for the long term prevention of oil spills and pollution in the region.2

Passiv e samplers will be deployed for a month at a time, several times throughout the ye ar at several sites near the villages of Ak utan, Atka, False Pass, King Cove, Nikolski, St. George and St. Paul. Locals were trained (under contract through local Tribes) to deploy and retrieve the passive samplers; anal ys es of the passive samplers will be conducted by chemists at the Auke Bay Laboratory . Sampling locations will include nearby subsistence areas as well as high use areas at each general location. Passive samplers : Passive accumulation devices (Figure 1) consist of a container with a low density pol yethyl ene membrane that allows organic compounds to penetrate and absorb hydrocarbons over a period of time, in contrast to a “grab” sample which is a “snap sho t” in time. Consequently , passive sampling devices are more effective in capturing hydrocarbon signals from chronic low level events or events that are intermittent, and they are very sensitive. Mussels are often used as biological sampling devices in many habitats worldwide, but are often not available on the coastlines of the Bering Sea, at least in numbers that permit sampling across time and space. Figure 2. T yl er Melovidov is deploying a passive sampler in the intertidal zone on St. Paul I sland.3

Passive samplers can sample large volumes of water, amplify trace hydrocarbon quantities (part -per- billion or part -per- trillion) to detectable levels, and average the signal over time. In addition, they are cheaper and easier to anal yz e than biolo gical tissue and can be deployed over a greater range of environmental conditions. Composition of PAH accumulated by the passive samplers can be used to identify hydrocarbon sources in situations not complicated by multiple sources (not the case with biolo gical tissue samples). Usually the sampling for this project takes place in the ocean and along the beaches, but we adapted the sampling design for a special situation in Atka. Some of the residents of the new part of Atka have been complaining of smelling diesel or gas in their water. We suspected the water line may be attracting hydrocarbons where it traveled through a polluted area and was transferring the po llution (diesel) to the drinking water. For the first time for this project, we deplo ye d a samp ling device in the freshwater holding tank for a month. The Atka water tank sample had a total PAH of 82 parts per billion/device, and very comparable to the controls. This m eans the water in the tank tested at very , very low levels of hydrocarbons and is safe to drink from that perspective based on this one test. With the proposed development of the East Aleutian Basin Outer Continental Shelf lease sale and environmental impact statement, APIA requested Minerals Management Service (MMS) to continue our co mmunity- based contaminant monitoring project. MMS is considering our proposal. **OBJECTIVES** Objective 1. To increase the capacity of tribal environmental staff to monitor for oil in the environment which could impact subsistence resources. Objective 2. T o develop a program for monitoring the marine environment for oil from spills and other pollution events including chronic releases of oil from the land, natural seeps in the ocean and spills and discharges from sea going vessels. Objective 3 . To perform monitoring of the water in villages on islands neighboring to Unalaska where the Selendang Ay u oil spill occurred. Objective 4 . To provide recommendations based on the findings for the long - term prevention of oil spills & pollution in the Aleut Region.4

**ACCOMPLISHMENTS** Objective 1. Increase the capacity of tribal environmental staff to monitor for oil in the environment which could impact subsistence resources. We trained technicians, usually Tribal members who were IGAP coordinators , to deploy the moni toring equipment and retrieve and ship the samplers. The offshore deplo ym ent method (Appendix A) failed in some locations, lost to strong currents and winds . The new method (Appendix B) required on - site re - training of local technician s and tracking of samp ler recovery and second deplo yment and recovery (see Appendix C) . Accordingl y, one community at a time was sampled with two deploy ments each. Seven communities participated ; Akutan, Atka, False Pass, King Cove, Nikolski, St. George and St. Paul. Objectiv e 2. D evelop a program for monitoring the marine environment for oil from spills and other pollution events including chronic releases of oil from the land, natural seeps in the ocean and spills and discharges from sea going vessels. The surface sampling devices (see Appendix A) were deployed in Akutan, St. Paul and Nikolski in FY 2006, but the sampling devices were lost in two of the three villages where deploy ments took place. Strong currents and large waves in Nikolski and St. George cause loss of offsho re mooring equipment. New methods (Appendix B) were developed using on - shore deploy ments. Shipping of sampling devices has taken much time to coordinate transportation of supplies (sampling devices) between Auke Bay Lab and the field an d back and additional time has been needed to train local technicians and coordinate tracking of sampler recovery and second deplo yment and recovery . Using the new methodology we were finally

successful developing the oil monitoring program. And, we p rovided a proposal to US Minerals Management Service to continue monitoring for hydrocarbons in Aleut communities. Objective 3 . P erform monitoring of the water in villages on islands neighboring to Unalaska where the Selendang Ay u oil spill occurred. Training in the first three c ommunities (Akutan, Nikolski and St. George) took place in April and May 2006. Akutan sampling went well even with some early problems with shipping samples to the Juneau lab. Year 2 study design called for two deplo ym ents with three sampling stations mounted onshore in each of the 7 communities. Sampling using the new methods was completed in all 7 communities. Objective 4 . P rovide recommendations based on the findings for the long - term prevention of oil spills and pollution in the Aleut Region. Results f rom the Akutan sampling lend eviden ce that the waters in most of the monitored villages are not very contaminated with polycyclic aromatic hydrocarbons (PAHs) . However, occasional spill s and active incinerators and outfalls continue to be a concern for pol lution. The shore - based redeplo ym ent in Akutan Harbor move d the sampling devices close to mussel beds used for subsistence food and nearer the fish processing plant ; this resulted in a very high reading . During the first deploy ment in Atka we also sampled the freshwater tank for PAHs. We found no indication of hydrocarbon contamination in the water tank. We strongl y recommend5

