Marine Offshore and Beach Water Monitoring: Sampling and ... · The tasks involved in sampling and...

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Marine Offshore and Beach Water Monitoring: Sampling and Analysis Plan May 2020 Alternate Formats Available 206-477-4800 TTY Relay: 711

Transcript of Marine Offshore and Beach Water Monitoring: Sampling and ... · The tasks involved in sampling and...

Page 1: Marine Offshore and Beach Water Monitoring: Sampling and ... · The tasks involved in sampling and analysis of marine offshore and beach waters and the personnel responsible for those

Marine Offshore and Beach Water Monitoring:

Sampling and Analysis Plan

May 2020

Alternate Formats Available 206-477-4800 TTY Relay: 711

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Marine Offshore and Beach Water Monitoring: Sampling and Analysis Plan Submitted by: Kimberle Stark King County Water and Land Resources Division Department of Natural Resources and Parks

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Marine Offshore and Beach Water Monitoring: Sampling and Analysis Plan

King County Science and Technical Support Section i May 2020

Citation King County. 2020. Marine Offshore and Beach Water Monitoring: Sampling and Analysis

Plan. Prepared by Kimberle Stark, Water and Land Resources Division. Seattle, Washington.

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King County Science and Technical Support Section ii May 2020

Table of Contents Acronyms and Units of Measurement ........................................................................................................... v

1.0 Introduction .............................................................................................................................................. 1

1.1 Project Background ........................................................................................................................... 1

1.2 Project Goals ........................................................................................................................................ 2

1.3 Project Staff and Responsibilities ................................................................................................ 3

2.0 Sampling Design ...................................................................................................................................... 4

2.1 Sampling Area ..................................................................................................................................... 4

2.1.1 Sampling Area Characteristics ................................................................................................ 4

2.2 Sampling Strategy .............................................................................................................................. 5

2.2.1 Offshore Station Locations and Sampling Frequency .................................................... 5

2.2.2 Beach Station Locations and Sampling Frequency ......................................................... 9

2.2.3 Field and Laboratory Parameters ........................................................................................11

2.2.4 Data Quality Objectives ............................................................................................................13

2.2.5 Measurement Quality Objectives .........................................................................................14

3.0 Field Sampling Procedures ...............................................................................................................17

3.1 Station Positioning ..........................................................................................................................19

3.1.1 Offshore Water ............................................................................................................................20

3.1.2 Beach Water .................................................................................................................................20

3.2 Sampling Equipment and Procedures .....................................................................................21

3.2.1 Offshore CTD Water Collection .............................................................................................21

3.2.2 Offshore Discrete Water Collection.....................................................................................23

3.2.3 Beach Water Collection ............................................................................................................23

3.2.4 Thermosalinograph (TSG) Data Collection ......................................................................24

3.3 Equipment Decontamination ......................................................................................................24

3.4 Sample Handling Procedures ......................................................................................................24

3.4.1 Sample Storage and Holding times .....................................................................................24

3.4.2 Chain of Custody Procedures ................................................................................................27

3.4.3 Sample Documentation ............................................................................................................27

4.0 Laboratory Procedures .......................................................................................................................30

4.1 Quantitation Limits .........................................................................................................................30

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4.2 Fecal Indicator Bacteria .................................................................................................................31

4.3 Water Clarity and Salinity .............................................................................................................32

4.4 Nutrients .............................................................................................................................................32

4.5 Phytoplankton Pigments ...............................................................................................................33

4.6 Organic Carbon .................................................................................................................................33

4.7 Dissolved Oxygen .............................................................................................................................33

5.0 Quality Control .......................................................................................................................................34

5.1 Field Instrument Calibration and Maintenance ...................................................................34

5.1.1 Laboratory Equipment Calibration and Maintenance .................................................35

5.2 Field Blanks and Replicates .........................................................................................................35

5.2.1 Field Filtration Blank ................................................................................................................36

5.2.2 Field Replicate .............................................................................................................................36

5.3 CTD Hydrocast Quality Control ..................................................................................................36

5.4 Laboratory Quality Control Samples ........................................................................................37

5.5 Corrective Action Procedures .....................................................................................................39

6.0 Data Management and Reporting ...................................................................................................40

6.1 CTD Hydrocast Data ........................................................................................................................40

6.2 Data Storage .......................................................................................................................................40

6.3 Data Validation and Usability ......................................................................................................41

6.4 Data Reports ......................................................................................................................................43

7.0 Training and Safety Protocols ..........................................................................................................44

7.1 Field Safety Procedures .................................................................................................................44

8.0 References ...............................................................................................................................................46

Figures Figure 1. Marine offshore station locations. ......................................................................................... 7

Figure 2. Marine beach station locations. ............................................................................................10

Figure 3. Field observation form ............................................................................................................18

Figure 3 (cont.). Field observation form. ..................................................................................................19

Figure 4. Example of positioning software. ........................................................................................20

Figure 5. Example of CTD hydrocast data acquisition. ...................................................................22

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Figure 6. Field sheet for offshore samples. .........................................................................................28

Figure 7. Field sheet for beach samples. .............................................................................................29

