2.2 Field Collections Members of the field sampling crew had a range of experience in marine and contaminants sampling and in Cook Inlet. Due to intense field commitments elsewhere, most field participants could only participate for a portion of the field season. However, the schedule was arranged so that at least two personnel (and usually three) who were fully trained together at the beginning of the field program were onboard the vessel at all times. This ensured sampling consistency across the entire one-month training and sampling period that took place from 1-30 August 2010. One person was onboard the vessel for the entire sampling period and oversaw compliance with field sampling protocols that were finalized during the training period. The field personnel demonstrated individual and team proficiency during training that took place during the first several days of sampling in Kachemak Bay. Additional team members who rotated onboard at later dates were trained and evaluated by the existing scientific crew to ensure consistent sampling. Field training was led by the Lead Scientist for Alaska’s Gulf of Alaska EMAP efforts in 2002 and 2004 to ensure that the information and data gathered will be compatible with prior EMAP efforts. 2.2.1 Benthic Sediment Sampling The Integrated Cook Inlet Environmental Monitoring and Assessment Program (ICIEMAP) adopted the standards of the National Coastal Assessment Quality Assurance Project Plan (USEPA 2001) for sediment collections. Sediments are collected for numerous analyses; benthic species composition and abundance, sediment organic and inorganic chemical analyses, grain size analyses, and total organic carbon. Young-modified Van Veen grabs were used to collect sediments. When deployed from the R/V Island C (most stations >5m depth), a double Van Veen grab (two side-by-side 0.1 m2 grabs) was used for most stations, requiring fewer deployments to collect sufficient sediments for all analyses. Periodically a single Van Veen grab sampler (0.06 m2) was attempted to see if it could more successfully obtain sediments at difficult stations. For the shallower nearshore stations, the single Van Veen grab was used as it was easier to deploy from the skiff. All metal parts of the Van Veen grab were fabricated from stainless steel components. The grab was thoroughly scrubbed with Alconox prior to use at each station, then rinsed with ambient seawater. On retrieval, the hinged top was opened to determine whether the sample was successful. A successful grab had relatively level, intact sediment over the entire area of the grab and a sediment depth of preferably not less than 7 centimeters in the center. Grabs with disturbed sediments or where the original surficial sediments were not intact were not accepted. Sediments were processed for either sediment chemistry or benthic community analysis as described below. The first successful grab was used for sediment chemistry. Once the overlying water was siphoned off using pre-cleaned Tygon tubing (Alconox and seawater rinse) and sediment conditions were recorded (e.g. depth of penetration, odor, color, texture), the top 3 cm of sediments were collected as follows. Using an Alconox cleaned stainless steel spoon, 175 to 200 ml of sediment was transferred to a 250 ml I-Chem jar, sealed, and labeled for sediment organic analyses. A duplicate jar was filled, sealed, and labeled for Archiving. Approximately 150 ml of sediments were transferred to a whirlpack, sealed, and labeled for sediment grain size analyses. Approximately 100 ml of sediments was transferred to a 125 ml I-Chem sample jar using an Alconox cleaned plastic spoon, sealed, and labeled for sediment metals analyses. All samples were immediately transferred to appropriate storage conditions (Table 2.2-1) until shipped to the appropriate analytical laboratories (Table 2.2-2). Table 2.2-1. Sample containers, storage, and holding procedures for benthic sediment samples. Sample Type Container Field and Lab Holding/Storage Max. Holding Sediment Organics [Hydrocarbons (PAHs and Aliphatics) and POPs] Pre-cleaned IChem jars Freezer (-20oC) 1 year Sediment Metals Pre-cleaned IChem jars Freezer (-20oC) 1 year* Refrigerator (4oC) 7 days Water Column BTEX Pre-cleaned 40 ml Refrigerator (4oC) VOA bottles 7 days Water Column Metals Ultra-clean Teflon-coated bottles Particulates: Filter and Freeze (-20oC) 6 months Total Organic Carbon Pre-cleaned IChem jars Freezer (-20oC) 1 year Grain Size Whirlpacks Refrigerator (4oC) 1 year Sediment and Water Column Contaminants: Water Column Hydrocarbons 1-liter Pre(PAHs and TAH) cleaned Boston Brown I-Chem jars Dissolved: Filter and Preserve Sample Type Container Field and Lab Holding/Storage Max. Holding Chlorophyll a 25 mm GF/F in HDPE snap-tube Freezer (-20oC) 6 months Nutrients 60 ml Nalgene bottle Freezer (-20oC) 6 months Total Suspended Solids (TSS) 47 mm preweighted GF/F in petri dish Freezer (-20oC) 3 months 100-1000 ml wide-mouth Nalgene 10% buffered