continued monitoring in Aleut communities and further investigation of the possibly pollution coming from the Akutan fish processing plant. Year 2 study design altered significantly to overcome severe weather conditions and to insure safety of local staff (see APPENDIX B). Shore - based sampling replace d the offshore sampl ing. Shipping problems were overcome with implementation of closel y monitored tracking. We recommend the methodology be followed in future PAH testing projects. **Results** Total TPAH data summary for the Aleutian data : sorted by increasing TPAH concentrations. As for the general rules of interpretation, quality of data there are as foll ows for good data and what modifications to these rules for this data. The cleaner/tighter the blank and environmental samples are , the strict er can be th ese rule applications. Unfortunately this data set has the opposite application. 1. Blanks should be TPAH < 100 ng/device, loosen to TPAH < 200ng/device for these data 2. Environmental sample TPAH < 500ng/device, no real signal, loosen to TPAH < 1000 ng/device for these data 3. Environmental sample TPAH > 1000 ng/device start to b e useful signals for modeling, loosen to > 2000 ng/device for these data 4. Having modified these data interp. rules, there still is the problem from the model info below, that there is no clear or convincing pattern of p yro/petro origin, i.e. things are all over the board. **Sorted	by	TPAH Data	in	RED	are	blanks	(	38	blanks)**  82	total	LDPE	samples **Aleutian/Pribilof	Project	2006 -**  **2009 SIN**  **Days	exposed Site**  **Date	collected Comments**  **QCBatch TPA**  **H** 1700501 0 ABL 1 - Mar - 06 Lab	Blank	(batch	97) F071806 0.00 1702101 0 ABL 17 - Jul - 06 Lab	Blank	(Batch	104) F071806 0.00 1802901 0 ABL 25 - Jan - 08 Lab	Blank F062408 0.006

1701401 0 ABL 12 - Jun - 06 Lab	Blank	(batch	100) F072406 3.9 4 1900102 0 ABL 21 - Feb - 08 Lab	Blank R082609 13.31 1900101 0 ABL 21 - Feb - 08 Lab	Blank R081809 28.55 1802906 33	days Old	Village	Water	Tank - Atka 11 - Apr - 08 F062408 43.95 1800701 0 ABL 30 - Apr - 07 Trip	Blank R031308 44.99 1802907 0 ABL - Atka - ABL 17 - Apr - 08 Trip	Blank F062408 53.75 1800601 0 ABL 30 - Apr - 07 Lab	Blank R030408 109.82 1900407 28	days Chungusix	Beach 11 - May - 08 F071408 123.83 1702601 0 ABL 31 - Jan - 07 Lab	Blank R021108 129.88 1701402 Entrance	Pt	(Akutan) 24 - Jul - 06 Collectors	Code	(AK001) F081506 132.98 1900303 30	days S.	Side - False	Pass 17 - Jul - 08 R090109 140.12 1800506 34	days Nikolski - CoastGaurd	Gate 4 - Dec - 07 R081809 150.64 1800605 30	days Nikolski - Moa n	Lisa 31 - Oct - 07 R031308 156.98 1900403 0 ABL - Atka - ABL 19 - May - 08 Trip	Blank F062408 160.50 1802905 33	days Nazon	Beach - Atka 11 - Apr - 08 F062408 180.20 1800803 31	days St	Paul - Pier	Point 24 - Aug - 07 R031308 181.41 1701406 0 ABL - Akutan - ABL 31 - Jul - 06 Trip	Blank F081506 192.61 1900201 East	Landing - St.	George 2 - Feb - 09 R082609 218.02 1800508 34	days Nikolski - Mona	Lisa 4 - Dec - 07 R081809 227.09 1800703 42	days St.	Paul - Outfall 27 - Jun - 07 R031308 229 .65 1700602 Akutan 20 - Jun - 06 Collectors	Code	(AK001) F071806 239.06 1900202 North - St.	George 2 - Feb - 09 R082609 239.37 1900404 28	days Dump	Beach 11 - May - 08 F062408 257.53 1900103 0 ABL - King	Cove - ABL 27 - Oct - 08 Trip	Blank R082609 285.74 1800603 30	days Nikoski - Coast	Guard 31 - Oct - 07 R030408 287.31 1900401 33	days New	Subdivision - Nazon	Bay? - Atka 11 - Apr - 08 F062408 290.10 1900604 5	min? ? ? Field	Blank R090109 296.70 1900204 East	Landing - St.	George 2 - Feb - 09 Field	Blank	? R082609 299.02 1802902 10	min Nazon	Beach - Atka 9 - Mar - 08 Field	Blank F062408 311.65 1800403 32	days Akutan - east 5 - Jun - 07 R030408 319.93 1802904 33	days Nazon	Beach - Atka 11 - Apr - 08 F062408 369.73 1900502 North - St.	George 4 - Mar - 09 R090109 370.22 1900205 ABL - St.	George - ABL Trip	Blank R082609 376.21 1800604 30	days Nikoski - Boat	Launch 31 - Oct - 07 R030408 394.82 1900107 5	min? ? ? Field	Blank R082609 400.22 1900605 0 ABL - King	Cove - ABL 28 - Jul - 08 Trip	Blank R090109 411.307