Tables Marine offshore station sampling period of record and coordinates. ..................... 8

Marine beach station sampling period of record and coordinates. ........................11

Field parameter sensor specifications. ..............................................................................15

Sample storage, preservation, and holding times. ........................................................26

Quantitation limits for laboratory parameters. .............................................................31

Appendices Appendix A: Station Parameters and Depths Appendix B: King County Environmental Laboratory standard operating procedures cover

pages

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King County Science and Technical Support Section v May 2020

Acronyms and Units of Measurement CTD Conductivity-Temperature-Depth DO Dissolved oxygen DQO Data quality objective Ecology Washington Department of Ecology EPA Environmental Protection Agency FC Fecal coliform bacteria FIB Fecal indicator bacteria Geomean Geometric mean GPS Global Positioning System KCEL King County Environmental Laboratory LIMS Laboratory Information Management System MDL Method detection limit MP Monitoring portal MS/MSD Matrix spike/matrix spike duplicate NAD 83 North American Datum of 1983 NH3-N Ammonia nitrogen NO2/NO3-N Nitrite/nitrate nitrogen OrthoP Orthophosphate phosphorus PAR Photosynthetically active radiation PST Pacific Standard Time PSEMP Puget Sound Ecosystem Monitoring Program QA/QC Quality assurance/quality control RPD Relative percent difference SOP Standard operating procedure TSG Thermosalinograph Units of Measurement °C degree Celsius cfu/100 mL colony forming units per 100 milliliters ft feet g gram m meter mg/L milligrams per liter (parts per million) NTU nephelometric turbidity units psu practical salinity units sigma-t a measurement of density µg/L micrograms per liter (parts per billion) µmhos/cm micromhos per centimeter µS/cm microsiemens per centimeter, a unit of conductivity µm/s/m3 micromoles per second per meter cubed, a unit of PAR

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1.0 INTRODUCTION King County Department of Natural Resources and Parks and its predecessor agency Municipality of Metropolitan Seattle (Metro) have a long history of water quality monitoring in Puget Sound. As part of an ongoing effort to maintain and improve Puget Sound's water quality, the King County Wastewater Treatment Division oversees regional sewage collection, treatment processes, and disposal systems that discharge wastewater to the Central Puget Sound Basin and waters flowing into the Sound. King County's Marine and Sediment Assessment Group supports a comprehensive long-term marine monitoring program that assesses water quality in the Central Puget Sound Basin on behalf of and in coordination with the Wastewater Treatment Division.

The County maintains a long-term water quality dataset, consisting of over 50 years of data collected at some stations. These data provide insight into natural variations and a basis from which recent water quality conditions near outfalls and throughout the entire Puget Sound Central Basin can be assessed.

1.1 Project Background King County’s marine monitoring program focuses primarily on water quality within King County’s boundaries. King County collaborates with other agencies that monitor water quality and/or the environmental health of Puget Sound through the intergovernmental monitoring effort, the Puget Sound Ecosystem Monitoring Program (PSEMP). Other agencies, such as the Washington Department of Ecology (Ecology) and the University of Washington also assess water quality within the Central Basin. However, the main distinction between these programs and King County’s monitoring program is that the County has a larger number of stations within a concentrated area, with some sampling locations targeted near wastewater treatment plant point source discharges (outfalls). Although other agencies have monitoring stations within King County, the stations do not overlap with the County's stations which allows a broader area of Puget Sound marine waters to be monitored.

The Federal Clean Water Act states that all sewage treatment plants that discharge effluent from a point source into surface waters must have a National Pollutant Discharge Elimination System (NPDES) permit. The permit delineates conditions and quantities that a municipality can discharge to a receiving waterbody. In Washington State, Ecology administers the NPDES permit program by delegation from the U.S. Environmental Protection Agency (EPA). King County has four NPDES permits to discharge treated wastewater to Puget Sound marine waters. The permits can be accessed at the following website at https://www.kingcounty.gov/depts/dnrp/wtd/system/npdes.aspx.

King County’s monitoring program contains elements of baseline sampling to assess background conditions (ambient monitoring) and also sampling to assess conditions around King County’s marine outfalls (point source monitoring). The marine monitoring program currently consists of several sampling components including: water column, beach water,

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in-situ water, beach sediment, offshore sediment and benthic infauna, and phytoplankton and zooplankton. The in situ and plankton monitoring are the most recently added sampling components, while all other sampling has been conducted for decades. In situ automated sampling began in 2008 and has since expanded to four systems. Phytoplankton abundance and community composition was also added in 2008 but the monitoring program was significantly expanded in 2014 (King County, 2016). The zooplankton abundance and community composition component was added in 2014 (King County, 2015). This sampling and analysis plan provides information only for the water column and beach water sampling components. Sampling and analysis plans for sediment monitoring can be accessed at https://green2.kingcounty.gov/ScienceLibrary/default.aspx?&CategoryID=2. Updated sampling and analysis plans for the in situ and overall monitoring program are currently under development and will be available at the website listed above when complete.