formalin and final transfer to isopropyl alcohol Indefina tely Water Quality: Biota: Benthos (0.5 and 1.0 mm sieved) Table 2.2-2. Laboratories contracted for analytical procedures for the identified parameters. Laboratory TDI Brooks International 1902 Pinon, College Station, TX 77845 Phone: (979) 693-3446 Fax: (979) 693-6389 Florida Institute of Technology College of Engineering, Department of Marine and Environmental Systems 150 West University Blvd. Melbourne, FL 32901-6975 Contact: Dr. John Trefry 321-674-7305 Dr. Alan Fukuyama 7019 157th SW Edmonds, WA 98026 Contact: 425-745-3349 University of Washington School of Oceanography Box 357940 University of Washington Parameter Sediment Organics, Sediment TOC, Sediment Grain Size; Water Column Organics Sediment Metals; Water Column Dissolved and Particulate Metals; Fish Tissue Metals Benthic Invertebrate Sorting, Taxonomy, and Abundance Nutrients, Chlorophyll-a, Total Suspended Solids Seattle, WA 98195 Contact: Kathy Krogslund SeaBird Electronics 1808 136th place NE Bellevue, WA 98005 Contact: 425-643-9866 CTD and Sensor Calibrations Figure 2.2-1 shows the site names and locations where sediment sampling was either unsuccessfully attempted or where sediments were successfully obtained. Also shown is the number of attempts made at each location before the site was abandoned or until sediments were successfully obtained. The range in attempts reflect the type of habitat encountered or whether sampling was attempted in areas of high tidal currents when sampling efforts were limited to a short window of time during the slackest parts of the tidal cycle. To minimize damage to the sensitive “biting” edges of the Van Veen grabs, if it was clear there was rocky habitat at the target site and in the nearby areas, the site may have been dropped after only one attempt. The map clearly shows that it was more difficult to find sampleable habitat in the deeper channels and more tidally swept areas compared to many nearshore areas where the currents are not as strong and there are often eddies to deposit finer particles. Table 2.2-3 lists the sampling locations where sediments were successfully collected for either sediment chemistry or benthic infaunal analyses. The latitudes and longitudes reflect the location of the first successful grab at that station. If more than one deployment of the either single or double Van Veen grab was required to obtain the sediments for analyses, subsequent locations were also noted on the data sheet, but are not reported in table 2.2-3 as they were sampled as close to the original location as possible. Table 2.2-3 is organized to reflect design strata and that will be used for subsequent statistical comparisons among and between sampling areas to address the goals of ICIEMAP. These strata include the Cook Inlet EMAP strata (CIEMAP) - or non-industry Cook Inlet sampling area, the Trading Bay Production Facility mixing zone strata (TB Mixing Zone), the East Forelands Treatment Facility mixing zone strata (EF Mixing Zone), and the Oil Industry Area strata. Also listed in Table 2.2-3 are locations of additional sampling sites for the NS&T study in Kachemak Bay and sites were opportunistic sampling took place for benthic sediments in areas of interest (Supplemental). These sites were not part of the original sample design (Section 2.1) and were not used for statistical comparisons, except as noted in individual chapters. Kathleen – this is where Allan’s section on benthic sampling should be that you have already formatted for Chapter 2…Delete that whole section because it has been incorporated within the methods described below. A new table was made that incorporated both types of sediment sampling. But, keep the map that was part of that sampling… If both sides of a double Van Veen grab successfully collected sediments, the other sample was retained for benthic invertebrates. If not, additional deployments of the Van Veen grab were conducted until a successful benthic sediment sample was obtained. For each successful invertebrate sample obtained, the sediments were gently sieved through a 1.0-mm sieve. The five samples collected from Kachemak Bay were sieved through stacked 0-5-mm and 1.0-mm sieves. All animals and debris left on the sieve were immediately transferred to plastic jars with both internal and external labels with station identification information, preserved with a 10% formalin solution, and sealed. After a minimum of 72 hours, samples were re-screened through a 0.5-mm sieve, gently rinsed with saltwater and preserved in a 70% isopropanol solution with Rose Bengal added. All benthic samples were shipped to the sorting and taxonomy laboratory shown in Table 2.2-2. Figure 2.2-2 shows locations of successful sediment collections for benthic invertebrate analyses – indicating the Van Veen grab size that was used. The grab size later normalizes the surface area so that invertebrate abundance data can be normalized and reported on a per area basis. A total of 44 stations had samples collected for benthic invertebrate analyses (Figure 2.2-2). One of the stations (Station 007) was used only for presence/absence of species as the sample did not meet quality standards. Of the 43 stations used for benthic community analyses, 12 came from the Cook Inlet Oil Industry strata and 31 stations were from outside of the industry area. Insert Table 2.2-3 Here Figure 2.2-1. Number of sediment sampling attempts before either abandoning a site or until a successful sediment sample was obtained. Figure 2.2-2. Map of all stations successfully sampled for benthic infaunal analyses. Note two different grab sizes and the one station used only for presence/absence data. Numbers reflect station names. 