1702602 0 Trip	Blank 18 - Apr - 07 Trip	Blank R021108 421.04 1900504 Wind,	South - St.	George 4 - Mar - 09	? Field	Blank	? R090109 422.99 1700603 Akutan 20 - Jun - 06 Collecto rs	Code	(AK002) F071806 423.27 1800706 0 ABL - St.Paul - ABL 6 - Jul - 07 Trip	Blank R031308 427.60 1800404 ? Akutan	(FB/TB?) ? seal	broken	field/trip	blank?	where? R030408 430.63 1701404 Across	The	Bay	(Akutan) 24 - Jul - 06 Collectors	Code	(AK003) F081506 469.60 1700604 Akutan 20 - Jun - 06 Collectors	Code	(AK003) F071806 471.51 1701405 0 Head	Of	Bay	?	(Akutan) 20 - Jun - 06 Field	Blank	@	AK002? F081506 475.27 1802903 33	days Puyakix	Beach - Atka 11 - Apr - 08 F062408 487.52 1900203 South - St.	George 2 - Feb - 09 R082609 503.61 1800602 10	min? Nikoski	(Coast	Guard) 1 - Oct - 07 Field	Blank R030408 520.21 1900402 28	days Puyakix	Beach - Atka 11 - May - 08 F062408 539.17 1900106 37	days Airport	Beach - King Cove 28 - Aug - 08 R082609 540.56 1800507 34	days Nikoski - Boat	Launch 4 - Dec - 07 R081809 577.75 1702604 32	days Akutan - east 13 - Apr - 07 R021108 590.06 1900304 5	min? False	Pass 17 - Jul - 08	? Field	Blank R090109 608.31 1900305 0 T SMRI - False	Pass - TSMRI 24 - Jul - 08	? Trip	Blank R090109 678.78 1800702 10	min? St.	Paul - Rookery 16 - May - 07 Field	Blank R031308 681.48 1800801 31	days St.	Paul - Island	Harbor 24 - Aug - 07 R031308 687.51 1800405 ? Akutan	(FB/TB?) ? seal	broken	field/trip	blank?	where? R030408 697.15 1900505 ABL - St.	George - ABL Trip	Blank R090109 769.36 1900301 30	days N.	Side - False	Pass 17 - Jul - 08 R082609 802.44 1800606 0 ABL - Nikoski - ABL 8 - Nov - 07 Trip	Blank R031308 818.00 1800704 42	days St.	Paul - Island	Harbor 27 - Jun - 07 R031308 834.46 1900603 30	days Airport	Lagoon - King	Cove 21 - Jul - 08 R090109 913.19 1800804 10	min? ? 24 - Aug - 07 Field	Blank R031308 931.94 1702603 15	min Field	Blank - Locat ion? 13 - Apr - 07 Field	Blank R021108 991.51 1800503 0 ABL - Nikolski - ABL 26 - Dec - 07 Trip	Blank R081809 1001.15 1800502 15	min Field	Blank - Nikiski 31 - Oct - 07 Field	Blank F062408 1053.57 1800805 0 ABL - St.Paul - ABL 24 - Aug - 07 Trip	Blank R031 308 1254.93 1700601 0 Akutan 12 - May - 06 Field	Blank F071806 1407.99 1702605 32	days Akutan - center 13 - Apr - 07 R021108 1682.62 1700605 0 ABL - Akutan - ABL 11 - Jul - 06 Trip	Blank F071806 1775.11 1900601 30	days Below	Esiahs - King Cove 21 - Jul - 08 R090109 1814.91 1701403 Head	Of	Bay	(Akutan) 24 - Jul - 06 Collectors	Code	(AK002) F081506 1894.02 1900104 37	days Beach	Below	Esiahs - King	Cove 28 - Aug - 08 R082609 2284.938

1900105 37	days Harbor	Bridge - King	Cove 28 - A ug - 08 R082609 2394.26 1702606 32	days Akutan - west 13 - Apr - 07 Very	sticky	film	on	puck R021108 3087.17 1900602 30	days Harbor	Bridge - King	Cove 21 - Jul - 08 R090109 3118.53 1800402 32	days Akutan - center 5 - Jun - 07 R030408 3408.22 1900302 30	days PPSF - False	Pass 17 - Jul - 08 R082609 7188.01 1800401 32	days Akutan - west 5 - Jun - 07 R021108 52594.97 1800501 0 ABL 30 - Apr - 07 Lab	Blank	(lost) 1800504 SIN	never	Assigned SIN	never	Assigned SIN	never	Assigned 1800505 SIN	never	Assigned SIN	never	Assigned SIN	never	Assigned 1800705 St.	Paul - Rookery Lost?	Never	rec'd 1800802 St.	Paul - Outfall Puck	apart	@	receipt	no	LDPE 1900405 NO	SAMPLE - Line	Blank 190 0406 NO	SAMPLE - Line	Blank 1900501 East	Landing - St.	George 4 - Mar - 09 Sample	Lost? 1900503 South - St.	George 4 - Mar - 09 Sample	Lost?9

**DISCUSSION** The laboratory

blanks are within tolerances, but many of th e field and trip blanks are high and indicate some level of contamination possibly from shipping and/or storage. Further investigation may reveal what happened with the blanks but currentl y the model s cannot discern the problem with these inconsistent data . Figure 3. This is the incinerator at the Trident fish processing plant. It is used to burn cardboard, wood and a variety of plastic materials. The field samples TPAH range 44 to 53000 with Akutan having the highest reading . The PAH weathering model indicates the source of the PAHs as combustion by products. Th is may

be explained by

the active incinerator found at the Trident fish processing facility

onl y a few hundred meters from the village (Figure 3).10

Below are the PAH data by village. Akutan Entrance Pt (Akutan) 24 - Jul - 06 F081506 132.98

Akutan 20 - Jun - 06 F071806 239.06 Akutan - east 5 - Jun - 07 R030408 319.93 Akutan 20 - Jun - 06 F071806 423.27 Across The Bay (Akutan) 24 - Jul - 06 F081506 469.60

Akutan 20 - Jun - 06 F071806 471.51 Akutan - east 13 - Apr- 07 R0211 08 590.06 Akutan - center 13 - Apr- 07 R021108 1682.62 Head Of Bay (Akutan) 24 - Jul - 06 F081506 1894.02 Akutan - west 13 - Apr- 07 R021108 3087.17 Akutan - center 5 - Jun - 07 R030408 3408.22 Akutan - west 5 - Jun - 07 R021108 52594.97 Atka Old Village W ater Tank - Atka 1 1 - Apr- 08 F062408 43.95 Chungusix Beach 11 - May- 08 F071408 123.83 Nazon Beach - Atka 11 - Apr- 08 F062408 180.20 Dump Beach 11 - May- 08 F062408 257.53 Nazon Beach - Atka 11 - Apr- 08 F062408 369.73 Pu yak ix Beach - Atka 11 - Apr- 08 F062408 487.52 Pu yak ix Beach - Atka 11 - May- 08 F062408 539.17 False Pass S. Side - False Pass 17 - Jul - 08 R090109 140.12 N. Side - False Pass 17 - Jul - 08 R082609 802.44 PPSF - False Pass 17 - Jul - 08 R082609 7188.01 King Cove Airport Beach - King Cove 28 - Aug - 08 R082609 540.56 Airport Lagoon - King Cove 21 - Jul - 08 R090109 913.19 Below Esiahs - King Cove 21 - Jul - 08 R090109 1814.91 Beach Below Esiahs - King Cove 28 - Aug - 08 R082609 2284.9311