1.2 Project Goals The objective of the marine monitoring program is to provide an understanding of water quality within King County and to assess water quality near the County's wastewater treatment plant outfalls to identify if discharges are affecting water quality. The goals of the marine monitoring program are to identify sources of water pollution, provide water quality information for management decisions, and evaluate status and trends of marine waters within King County. In order to meet the objective and goals, the monitoring program works within a framework of the following elements:

• implement a long-term ambient monitoring program to characterize water quality in King County marine waters;

• implement a long-term monitoring program to characterize water quality near King County marine outfalls;

• evaluate data results in regard to applicable State water quality guidelines; • gather sufficient data to determine both short and long-term water quality

conditions; • determine physical and chemical dynamics that influence water quality; • support coordinated regional monitoring efforts; and • collect scientific data of high quality to inform water quality management decisions.

Water quality may be affected by natural processes as well as by point and nonpoint source pollution. King County’s marine monitoring program assesses both point and nonpoint source pollution in nearshore and offshore environments, as well as assessing ambient (background) conditions. Within these categories, sampling locations are classified as either beach (+3 to -3 meter mean lower low water) or offshore (bottom depth greater than -3 m mean lower low water).

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Obtaining background data from areas in receiving waters that are not influenced by point sources is important in order to accurately evaluate the overall condition of receiving waters. King County has established an ambient monitoring program in the Central Puget Sound Basin to better understand regional water quality and provide data needed to identify trends that might indicate impacts from long-term cumulative pollution.

1.3 Project Staff and Responsibilities The tasks involved in sampling and analysis of marine offshore and beach waters and the personnel responsible for those tasks are shown below.

• Kimberle Stark. King County Marine and Sediment Assessment Group. 206-477-4829. [email protected]. Marine monitoring program coordinator and project management, preparation of SAP, data quality assessment, data analysis, and preparation of reports.

• Wendy Eash-Loucks. King County Marine and Sediment Assessment Group. 206-477-4683. [email protected]. Data quality assessment, data analysis, and preparation of reports.

• Taylor Martin. King County Marine and Sediment Assessment Group. 206-263-9879. [email protected]. Data quality assessment, data analysis, and preparation of reports

• Jeff Lafer. King County Wastewater Treatment Division. 206-477-6315. [email protected]. Internal review of draft SAP and draft water quality reports.

• Jean Power. King County Environmental Laboratory. 206-477-7149. [email protected]. Coordination of field activities for offshore and beach sampling events.

• Bob Kruger. King County Environmental Laboratory. 206-477-7147. [email protected]. CTD raw data processing and upload of profile data to internal database.

• Erin McCabe. King County Environmental Laboratory. 206-477-7205. [email protected]. Coordination of all King County Environmental Laboratory activities, data verification, and internal data reporting.

• Quality Assurance/Quality Control Officer (currently vacant). King County Environmental Laboratory. Data verification, coordination of King County Environmental Laboratory QA/QC programs.

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King County Science and Technical Support Section 4 May 2020

2.0 SAMPLING DESIGN King County Department of Natural Resources and Parks and its predecessor agency Municipality of Metropolitan Seattle (Metro) have a long history of water quality monitoring in Puget Sound. As part of an ongoing effort to maintain and improve Puget Sound's water quality, the King County Wastewater Treatment Division oversees regional sewage collection, treatment processes, and disposal systems that discharge wastewater to the Central Puget Sound Basin and waters flowing into the Sound. King County's Marine and Sediment Assessment Group supports a comprehensive long-term marine monitoring program that assesses water quality in the Central Puget Sound Basin on behalf of and in coordination with the Wastewater Treatment Division. The County maintains a long-term water quality dataset, consisting of over 50 years of data collected at some stations. These data provide insight into natural variations and a basis from which recent water quality conditions near outfalls and throughout the entire Puget Sound Central Basin can be assessed.

2.1 Sampling Area King County's sampling area is located within the Puget Sound Central Basin, extending south to Dumas Bay and north to Point Wells at the King/Snohomish County line. Elliott Bay, a large urban embayment which includes the City of Seattle waterfront, is located within the County's monitoring area. Quartermaster Harbor, a shallow embayment between Vashon and Maury Islands, is also located within the monitoring area. Besides the sites sampled in marine waters, an additional four sites are sampled in the Duwamish River subestuary.

2.1.1 Sampling Area Characteristics Puget Sound consists of a series of underwater valleys and ridges (called basins) and submerged hills (called sills). Sills impede the flow of water in and out of the Sound and also induce vertical mixing as water moves over the sill. The Sound consists of the following interconnected basins, including the Main (Admiralty Inlet and the Central Basin), Whidbey, Southern, and Hood Canal Basins. Water from the Pacific Ocean enters the Sound primarily through Admiralty Inlet and secondarily through Deception Pass. The Central Basin, with depths greater than 280 m, is shielded at the northern entrance to the Sound by the Admiralty Inlet Sill which impedes the exchange of deep waters. However, Puget Sound has near-oceanic salinity throughout the year and is supplemented with cold, nutrient-rich, low-oxygenated, deep oceanic water upwelled off the Washington coast during the late summer months. A mixed semi-diurnal tide, which is characterized by two unequal high tides and two unequal low tides occurring each day, dominates the tidal pattern within Puget Sound. The average tidal range is 3.7 to 4.3 m and an average water volume exchange of 8 billion cubic meters occurs with each tidal cycle (King County, 2009). These relatively high water