2.2.2 Water Column Sampling A range of water quality measurements and collections were made at each station. Some of these measurements were done using a Conductivity-Temperature-Depth (CTD) instrument that measures conductivity (salinity) and temperature with depth, as well as ancillary sensors that measure turbidity, pH, and dissolved oxygen (DO). Other water quality measurements were made by collecting water samples from the water column for shipboard or laboratory processing and analyses (pH, Total Suspended Solids (TSS), chlorophyll-a, and nutrients). At a subset of all stations, water column contaminant samples were collected. Table 2.2-4 lists stations where the various water column samples were collected. The table lists only stations where at least one sample of the parameter listed was collected, but does not reflect multiple samples collected at each station for different depths (see individual chapter results). Specific latitude and longitude data are reported in the Appenices, but sample locations were tied as close as possible to where sediment grabs were collected (Table 2.2-3), although for some collections significant vessel drift during the water column sampling took place and the locations plotted on maps reflect slight differences in locations. Insert Table 2.2-4 somewhere after this paragraph where it fits… 2.2.2.1 CTD Profiling Continuous water column profiles were taken at each site using a Conductivity Temperature and Depth (CTD) instrument with additional sensors. A Seabird SBE 19 CTD with ancillary SBE43 DO sensor, a SBE 18 pH sensor, and a D&A Instruments optical backscatter sensor was programmed to sample every 0.5 seconds. The instrument was allowed three minutes of warmup while at the surface and was lowered at a rate of one meter per second or less during the down-cast and up-cast. Near bottom conditions were measured as close to one meter off of the bottom as possible. Data were uploaded to a computer immediately after each cast using Seabird SeaTerm software. The hex files for each cast were named by the station number and backed up to disk. Seabird’s Seasave software was used to view data. The *.con conversion and calibration file associated with the CTD unit was 376AUG08.con and was used to convert the data from hexadecimal stored voltages into proper engineering units that incorporate calibration information for the CTD data. Periodic checks of the Dissolved Oxygen readings from the CTD were done using a LaMotte water sampling titration kit and daily checks of pH were conducted using Orion 3 Star Model pH meter with a 9107BNMD Triode. In the event that the optical backpscatter sensor failed, a secchi depth was recorded at each station, as well. 2.2.2.2 Discrete Water Quality Sampling Water samples were collected at each site for pH, chlorophyll-a, dissolved nutrients, and Total Suspended Solids (TSS) analyses. At most stations, samples were collected at three depths; surface, mid-water, and bottom. At stations where the depth was less than 10 m, only surface and bottom samples were collected. These samples were collected at all stations for the Cook Inlet background and the Cook Inlet Oil Industry strata. Processing of these samples can take up to an hour per station and due to the limited time between sampling stations when conducting the intense water column sampling within the mixing zone strata, they were collected at only a few stations within the Mixing Zone strata during the intense water column sampling period. Since these data were collected to provide general oceanographic conditions in the Inlet and not to compare strata, the CTD data collected at all sites provided the higher spatial resolution oceanographic data for interpreting water column contaminants. Water grab samples were collected with wire-cast 5.0 L polycarbonate Niskin bottles at the surface (~0.5 m), mid-water, and near the bottom (~1 m above bottom). If the depth at the station was less than 10 m, water samples were collected only at the surface and bottom. The Niskin bottles were rigged for wire-casts and triggered to sample at depth using messengers. After the Niskins bottles were retrieved to the surface, water was collected into the appropriate sample containers (each