Harbor Bridge - King Cove 28 - Aug - 08 R082609 2394.26 Harbor Bridge - King Cove 21 - Jul - 08 R090109 3118 .53 Nikolski Nikolski - CoastGaurd Gate 4 - Dec - 07 R081809 150.64 Nikolski - Moan Lisa 31 - Oct - 07 R031308 156.98 Nikolski - Mona Lisa 4 - Dec - 07 R081809 227.09 Nikoski - Coast Guard 31 - Oct - 07 R030408 287.31 Nikoski - Boat Launch 31 - Oct - 07 R030408 394.82 Nikoski - Boat Launch 4 - Dec - 07 R081809 577.75 St. George East Landing - St. George 2 - Feb - 09 R082609 218.02 North - St. George 2 - Feb - 09 R082609 239.37 North - St. George 4 - Mar- 09 R090109 370.22 South - St. George 2 - Feb - 09 R082609 503.61 St. Paul St P aul - Pier Point 24 - Aug - 07 R031308 181.41

St. Paul - Outfall 27 - Jun - 07 R031308 229.65 St. Paul - Island Harbor 24 - Aug - 07 R031308 687.51 St. Paul - Island Harbor 27 - Jun - 07 R031308 834.46 **CONCLUSIONS** This project was full y successful in meeting the ob jectives. We increase d the capacity of tribal environmental staff to monitor for oil in the environment which could impact subsistence resources. We develop ed a program for monitoring the marine environment for oil from spills and other pollution events in cluding chronic releases of oil from the land, natural seeps in the ocean and spills and discharges from sea going vessels. We perform ed monitoring of the water in villages on islands neighboring to Unalaska where the Selendang Ay u oil spill occurred. Our recommendations based on the findings for the long - term prevention of oil spills & pollution in the Aleut Region. Results from the Akutan sampling lend eviden ce that the waters in most of the monitored villages are no t very contaminated with PAHs, but occa sional spills and active incinerators and outfalls continue to be a concern for pollution. We strongl y recommend continued monitoring in Al eut communities and further investigation of the possibly pollution coming from the Akutan fish processing plant. We recommend the methodology (see APPENDIX B) be followed in future PAH testing projects.12

**ACKNOWLEDGEMENTS** During this project many people offered their time, knowledge and support. Their help in making this a useful and informative project was greatly

appreciated. Thanks to: Santina Baumeister, George Bereskin, Cara Bethe , Michael Brubaker, Mark Carls, Tami Fordham , Charley (Akutan), Siri Goulette, Larry Holland, Scott Kerr , Patricia (St. George), Tyler Melovidov, Jeep Rice, Desirae Roehl, Bill y Shellikoff , Gilda Shellikoff, (Akutan) Stepenson, Andrew Zaochney and Phil Zavadil13

**APPENDIX A Standard Operating Procedures for**  **Preparing , Handling, Deploying**  **, Retrieving**  **and Shipping Polyethylene Membrane**  **Devices ( PE**  **MDs )**  **Introduction** Passiv e accumulation devices (PADs) are hydrophilic (fat loving) membranes with or without hydrophilic reservoirs and they are designed to sample non - polar hydrophobic hydrocarbons, including pol ynuclear aromatic hydrocarbons (PAH) (oil and petroleum products) and persistent organic pollutants (POPs) (contaminants like PCBs) from air, water, and sediment. A commerciall y available PAD commonly

available in the USA is the semi - permeable membrane device (SPMD); its central reservoir is triolein (e.g., Huckins et al. 1990). Hydrocarbons in SPMDs diffuse through pores in the membranes and are trapped in the central triolein matrix, mimicking uptake b y living organisms. Advantages of passive sampling are that they can sample large volumes of water, amplify trace hydrocarbon quantities (part -per - billion or part - per- trillion) to detectable levels, and average the signal over time. In addition, they are cheaper and easier to analy ze than biological tissue and can be deployed over a greater range of environmental conditions. At low ambient hydrocarbon concentrations, low - density pol yethyl ene membrane devices (PEMDs) deployed without inclusion of the central hydrocarbon reservoir are simpler and less expensive sampling devices than SPMDs, yet provide the same benefits (Carl s et al. 2004). L oss of accumulated PAH is slow, thus PEMDs reliabl y capture sporadic or fluctuating events. Composition of PAH accumulated b y PEMDs can be used to identify hydrocarbon sources in situations not complicated by multiple sources. At the Au ke B ay L aboratory , we also refer to PEMDs as LDPEs (low density pol yethyl ene devices) or PMDs (polyethyl ene membrane devices). A universal moniker has not yet been established in the literature. **Laboratory preparation** Low - density polyethyl ene tubing (98 μm × 4.9 cm × 50 cm) is sonicated twice in pentane to remove hydrocarbons, placed in aluminum samplers (11.5 diameter × 6.6 cm with perforated endplates, 3 mm holes spaced 4.8 mm apart, precleaned in dichloromethane), wrapped with two layers of aluminum foil, heat - sealed in two plastic bags, and frozen until shipment (Fig. 1; Carls et al. 2004).1415 **Caution These devices are incredibly sensitive!!! Be careful!!!**  PEMDs sample both air and water and tiny unwanted quanti ties can swamp the target signal! For example, a venting gas tank in a skiff is very bad. (Solution

– do not fill the tanks full!) The person who deploy s or retrieves the PEMDs should NOT be the same one running the engine, handling the trailer, or fiddling with gas!!! Petroleum products have a way

of migrating from hands/clothing to the PEMDs. Open the devices only when ready to deplo y without delay ; wrap and bag them without delay upon retrieval. Practice yo ur moves and carefully arrange your tools ahead of time to minimize time and the possibility

of contamination. Wear disposable gloves and change them between every set and retrieval. If available, an assistant (also with clean gloves) can open or close pails/bags. Do not allow devices to come in contact with clothing, the boat etc; it should go straight from bag to water and vice versa. Design your fastening s ys tem to work with minimal effort