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exchange rates are conducive to maintaining overall favorable water quality conditions in the Central Basin, with the exception of Quartermaster Harbor. The physical characteristics of Quartermaster Harbor (shallow and South facing) causes poor tidal flushing and water exchange compared to other locations in the Central Basin. There are two main freshwater inputs into the Central Basin marine waters: the Green/Duwamish River system, which enters Elliott Bay and the Lake Washington Drainage Basin (Cedar River) which flows into the Sound primarily through the Lake Washington Ship Canal. The Skagit, Stillaguamish, Snohomish, and Puyallup Rivers all have substantial freshwater flows, particularly the Skagit River, and can affect marine waters within the Central Basin. There are also numerous smaller streams that discharge directly into nearshore Puget Sound waters.

2.2 Sampling Strategy Water monitoring for physical, chemical, and biological parameters is an important component of the County’s monitoring programs. Water is analyzed from multiple depths at a total of 14 Central Basin offshore stations (7 ambient and 7 outfall) and four Duwamish River subestuary stations. Water is also analyzed from a single depth at 20 beach stations, 10 of which are in the vicinity of an outfall. Specific locations, sampling frequency, and the parameters measured at all the stations is provided below.

2.2.1 Offshore Station Locations and Sampling Frequency Ambient stations are located away from an outfall in order to: characterize the sampling area, capture both large scale and more localized Puget Sound oceanographic processes, and compare results at outfall discharge points to “reference” conditions. Outfall stations are located at the terminus of a treatment facility outfall. Offshore station locations are shown in Figure 1 and the coordinates and period of sampling record is provided in Table 1. All offshore stations are sampled once a month in January and December, and twice monthly the remainder of the year. Typically for twice monthly sampling, samples are collected on the first and third weeks of each month. Due to the amount of time required to sample all locations and initiate laboratory analyses within a short timeframe for some parameters, two days are required to collect most of the samples for each sampling event. The northern stations from Point Wells to West Point (JSUR01 to KSSK02), two Elliott Bay stations, and three of the Duwamish River subestuary stations are sampled by boat on one day. The remaining stations with the exception of Quartermaster Harbor and the most upstream Duwamish River subestuary station are sampled by boat the following day. The two Quartermaster Harbor stations and one Duwamish River subestuary station are sampled off a dock or bridge on the day beach samples are collected. These three stations are typically sampled either one day prior or after all the other offshore stations. All other offshore stations are to be sampled consecutive days. A summary of the offshore sampling schedule is as follows:

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• Day 1: JSUR01, KSBP01, CK200P, KSSK02, LTBC43, LTED04, HNFD01, LTKE03, LTUM03

• Day 2: LSEP01, LSKQ06, LSNT01, LSVV01, MSJN02, NSEX01 • Day 3: MSWH01, NSAJ02, LTXQ01

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Figure 1. Marine offshore station locations.

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Marine offshore station sampling period of record and coordinates.

2.2.1.1 Ambient Stations

Locations for ambient offshore water samples were chosen based on continuation of a long-term dataset (e.g., station KSBP01) or for spatial coverage to assess water conditions away from direct discharges within the Central Basin. Station NSEX01 located in East Passage was added to the ambient sampling program in 2003 to represent conditions in the southern area of the Central Basin. This area had not been routinely sampled prior to 2003 and is the most southern monitoring station. Although there are multiple stormwater outfalls and the Barton CSO outfall located in Fauntleroy Cove, station LSVV01 is not located at a direct discharge point and is considered an ambient station. Three of the seven ambient stations are considered deep water locations, with bottom depths greater than 150 meters (m). The Elliott Bay station (LTED04) has a bottom depth of approximately 100m. The remaining three ambient sites are considered shallow water stations, with bottom depths of 10m or less.

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2.2.1.2 Outfall Stations

Locations for outfall water stations were based upon the following: stations KSSK02, LSEP01, MSJN02, LTBC43, CK200P, and LSKQ06 were established in the water column at the end of outfall pipes. Station KSSK02 is located at the end of the West Point TP outfall diffuser, LSEP01 is located at the end of the South Plant’s north diffuser, MSJN02 is at the end of the Vashon TP outfall, LTBC43 is at the end of the Denny Way/Elliott West CSO outfall along the Seattle waterfront, CK200P is at the end of the Carkeek CSO TP outfall, and LSKQ06 is located at the end of the Alki CSO TP outfall. Stations were placed at these locations in order to characterize water quality at the point where effluent is discharged into the marine environment. Two of the seven outfall stations, JSUR01 and LSEP01, are considered deep water locations, with bottom depths greater than 150 meters (m). All other sites have bottom depths less than 100m, with station LTBC43 the shallowest at approximately 22m.

2.2.2 Beach Station Locations and Sampling Frequency All beach waters are sampled at a single depth once a month throughout the year. All stations are sampled in a single day. Station locations are shown in Figure 2 and the coordinates and period of sampling record is provided in Table 2.