pre-rinsed three times with the sample water) for the following analyses as follows: 2.2.2.2.1 Chlorophyll a Chlorophyll a samples were filtered within one hour after collection A 25 mm filter rack was used with a vacuum pressure less than 12 psi to minimize cell lysis. The volume of water required to turn the 25 mm GFF filter green was recorded. A standard volume was not used as the suspended sediment loads affected the volume that could be realistically filtered. The filter was removed using forceps, folded with the pigment side on the inside of the fold, and placed into a prelabeled, disposable screw-top polypropylene tube. The tube was wrapped in aluminum foil, labeled with the station and sample name, and stored as identified in Table 2.2-1 until shipped to the laboratory identified in Table 2.2-2. 2.2.2.2.2 Dissolved Nutrients Up to 50-ml of sample filtered through a 0.45 micron filter and collected into a pre-labeled, clean 60-ml polyethylene screw-capped bottle which was labeled with sample depth, sample ID, bottle number and date. The bottle and cap was rinsed 3X with the filtered water before it was filled and labeled. The salinity for each sample was recorded to be provided to the analytical laboratory for adjusting their procedures to the appropriate salinity. The bottles were stored as identified in Table 2.2-1 until shipped to the laboratory identified in Table 2.2-2. 2.2.2.2.3 Total Suspended Solids Up to one liter of seawater was collected for TSS at each water sampling depth and filtered through a pre-weighed, numbered 25-mm GF/F filter. A sufficient amount of the sample was filtered until the filter was almost clogged. The total volume varied at each station depending on the amount of suspended sediments in the water. In areas with high TSS, such as upper Cook Inlet, relatively small (<100 ml in some cases) volumes were filtered. After filtration, the filter was removed with forceps and stored in the original container (flat petri-type dish) that the preweighed filter was removed from. These containers were pre-numbered and correlated to the known weights of each filter for subsequent laboratory analyses. The filters were stored in dark, frozen conditions until prepared for analysis at the University of Washington. The filters were stored as identified in Table 2.2-1 until shipped to the laboratory identified in Table 2.2-2. 2.2.2.3 Discrete Water Column Contaminant Sampling In addition to the hydrographic profiles and benthic sediment collections, at each of the 37 sites that fall within the CCI and Mixing Zone Areas and at several stations in the Cook Inlet Background strata, water column samples were collected for contaminant analyses. Station sampling locations are described in detailed in Chapter 4 for water column metals and Chapter 5 for water column organics. 2.2.2.3.1 Seawater Organics At all of the framework sites that fell within the Cook Inlet Oil Industry Area and Mixing Zone strata, and at 7 background Cook Inlet EMAP sites, samples for Total Aromatic Hydrocarbons (TAH) and Polynuclear Aromatic Hydrocarbons (PAH) were collected in one of two ways into 1 liter pre-cleaned Boston Brown I-chem bottles. Surface samples were directly collected by holding the I-chem bottle under the surface at 0.5 m until full. At mid-water depths and at one meter off the bottom, samples were collected using a Valscom sampling device, which allows the I-chem bottle to be lowered to depth and then seals the lid before the device is retrieved to the surface. The device seals the bottle in a way that no water can be released or introduced as it is raised from its sampling depth. Once onboard, small amounts of water were transferred to BTEX sampling jars as described below. The Boston-brown I-Chem bottles were labeled, sealed, and as identified in Table 2.2.1-1 until shipped to the laboratory identified in Table 2.2.12 within 7 days. At all framework sites that fell within the Cook Inlet Oil Industry Area and Mixing Zone strata and at one background Cook Inlet EMAP site, water samples were collected for analyses of benzene, toluene, ethylbenzene, and xylene (BTEX). Sampling for BTEX was concentrated in oil industry areas, specifically within the mixing zone areas, as they are extremely volatile compounds compared to TAH and PAH. Samples were be collected into pre-cleaned sample bottles by filling completely to ensure no headspace or air bubbles and stored in a refrigerator until shipped to the laboratory. 