– rusty

shackles that require wrenches add time and increase the odds of unwanted contamination. Any necessary

to ols should be cleaned ahead of time; this may include the boat. Oil or gas weeping from a boat will ruin samples! **Deployment & Retrieval** These s afety r

ules MUST b e followed when deploying PEMDs from a boat: 1) Leave a float plan with a friend or famil y member. 2) Two people are required to deploy PEMDs from a boat. 3) Wear a personal floatation device (PFD). 4) Take a VHF radio and make sure the battery is charged. 5) Have flares, light, or signaling device in working order. 6 ) Have enough fuel (but do n’t overfill). 7) Report to your friend upon your return. The general strategy

is to determine where the devices are to be located, deploy suitable anchors for them, then deploy sampling device . All hardware must be very clean; hydrocarbons that leach fro m anchor cable, for example, will become the sample, compromising the study. “Very clean” ty picall y means solvent - washed in the laboratory and transported appropriately (e.g., in Ziploc bags) so that hydrocarbons are not accumulated along the way . Anchors, other hardware, floats, and rope can be reused repeatedly

without further cleaning assuming that it is not contaminated during exchanges. New rope (nylon, poly prop yl ene) does not cause contamination. Do not use old rope that has an unknown history or rope that has been exposed to bilge water, etc. Rope should be placed in suitable bags (e.g., garbage or Ziploc bags) when transported to avoid contamination! The same is true for transportation of every other item and tool.16

Clean bags are acceptable storage for PEMDs, tools, & gear. Start with new clean Ziploc and garbage bags and keep them clean in other bags & in pails.

Five gallon pails are excellent for transportation and collection. Buy new ones and keep the insides clean! Stacking pails with hydrocarb ons stuck to the outside will contaminate pail insides! (Buckets can be stacked if lined with clean garbage bags.) Screw - top l ids are very useful in this context and a variety of colors is recommended buckets are easily distinguished (see Table 1 for examp le bucket contents). Two or three half - gallon plastic drinking containers placed inside can provide structure for pail s used for tools and small gear (Fig. 2). Place bagged PEMDs inside garbage bags inside pails. When open, place lids upside down (inside s howing) on the ground or other surfaces to avoid transferring potential external contamination into buckets. Keep buckets closed as much as possible. Deployment . Do not open a PEMD until you are ready to place it. Put on clean disposable gloves. Tear through the two heat - sealed Ziploc bags and remove the aluminum foil. A second person to manage the waste can be helpful, particularl y under windy conditions. Fasten the PEMD onto its anchoring device and back/drift away . (Do not contaminate newly installed d evices by

standing upstream of them, running boat exhaust by them , etc.)17

Retrieval . Retrieval is essentially the reverse of deploy

ment and should occur first when swapping. ‘Collection kits’ are needed; these are simply pre - cut aluminum foil sheets place d in Ziploc bags. Arrange collection gear to optimize efficiency and minimize time; put on clean disposable gloves. Retrieve the PEMD; this may require tools, such as wire cutters, wrenches, etc. Be sure to swirl sediment out of the canister with the water it has been in. Fold the shackle to the canister and place the PEMD at the center of an aluminum sheet; fold to cover completel y. Repeat with a second sheet, starting at the opposite side. (A helper makes this process easier, particularl y in wind. Avoid c ontact with clothing!) Then place the PEMD in a Ziploc bag; close (with as little air as practical). Place this in a second Ziploc bag. Add a label and seal. Put this package in a garbage bag inside a bucket. Depending on time and sampling circumstances, you might wish to bundle groups of PEMDs in separate garbage bags, tied shut at intervals to minimize any

possibility

of contamination. Freeze as soon as possible. Blanks. Site blanks are a necessary quality assurance technique. Open one container per sit e / trip, depending upon agreed - upon design. Expose to air about 1 minute, then re - bag, label, and freeze as above. Labels &record keeping . Make labels out of paper; “Rite in the rain” all weather paper is nice. Pre -printed labels with a minimum of nece ssary identification information are nice; keep them clean in a small Ziploc bag. Each label should have a sample number; use a pencil to write the information. Place labels outside of the inner PEMD bag and inside the second bag. A complete record of coll ection, including location and time should be kept in a separate notebook. In addition, complete chain of custody forms; these are required by the Auke Bay

L aboratory

for record keeping and processing (Table 2). **Stream deployment** Subdivide streams into oiled/polluted (ty picall y downstream) and non - oiled/non - polluted (upstream) sections. Non - oiled sites are intended to be stream - specific references. Id entify and similarl y sample matched reference streams. Where feasible, consider determining stream gradients and place samplers at the same elevation in multiple streams. Be aware, however, that stream gradients can vary considerably , thus site elevations and spacing between sites cannot always be uniform from stream - to - stream. To sample the hyporheic zone, b ury the PEMDs below the stream bed (e.g., 10 to 20 cm deep; Fig. 3; Carls et al. 2004). Sometimes stream activity will excavate buried devices. PEMDS can be anchored with duckbill anchors (attach shackle to cable with zip ties) or weighted poly

propylene me sh bags. Partially fill anchor bags with stream rock. Mark positions with GPS. Floats located downstream of the PEMD, stakes or cairns on the bank, or other identifying marks can be helpful. Photographs are also helpful for locating PEMDs. **Intertidal dep loyment**  We have successfully

used several techniques for anchoring PEMDs in intertidal areas. These include weighted bags, duckbill anchors, and expansion bolts drilled into rock. Zip ties or nylon rope are used as connectors. PEMDs can be buried or place d on the surface,18

depending on objectives. Objectives should also be considered when deciding sampler elevation. **Marine water deployment** Place anchors on poly

propylene rope in desired depth of water. Consider using chain on Danforth anchors, then rope ( Fig. 3). Alternatively , fasten the rope to the anchor and place a lead cannonball weight about 10’ up the rope: this should force the anchor to dig. When tying rope to anchors, be sure to smooth sharp edges on the anchor if present