2.2.2.1 Beach Ambient Stations

Ambient beach station locations are located along the shoreline away from either a nearshore or offshore wastewater treatment plant outfall to assess background conditions. However, stormwater outfalls are located about every 50 ft along the shoreline within the City of Seattle limits, therefore beach water quality may be affected by stormwater input. Locations for ambient sites were chosen based on continuation of a long-term dataset (e.g., multiple stations sampled since 1970), high-use public beach, or for spatial coverage to assess beach water quality away from direct wastewater discharges. Beach stations were most recently added to the ambient program in 2007 to increase spatial coverage within King County waters.

2.2.2.2 Beach Outfall Stations

Outfall beach stations are located in the vicinity of either a nearshore or offshore treatment plant outfall. Although most treatment plant outfalls are located substantially offshore, sampling locations were placed along the nearshore in order to evaluate water quality at beach sites in the vicinity of effluent discharges. Station JSVW04 is located east of the Brightwater Treatment Plant outfall, which is over 1,600m (1 mile) offshore. Two stations, KSSN04 and KSSN05, are located on the north and south side of West Point, respectively. Station LSKR01 is located north of the location where the Alki CSO TP outfall exits the shoreline. Station MSJL01 is located on the beach directly west of the Vashon TP outfall and KSHZ03 is located directly east of the Carkeek CSO TP outfall. A beach station is not located near the South TP outfall as the outfall is over 10,000 feet offshore. Station MTLD03 was initially sampled as an ambient location; however, it was subsequently determined that the Miller Creek Wastewater Treatment Plant outfall was offshore of this location.

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Figure 2. Marine beach station locations.

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King County Science and Technical Support Section 11 May 2020

Marine beach station sampling period of record and coordinates.

2.2.3 Field and Laboratory Parameters Water column profile data at offshore stations are collected in situ using a conductivity-temperature-depth (CTD) sampler. Discrete samples for laboratory analyses are collected at specific depths using Niskin bottles concurrent with the water column profile data. Specific parameters analyzed at both offshore and beach stations are provided in Appendix A.

2.2.3.1 Field Parameters

The following field in-situ parameters will be collected throughout the water column at all offshore stations, with the exception of the three land-sampled stations:

• temperature, • salinity,

Locator Description CategoryYear first sampled1 Northing2 Easting2

JSVW04 Richmond Beach/Point Wells Outfall 1972 286171 1257194

ITCARKEEKP Carkeek Park Ambient 2000 263756 1259915

KSHZ03 Piper's Creek Mouth Outfall 1970 263736 1259784

KSLU03 Golden Gardens Ambient 1970 256354 1253305

KSSN04 West Point North Outfall 1970 245729 1246032

KSSN05 West Point South Outfall 1970 245272 1245980

KSYV02 Magnolia CSO Outfall 1985 234547 1254488

LTBD27 SAM Sculpture Park Ambient 2007 228851 1264297

LSGY01 Seacrest Park Ambient 1997 218711 1258776

LSHV01 Alki Beach Ambient 1970 216852 1253532

LSKR01 Alki North Outfall 1972 213666 1249416

LSKS01 Richey Viewpoint Outfall 1970 212668 1250283

LSVW01 Fauntleroy Cove Ambient 1972 194969 1254846

MTLD03 Normandy Park Outfall3 1998 165142 1263285

MTUJ01 Des Moines Creek Park Ambient 2007 151129 1269533

NTFK01 Redondo Beach Ambient 2007 131067 1270899

NSJY01 Dumas Bay Park Ambient 2007 122831 1255835

MSJL01 Vashon - Gorsuch Creek Outfall 2002 169666 1241897

MSSM05 Vashon - Tramp Harbor Ambient 1990 154908 1243459

MSXK01 Vashon - Burton Acres Park Ambient 2007 146481 1240772

1 Some parameters changed over the years.2North American Datum 1983 (NAD83) - State Plane Coordinate System - Washington North 46013 This station is nearshore of the Miller Creek Wastewater Treatment Plant outfall

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• density (calculated), • dissolved oxygen (DO), • transmissivity, • light intensity (photosynthetically active radiation or PAR), • light intensity-surface (PAR), • chlorophyll fluorescence, • Secchi water transparency, • depth, and • nitrate + nitrite nitrogen (NO23).

While the boat is in transit during the sampling of all offshore stations, a thermosalinograph (TSG) will continuously record surface water temperature and salinity. For the three land-sampled offshore stations, temperature, salinity, dissolved oxygen, depth, and pH will be collected in the field at specific depths rather than the entire water column. In addition to the parameters listed above, Secchi transparency will also be determined for all offshore stations. For beach waters, only temperature will be determined in the field at a single depth.

2.2.3.2 Laboratory Parameters

The following parameters will be analyzed in the laboratory at all offshore stations, with the exception of the Duwamish River subestuary stations:

• fecal indicator bacteria (FIB) (fecal coliform and enterococcus bacteria), • ammonia-nitrogen, • nitrate+nitrite-nitrogen, • silica, • orthophosphate phosphorus, • chlorophyll-a, • pheophytin, and • total suspended solids.