2.2.2.3.2 Seawater Metals At all of the framework sampling sites that fell within the Cook Inlet Industry Area and Mixing Zone strata, and at one Cook Inlet Background station, water samples were collected for water column metals analyses into pre-cleaned bottles. Different sample bottles were used for Hg and other trace metals. Low-density polyethylene (conventional polyethylene) bottles of 1-L or 2-L volume were chosen for trace metal sampling (excluding Hg) due to their low metal content and flexibility relative to high-density (linear polyethylene). New bottles were acid-washed prior to use. The bottles were first filled with hot, concentrated (16 N), trace metal grade, nitric acid for a minimum of 12 hours followed by two 12 to 24 hour reconditioning rinses with 18 megohmresistivity distilled water. The final rinse was decanted within a Class-100 laminar flow hood where the empty bottle was sealed inside a heavy duty plastic bag for storage in lots of 2 to 6 within a second larger plastic bag. Sample bottles that were previously used to hold seawater or freshwater were cleaned and reused; however, containers that previously held produced water or water with a high organic carbon concentration were discarded after a single use. A reused sample bottle was first rinsed repeatedly with a high pressure distilled water jet and then inspected for residual solids or discoloration. If either condition was present, the bottle was discarded. Detergents or brushes with metal components were never used in the cleaning process. Containers to be used for Hg were made of Teflon (PFA formulation, 500-mL) with high-torque, tight fitting screw caps. The cleaning procedure and restrictions for use were the same as for low-density polyethylene bottles with the exceptions described below. Used bottles were filled with a 10% v/v solution of trace metal grade hydrochloric acid for a minimum of 12 hours, followed by a 12-24 hour distilled water rinse before being acid-washed with nitric acid as above. After the second distilled water rinse was discarded, the bottle was refilled with a third distilled water rinse and acidified to 1% v/v with Ultrex II (J. T. Baker, Inc.) or similar ultra high purity hydrochloric acid and then double bagged in heavy duty plastic for storage in lots of three within a third heavy duty plastic bag. Water samples were collected by pumping water through clean Teflon tubing using a peristaltic pump. All personnel involved with the sampling process wore plastic gloves. The tube was fitted with a Teflon weight and lowered to the desired depth and a volume of water equal to two tube volumes was pumped and discarded. Then, the sample bottle was rinsed twice and filled. For each successive depth, the tube was lowered and the rinsing of the tube and bottle were repeated. 2.2.2.3.3 Produced Water Samples During the roughly ten-day sampling period when water column contaminant samples were collected from the Cook Inlet Oil Industry and Mixing Zone strata, six unique samples of pure undiluted effluent from each facility to represent “end-of-pipe” concentrations were collected by Chevron and XTO Energy personnel. Four produced water samples were collected from in-line at the Trading Bay Production Facility prior to discharging and two samples were collected from the East Forelands Treatment Facility. Samples were collected directly into the appropriate precleaned sampling jars as described above for BTEX, PAH, and metals. These samples were necessary to the ICIEMAP, especially for the Produced Water Fates Study, to provide background on the discharge concentrations and fingerprints. 2.2.2.3.4 River Samples In May and September 2009, water samples were collected from 18 rivers to look for natural sources and potential anthropogenic sources of hydrocarbon and metal contamination to Cook Inlet. Water was collected into the appropriate pre-cleaned sampling jars as described above for BTEX, PAH, and metals. Rivers were accessed by helicopter and were sampled above tidal influence. Samples were collected by wading into the river until the sampler was standing in the main flow. Wearing gloves, the collector held each sample bottle facing upstream and underneath the surface until the bottle was full. BTEX bottles were carefully filled from the Boston brown I-Chem bottles filled with river water for PAH analyses. All bottles were labeled and immediately placed in a cooler and shipped within 24 hours to the appropriate laboratory identified in Table 2.2-2. Rivers sampled in early May 2009 included the Chinitna, Drift, Big, McArthur, Beluga, Susitna, Matanuska, Kasilof, and Kenai Rivers. Rivers in the Kamishak Bay area of Cook Inlet were still too frozen to sample in May. Rivers sampled in September 2009 included the Douglas, Kamishak, McNeil, Fox, Bradley, and Grewingk Rivers. 2.2.2.3.5 Summary Sampling Locations Due to nature of ICIEMAP, where the goals of multiple studies were coordinated to share sampling and analytical resources, the samples collected were not the same at every site. More detail on specific sampling locations are presented in Chapters 3, 4, 5, 6, and 7, where the results of the various parameters and studies are presented and discussed in detail. A less detailed depiction of where various types of samples were collected is provided in Figure 2.2-3. Specific site information can also be obtained from the Appendices. Figure 2.2-3. Locations of different samples collected during ICIEMAP. Numbers represent station names.