– or use a shackle. Make eye splices with protective sleeves if possible, or reweave rope ends back into the rope several times after knotting (e.g., bowline or rewoven figure eight). Use 3/8” line or larger. Keep float sizes small to reduce lift on the anchors

– but large enough to float the hardware and big enough that you can find them. Bullet or seine floats are ok. Assuming the anchors (& other bottom hardware) are reasonabl y cl ean (consider a detergent wash) and that there are several meters between the anchor and buoy , solv ent cleaning isn’t needed. Allow enough line for tidal fluctuation, extra slack, etc. Consider weighting partway

down so it sinks to prevent navigation hazard. Gear has a better chance of surviving if placed outside the surf zone and on a broad flat shelf . Lines will eventually

part if there is too much wave energy , so inspect them periodicall y for wear. Anchors have a habit of moving around even if they initially appear to be well set; if they slide too far down a slope the buoy s will be pulled under and the gear will be lost. Deploy/retrieve sequence : set anchor, mark position with GPS. Shut engine off!!! Swing on the anchor until fumes clear from the air. **No smoking** ; it will contaminate the sampler. Onl y then, deploy (or retrieve) the PEMD. Subsurfac e deployment. PEMDs deployed below the surface are designed to assess average hydrocarbon concentrations in various water layers. We typicall y deploy 1 m below the surface to characterize this layer. The most efficient method is to pass a loop of anchor rope through the shackle on the PEMD and around the PEMD, then cinch it tight (Fig. 4). In our experience, the PEMD will stay put (not sink) on 3/8” poly propylene rope and 3/8” may

be the largest rope diameter possible for this method. To preclude sinking, c onsider hanging the PEMD from a loop attached directly to the19

buoy ; the disadvantage is that this can snarl. Another way to stop potential sinking is to place a knot in the anchor rope below the device loop. For line larger than 3/8” a second larger shac kle will be necessary (precleaned, of course). Obviousl y, a knot (e.g., butterfly) can be placed in the anchor line at the appropriate depth (e.g., 1 m below the buoy) and the PEMD can be shackled to it. Shackles can add time at retrieval and are difficult when rusty. One solution is to place a rope loop between both shackles, again passed around the PEMD. (An effective knot for making loops is the double fisherman’s bend; Fig. 5). Shackles could be potentially linked together with zip ties, but this has no t ye t been tried with this type of deploy ment and is not recommended.

Surface deployment . PEMDs deployed at the surface are designed to sample the surface microlayer. Well known is the propensity for hydrophobic compounds to accumulate in this layer, increasing the probability of detecting very

low hydrocarbon levels. A technique we previousl y used was to pass a threaded shaft through the center of the PEMD canister; floats were placed at each end of the shaft and the PEMD shackle was tied to the ancho r rope. A major disadvantage with this system was that field assembly was necessary

and slow. A suggested modification is to revise the sequence; place the two floats near the center of the shaft with a gap for a shackle; this will connect to the anchor rope (Fig 6). Place a dummy (or replicate) PEMD at one end of the shaft; place another PEMD at the other end. These will be held in place with nyl on - bushed nuts to prevent unthreading. Two nuts at each end are advisable and an ancillary rope or cable from th e PEMD shackle to the anchor line is possible.20

**Shipping** PEMDs in buckets and bagged as outlined above can be shipped via Alaska Air Freight. Indicate that the buckets are to be kept frozen. General delivery is ok under these conditions. I f freezers ar en’t working or are not available, then ship priority (or Gold Streak). **Laboratory Analysis** PEMDs are extracted with organic solvent after wiping to remove gross surface contamination. Membranes are placed in centrifuge tubes and spiked with six deuterated PAH standards (Carls et al. 2004). Spike solvent (hexane) is allowed to evaporate, then the tubes are placed in a sonic bath, and extracted in 80:20 ml pentane/dichloromethane for 130 min. The sonicator is on for the first 20 min o f each 50 min period . The PEMDs are rinsed with pentane as they were removed without delay after the final sonication. Extracts are concentrated to 20 to 30 ml, dried with 2 to 4 g of sodium sulfate , concentrated to 1 to 2 ml in hexane, and passed through 1.5 g silica gel co lumns. All extracts were spiked with an internal standard (hexamethyl benzene) and frozen pending anal ys is. Extracts are analyzed by

gas chromatography

equipped with a mass selective detector and PAH concentrations are determined b y the internal standard method (Short et al. 1996). Experimentally

determined method detection limits (MDL) are generall y 0.18 to 3.94 ng/g in PEMDs. Concentrations below MDL are considered equivalent to zero and are not reported. The accuracy of the hydrocarbon analyses is typi call y about " 15% based on21

comparison with National Institute of Standards and Technology values, and precision expressed as coefficient of variation is usually less than about 20%, depending on the PAH. Samples with questionable internal standard recoveri es (< 25% or > 150%) are ty picall y excluded from anal ys es unless the results can be independentl y corroborated b y other data. **References** Carls, M.G., L .G. Holland, J.W. Short, R. A. Heintz, and S. D. Rice. 2004. Monitoring poly nuclear aromatic hydrocarb ons in aqueous environments with passive low density pol yethyl ene membrane devices. Environ Toxicol Chem 23:1416 - 1424. Huckins JN, Tubergen MW, Manuweera GK. 1990. Semipermeable membrane devices containing model lipid: a new approach to monitoring the bi oavailability of lipophilic contaminants and estimating their bioconcentration potential. Chemosphere 20:533 - 552. Short JW, Jackson TJ, L arsen ML, Wade TL. 1996. Analy tical methods used for the anal ys is of hydrocarbons in crude oil, tissues, sediments, and seawater collected for the natural resources damage assessment of the Exxon Valdez oil spill. Am Fish Soc Sy