FIB are analyzed from the 1m depth at all offshore stations. Bacteria samples are analyzed from an additional depth at all outfall stations. The depth of the additional bacteria sample varies for each location and is dependent upon the expected trapping depth of the effluent plume.

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For other laboratory parameters, the number of samples for each station depends upon the bottom depth for the site. Samples from up to seven depths are collected at the deepest stations, while only two samples are collected at the shallowest stations. Sampling depths for each parameter and location are provided in Appendix A. Total nitrogen is analyzed in the 1m samples at a subset of 9 offshore stations, 3 of which are outfall stations. Additional total nitrogen samples are collected at various depths at the West Point and South Plant treatment plant outfalls (KSSK02 and LSEP01) and the two Quartermaster Harbor stations. Chlorophyll-a and pheophytin (phytoplankton pigments) are analyzed in offshore samples at four depths from 1-35m. An additional sample at the maximum chlorophyll concentration, as determined by the CTD fluorometric profile, is analyzed at a subset of seven stations. For the Duwamish River subestuary stations, the following parameters will be analyzed in the laboratory at two depths per station:

• FIB, • ammonia-nitrogen, • nitrate+nitrite-nitrogen, • silica, • orthophosphate phosphorus, • dissolved organic carbon (DOC), • total organic carbon (TOC), • DO, • salinity, and • total suspended solids.

For the most upstream Duwamish River subestuary station, silica, DOC, TOC, and DO are not analyzed. FIB, ammonia-nitrogen, nitrate+nitrite-nitrogen, orthophosphate phosphorus, and salinity are analyzed in the laboratory for all beach stations. Total nitrogen is also analyzed for a subset of six beach stations.

2.2.4 Data Quality Objectives Marine water column profile and discrete depth data are used to determine long-term trends and patterns in water quality and estuarine processes. The data are also used to assess water conditions near the County’s marine wastewater treatment plant outfalls and beaches to ensure discharges are not negatively impacting water quality. Consistent, high quality data are necessary to meet the monitoring program goal and objectives as well as determine water quality trends. The method detection limits (MDLs) are driven by the

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need for analytical testing to be sensitive enough to distinguish the parameters of concern both at and above background (ambient) levels.

2.2.5 Measurement Quality Objectives Monitoring data will be assessed in terms of precision, accuracy, representativeness, completeness, comparability, and sensitivity to ensure that all data generated during field surveys and laboratory analyses are of the highest quality and meet programmatic goals.

2.2.5.1 Precision, Accuracy, and Bias

Precision is the agreement of a set of results among themselves and is a measure of the ability to reproduce a result. Accuracy is an estimate of the difference between the true value and the determined mean value. The accuracy of a result is affected by both systematic and random errors. Bias is a measure of the difference, due to a systematic factor, between an analytical result and the true value of an analyte. Precision, accuracy, and bias for laboratory analyses will be measured by various laboratory quality control (QC) samples such as method blanks and laboratory duplicates. For water column profile data, precision and accuracy are established by calibrating the sensors annually as well as following the manufacturer’s operational specifications. Manufacturer precision and accuracy specifications are provided in Table 3. In addition, DO sensor accuracy is assessed by analyzing at least three samples per each sampling event by the Winkler titrimetric DO method. The sensor DO data is then compared with the Winkler results and sensor drift corrected if deemed appropriate. More detailed information is provided in Section 5.0. Precision and accuracy are established for beach data by calibrating the temperature probe according to the manufacturer’s operational specifications and the use of method blanks and duplicates for laboratory analyses. Water data collected for this monitoring program may be affected by a systematic bias. All samples are collected during daylight hours for safety of the field sampling crew and to initiate laboratory analyses within the required hold time. Therefore, the data may be biased, particularly for biological parameters such as DO and chlorophyll that are affected by sunlight/primary production.

2.2.5.2 Representativeness

Representativeness expresses the degree to which sample data accurately and precisely represent a characteristic of a population, parameter variation at the sampling point, or an environmental condition. To the extent possible, the long-term marine water column and beach monitoring programs are designed to collect data that sufficiently represent: the sampling area, seasonal variation, and spatial variation within the water column. Monthly and semimonthly data collection will ensure a variety of seasonal conditions are represented. Specific environmental conditions, such as tidal cycle and storm events, are not targeted in order to ensure a variety of conditions are sampled throughout the year.

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Sampling all offshore and beach sites will ensure spatial coverage within King County marine waters and adequately represent larger-scale spatial variation. Stations represent a variety of habitats (e.g., within an embayment, an outfall discharge point, or near the mouth of a subestuary) and bathymetric features (e.g., deep channel vs shallow nearshore) to reflect Central Basin waters. Following the guidelines described in Section 4 for sample collection, processing, storage, and handling will also help ensure that samples are representative. Field personnel will control sampling variability by strictly following all standard operating procedures. However, natural spatial and temporal variability may affect overall variability.