mp 18:140 - 148. Table 1. Example equipment and supply lists, arranged by

bucket. Buckets with colored screw - top lids are one convenient way to transport gear and retrieve PEMDs. A fourbucket sy stem is used in this example, each dedicated to a specific purpose. On a first trip, an installation bucket with appropriate gear might be substituted for the pickup kit. Yellow Red **Pickup kit Equipme**  **nt kit** field notebook YSIsalinity,

temperature meter labels Sonar (handheld) Aluminum foil GPS Disposable gloves VHF radio Ziploc bags pens, pencils,

markers garbage bags, large, black knife garbage bags, small, white wrench(es) nut driver cutters Blue wire cutters **PEMD deployment kit**  screw drivers New PEMDs spare batteries marlinspike or fid or plastic stake22 White **PEMD retrieval kit** garbage bags retrieved PEMDs **Supplies Quantity**  **Cost per unit Total**  gloves 3 b oxes samplers 21 Provided by ABL **0** 1” poly line 2,100 feet buoys 9 40# anchors 9 10# lead balls 9 Misc. hardware Line eyes,

small rope, shackle, etc . **~$250** Float coat PFD 6 write - in - the - rain notebook 3 write - in - the - rain pens 12 s harpies 6 Sample shipping supplies (boxes, tape, etc) For 18

shipments C oolers /buckets 323

Table 2. Example chain of custody form required by

the Auke Bay

L aboratory

as a data record and for anal ytical processing.24

**APPENDIX B** Year 2 study de sign altered significantly to overcome severe weather conditions and to insure safety of local staff. Shore - based sampling will replace the offshore sampling. Shipping problems have been overcome with implementation of closel y monitored tracking. **Oil Spil l Capacity Building, Preparedness and Monitoring Project**  **Standard Operating Procedures for Handling, Deploying, Retrieving and Shipping Polyethylene Membrane Devices (**  **PEMDs) Introduction**  Passive accumulation devices (PADs) are hydrophilic (fat loving) membranes designed to sample non -polar hydrophobic hydrocarbons, including pol ynuclear aromatic hydrocarbons (PAH) (oil and petroleum products) and persistent organic pollutants (POPs) (contaminants like PCBs) from air, water and sediment. Advantages of pa ssive sampling are they

can sample large volumes of water, amplify trace hydrocarbon quantities (parts -per- trillion) to detectable levels and average the signal over time. In addition, they

are cheaper and easier to anal yz e than biological tissue and can b e deployed over a greater range of environmental conditions. The PAD we will be using contains a polyethylene membrane and is called a polyethyl ene membrane device (PEMD), but it is often referred to as a ‘puck’ (Figure 1). **Deployment & Retrieval** Low - density polyethyl ene sampling material is placed in the pucks, wrapped with two layers of aluminum foil, heat - sealed in two plastic bags and frozen until shipment (Fig. 1; Carls et al. 2004). They

will be shipped in a 5 gallon plastic bucket. Auke Bay L ab sc ientist L arry

Holland will prepare 5 of these devices for each bucket. The contacts at Auke Bay

L ab are Larry

Holland (telephone 907 - 789 - 6083 and e - mail larry .holland@noaa.gov) who is a chemist and Mark Carls (telephone 907 - 789 - 6019 and e - mail mark.carls@noaa.gov) who is a biologist.25

PEMDs sample both air and water and tiny unwanted quantities of contaminants can swamp the target signal. For example, someone smoking a cigarette nearby can damage the PEMD. **So be cautious, these devices are incredibly sensitive!!!** Petroleum products have a way

of migrating from hands and clothing to the PEMDs. Open the PEMDs protective plastic and foil only when ready

to deploy witho ut delay ; wrap and bag them without delay

upon retrieval. Practice your moves and carefull y arrange yo ur tools ahead of time to minimize time and the possibility of contamination. Wear disposable gloves and change them between every set and retrieval. Do n ot allow devices to come in contact with clothing; it should go straight from bag to the rock and vice versa. Bruce Wright, the APIA project manager, will assist in establishing the sampling sites and anchoring locations. You will be trained how to deplo y and retrieve the pucks without contaminating them. The only tool you need is a clean wrench. This will be provided. You will be provided with wrenches, write in rain paper labels, pencils, indelible ink markers, 1 gallon Ziploc bags, chain of custody for ms (coming from ABL w/PEMD), latex gloves and aluminum foil in Ziploc bags. Five gallon pails are excellent for transporting and collecting PEMDs. When open, place lids upside down (inside showing) on the ground or other surfaces to avoid transferring pot ential external contamination into buckets. Keep buckets closed as much as possible. Do not open a PEMD until you are ready to place it. Put on clean disposable gloves. Tear through the two heat - sealed Ziploc bags and remove the aluminum foil. A second person to manage the waste can be helpful, particularl y under windy conditions. Fasten the PEMD onto its anchoring. **Retrieval and Deployment: Monthly Sampling** Retrieval is essentially

the reverse of deploy

ment. ‘Collection kits’ are needed; these are simpl y pre - cut aluminum foil sheets placed in Ziploc bags. Arrange collection gear to optimize efficiency

and minimize time; put on clean disposable gloves. Retrieve the PEMD using the wrench. Disconnect the redundant safety cable. (see Figure 3).26

Figure 2 . Puck mounted to bedrock and attached redundant cable also mounted to bedrock. Be sure to flush sediment out of the canister with seawater. Fold the shackle to the canister and place the PEMD at the center of an aluminum sheet; fold to cover completely . Repeat with a second sheet, starting at the opposite side. (A helper makes this process easier, particularly in wind. Avoid contact with clothing! ) Then place the PEMD in a Ziploc bag; close (with as little air as practical). Place this in a second Ziploc bag. Add a label and seal (The labels can be prepared before going into the field and contain the following information: date, location, operator and notes such as contamination problems). Put this package inside the bucket. Ship the bucket as soon as poss ible (address/shipping label below). During each trip to each sampling station you should inspect the sampling apparatus for corrosion and wear. Alert Bruce Wright if you believe there is a problem. Clean any biofouling (kelp, algae, barnacles, mussels, etc.) from the sampling apparatus. Field Blanks.. Field or s ite blanks are a necessary quality assurance technique. Open the plastic bags and remove the foil layers, expose to air about 1 minute, then re - bag and label. Label the field blank. Any of the p ucks can be used as a field blank or trip blank. Trip Blanks. Any

of the pucks can be used as a field blank or trip blank. Carry the trip blank with you, in the bucket with the samples and field blank. Don’t open or deploy the trip blank. There is no need to label the trip blank; it just rides along and insures the chemist back at Auke Bay L ab that clean procedures are being followed and the samples are not being compromised. **Never open the trip blank!**27

Labels &record keeping . Make labels out of paper; “Rite in the rain” all weather paper is nice. Pre -printed labels with a minimum of necessary identification information are nice; keep them clean in a small Ziploc bag. Each label should have a sample number, location, operator and date; use a pencil to writ e the information. Place labels outside of the inner PEMD bag and inside the second bag. A complete record of collection, including location and time should be kept in a separate notebook. The chain of custody

forms will be included in the bucket. The ch ain of custody form is required b y the Auke Bay Laboratory for record keeping and processing (example: Figure 3). Complete these forms after recovering the PEMDs from the field. Include as much information as you can, although you may not be able to complete all categories indicated. Make a cop y of the chain of custody for your files and send the original back to Auke Bay

L ab in the same bucket as the 5 PEMDs. **Shipping** Put PEMDs in bucket and bagged as outlined above. The bucket should be shipped via prio rity U.S. Mail. Ship collect or, if you pay for shipping, keep the receipt so you can get reimbursed. The shipping labels are below.

**References** Carls, M.G., L .G. Holland, J.W. Short, R. A. Heintz, and S. D. Rice. 2004. Monitoring poly nuclear aromatic hydrocarbons in aqueous environments with passive low density pol yethyl ene membrane devices. Environ Toxicol Chem 23:1416 - 1424. Short JW, Jackson TJ, L arsen ML, Wade TL. 1996. Analy tical methods used for the anal ys is of hydrocarbons in crude oil, tissues, sediments, and seawater collected for the natural resources damage assessment of the Exxon Valdez oil spill. Am Fish Soc Sy

mp 18:140 - 148.28

**Table 1.** Supplies needed for deplo ym ent and retrieval of PEMDs: new PEMDs (5) aluminum foil disposable gloves ( large) wrenches Attachment supplies pencil chain of custody forms Ziploc bags **Table 2. OIL MONITORING CONTACTS**

**ALEUTIAN PRIBILOF ISLANDS ASSOCIATION** Primary Contact: Bruce Wright, Senior Scientist Address: 1131 E. International Airport Rd. , Anchorage, AK 99518 Telephone: (907) 222 - 4260 or (800) 478 - 2742 Fax: (907) 222 - 4273 Email: brucew@apiai.org

**AUKE BAY LAB** Primary Contact: Larry

Holland, Chemist Secondary

Contact: Mark Carls, Bio logist Address: 17109 Pt. L ena Loop Road ,Juneau, AK 99801 Phone: (907) 789 - 6083 or (907) 789 - 6019 Fax: (907) 789 - 6094 Email: larry .holland@noaa.gov & mark .carls@noaa.gov29

**APPENDIX C** This is the document used to track deplo ying, retrieving and shipping the sampling devices, and interactive document. **Oil Monitoring Project Contacts, Schedule and Tracking Akutan:**  George Bereskin, PO Box 4, Akutan, 99553, 698 - 2399 (city office 698 - 2228) 1 st deployed 3/12/07, 1 st received ABL 4/18/07 2 nd deployed 5/1/07, 2 nd pulled 6/5/07 and shipped to ABL on 6/6/07, arrived ABL on 6/13/07. **Atka:** Andrew Zaochney. PO Box 47031, Atka, AK 99547, 839 - 2233 (office), 839 - 2208 (home), 301 - 2197 (mobile), andrewz@gci.net 1 st deployed 3/11/08, 1 st pulled 4/11/08, 1 st received ABL 4/16/08 2 nd deployed 4/11/08, 2 nd pulled 5/12/08. **False Pass** : Gilda Shellikoff, Tribal Administrator, PO Box 29 False Pass AK 99583, (907) 548 - 2227, fax (907) 548 - 2256, falsepasstc@gci.net (Bill y Shellikoff 548 - 2207) (Siri Goulette 548 - 2226) 1 st and ONLY deplo yed 6/16 - 6/17/08,1 st pulled , and 1 st received ABL . **King Cove** : Desirae Roehl, 497 - 2648, des_atcenvironment@yahoo.com , ATC, PO Box 5, King Cove, AK 99617 1 st deployed 6/21 - 6/22/08, 1 st received ABL 7/18/08 2 nd deployed 7/22/08, 2 nd pulled and shipped to ABL on 8/28/08 . **Nikolski:** Scott Kerr , A leutian I sland Adventures **,** PO Box 10 Nikolski, AK 99638 ( 576 - 2239) 1 st deploy ment 10/1/07, pucks picked up 10/31/07 and mailed to ABL. 2 nd bucket sent 10/24/07, pucks deplo yed 11/1/07 and picked up and sent to ABL 12/5/07. **St. George:** Patricia 85 9 - 2403. 1 st deployed January

3, 2009, 1 st received ABL 2 nd deployed February

3 (?), 2009 , 2 nd pulled, and shipped to ABL on ,arrived ABL on . **St. Paul:** Tyler Melovidov (546 - 2502), Phil Zavadil (546 - 3230 pazavadil@tribaleco.c om) 1 st deploy ment 5/16/07. 1 st deploy

ment pulled 6/27/07 and arrived ABL 7/5/07. 2 nd deploy

ment pucks arrived ABL 7/11/07 (2 days shipping). Puck deplo yed 7/24/07 and picked up and sent to ABL on 8/24/07. Arrived ABL on 8/27/07.