2.2.5.3 Completeness

Completeness is defined as the total number of samples for which acceptable analytical data are generated, compared to the total number of samples submitted for analysis. Adhering to standardized sampling and testing protocols will aid in providing a complete set of data for this long-term monitoring program. The goal for completeness is 100%. If 100% completeness is not achieved, the appropriate staff will evaluate whether the DQOs can still be achieved or if additional samples may need to be collected and analyzed. Because hydrographic data are acquired electronically and monitored in real time, no loss of data is expected.

Field parameter sensor specifications.

2.2.5.4 Comparability

Comparability is a metric expressing the confidence that one dataset can be compared with another. This goal is achieved through using standard protocols to collect and analyze all samples as well as standardized data validation and reporting procedures. By following the guidance of this SAP, the goal of comparability between current and future sampling events will be achieved. Historical data that also followed standardized procedures may be

Sensor Model Units Range Accuracy PrecisionFluorometer (chlorophyll) WET Labs WETStar ug/L 0.03 to 75 0.03 0.01Conductivity Seabird SBE 4 mS/cm 0 to 70 0.03 0.01Pressure (depth) Seabird SBE 29 decibars 0 to 1000 0.10% 0.1Dissolved oxygen Seabird SBE 43 mg/L 0 to 15 0.5 0.05Light transmision Wet Labs C-Star % light 0 to 40 0.2 0.01PAR (surface) Biospherical QSR2200 umol/sm/2 7uA to 1000 10 1PAR (water column) LI-COR LI-193-SA umol/sm/2 7uA to 1000 10 1Temperature Seabird SBE 3 oC -5 to +35 0.001 0.01Nitrate Seabird SUNA V2 mg/L 0.007 to 42 0.028 0.034

Thermosalinograph Seabird SBE 45 microTSG oC, mS/cm-5 to +35,

0 to 700.001, 0.03

0.01, 0.01

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compared with data generated from the current monitoring effort to enhance long-term data analysis. All protocols used by the King County Environmental Laboratory (KCEL) are based on the most current, standard, and internationally accepted seawater methods. This use of established sampling and analytical procedures enables comparability with other regional datasets. King County also compares nutrient standards and split field samples with other monitoring partners, such as Ecology’s Marine Unit. Standard protocols are followed for generating field and/or control samples for conducting laboratory analyses. Seawater nutrient standards are prepared by Ecology for comparative analyses by both the KCEL and the University of Washington’s Marine Chemistry Lab. At least once a year, both King County and Ecology will collect additional nutrient samples at a subset of stations to split with both laboratories, respectively. King County analyzes and reports the inter-laboratory comparison results (King County, 2014).

2.2.5.5 Sensitivity

Sensitivity is a measure of the capability of analytical methods to meet monitoring goals. Sensitivity of marine data is reported as the lowest value reliably detectable for a given parameter. The analytical methods and MDLs presented in Sections 3.2 and 4.0 are sensitive enough to allow for both spatial and temporal comparisons as well as long-term trends. More detailed information on how sensitivity is achieved and reported for each parameter is provided in the sections listed above.

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3.0 FIELD SAMPLING PROCEDURES Field sampling methods follow protocols described in the standardized international oceanographic sampling methods published by UNESCO (UNESCO, 1994) and the Puget Sound Estuary Program (PSEP) recommended protocols for sampling conventional water column and microbiological variables (PSEP; 1991, 1997). These protocols adhere to the most current sampling methods and are followed regionally as well as internationally. Following these protocols will ensure data consistency for long-term monitoring efforts as well as consistency with other Puget Sound monitoring programs. An example of the field observation form that is completed by Field Science Unit (FSU) staff for all offshore and beach sampling events is shown in Figure 3.

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Figure 3. Field observation form

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Figure 3 (cont.). Field observation form.

3.1 Station Positioning Reliable station positioning is essential for monitoring programs with established long-term stations. Inaccuracies in station positioning when conducting water column sampling, particularly in deep water, can result from the action of currents and wind on the sampling vessel as well as current forces and viscous drag on the CTD rosette sampler. As a result, inaccuracies in station positioning can affect the ability to conduct long-term trend analyses due to spatial variability. All offshore stations, with the exception of the three stations described below, are sampled by a research vessel. The two Quartermaster Harbor and the most upstream Duwamish River subestuary stations are sampled from docks (Quartermaster Harbor stations) and from a bridge (the Duwamish River subestuary station). All beach stations are sampled from land.

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3.1.1 Offshore Water Vessel station positioning will be achieved by utilizing a Furuno® global positioning system (GPS). Prior to each sampling event, the prescribed station coordinates will be entered into the shipboard GPS system. During the sampling event, the shipboard navigational system will utilize the differential data transmissions from regional Coast Guard base stations to automatically correct its GPS satellite data. The GPS receiver has twelve dedicated channels that are capable of locking onto twelve different satellites at one time. Figure 4 provides an example of the vessel positioning software. Positioning information is not recorded, but the vessel attempts to sample within 100 m of the prescribed locator coordinates. If this is not possible, a note will be made on the field observation form and the position information recorded.

Figure 4. Example of positioning software.

3.1.2 Beach Water Prior to each sampling event, the sampler will review detailed photographs of each station documenting the precise sampling location through shoreline benchmarks. In addition, prescribed station coordinates will be entered into a handheld dGPS. The coordinates for a given station are obtained along the upper part of the beach but the actual collection point is dependent upon the tide. Positioning information will include the local time and date and coordinate data in both latitude/longitude and NAD 83 State Plane formats. Sample

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collection will occur within a 25m transect parallel to the water’s edge at each station’s prescribed position. Samples will not be collected if the observed coordinates are outside of this limit. Any station relocation will be documented and reported. Samples are collected at a single depth just below the water surface. Actual sample depth may vary depending upon wave conditions. The sample collector will wade into the water to a depth of approximately one meter to collect the sample.

3.2 Sampling Equipment and Procedures Detailed information regarding sampling equipment and procedures for offshore and beach waters is provided in the KCEL Sampling and Operating Procedures (SOPs) for all parameters and are available upon request. Due to the page length of some SOPs, only the cover page of each SOP is provided in Appendix B. A brief summary of sampling equipment and procedures is provided below.

3.2.1 Offshore CTD Water Collection Hydrographic data are collected at all offshore stations sampled from the research vessel. A hydrocast will be conducted using a CTD system equipped with various sensors and a discrete water rosette sampling system equipped with up to 12 five-liter Niskin sampling bottles (see Section 3.2.2). Sensor measurements will be collected during both the downcast and the upcast from near surface (approximately 1-2 m) to within approximately 3–5 m of the sea floor at each station. Hydrocast measurements are collected at a rate of 2 hertz (Hz). Figure 5 provides an example of a hydrocast. Salinity and density (as sigma-t) will be calculated from the conductivity, temperature, and depth data. Photosynthetically active radiation measurements above the water surface will be recorded concurrently with the hydrocast measurements at one second intervals. Fluorescence (chlorophyll) downcast data are reviewed following data acquisition to ascertain the depth of the chlorophyll maximum layer. This is performed in order to determine at what depth to trigger the Niskin bottle on the upcast for the chlorophyll maximum sample. All hydrocast data are reviewed for acceptability at each station prior to transiting to the next station. The hydrographic profile sampling and real-time data acquisition equipment consists of the following instruments:

• Sea-Bird SBE-25 Plus Sealogger CTD system mounted on SBE 32 carousel sampler • Sea-Bird SBE 33 shipboard deck unit • Sea-Bird SUNA (submersible underwater nitrate analyzer) V2 sensor • Sea-Bird SBE 3 temperature sensor • Sea-Bird SBE 4 conductivity sensor

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• Sea-Bird SBE 5T water pump • Sea-Bird SBE 43 dissolved oxygen sensor • WET Labs C-Star 25 cm-pathlength transmissometer • WET Labs WETStar chlorophyll fluorometer • Biospherical QSR 2200 surface PAR sensor • LI-COR LI-193-SA underwater PAR sensor • Laptop computer with Microsoft Windows • Sea-Bird Seaterm, Seasave V7, and SBE data processing Win32 software • A-frame with electronic meter wheel

Secchi water transparency is determined at each station using a standard 30 cm black and white Secchi disk. Although Secchi disk measurements provide an additional measure of water clarity, they do not provide an exact measure of transparency due to inherent sampling errors from sun glare on the water and/or differences in eyesight between samplers. Due to potential variation between samplers, the method is standardized as much as possible. Whenever possible, Secchi disk measurements should be taken off the shady side of the boat and the same field sampler should take the measurements every time. Secchi disk depth, reported in 0.1m increments, is determined by lowering the disk to just beyond the point where it disappears in the water, raising it until the disk is visible again, and then lowering it slightly to take an average of the two depths.

Figure 5. Example of CTD hydrocast data acquisition.

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3.2.2 Offshore Discrete Water Collection Water samples for dissolved nutrients, total nitrogen, organic carbon, phytoplankton pigments (chlorophyll-a and pheophytin), TSS, Winkler DO, FIB, and phytoplankton will be obtained with an underwater rosette unit equipped with twelve five liter Niskin sampling bottles. The rosette system is combined with the hydrographic profiling system and the water samples are collected on the upcast at specific depths. See Table A-1 in Appendix A for sampling depths at each location. On the upcast, the Niskin bottles are closed at the prescribed depths and then verified they tripped at the proper depth. Once the bottles are on deck, the sample containers are filled from the Niskin following the proper techniques detailed in the SOPs (see Appendix B). Chemical reagents are used for the Winkler dissolved oxygen fixation. Alkali-Iodide-Azide (AIA) and Manganous Sulfate (MnS04) are added to the sample container once filled. Safety precautions are taken when working with chemicals on the sampling vessel. Samples for dissolved nutrients are filtered in the field using a 60 mL syringe and a 0.45µm surfactant free, cellulose acetate (SFCA) syringe filter. The first sample filtered on a given field run should be the first field filter blank of the day. Dissolved nutrient bottles are filled to near the shoulder and the filters are changed for every sample collected. However, syringes may be rinsed with ambient water thoroughly and used multiple times. The samples should be filtered within 15 minutes of the Niskin rosette or Scott bottle emerging from the water and being placed on the deck. The samples are then filtered using a 60 mL syringe and a 0.45µm SFCA syringe filter.

3.2.3 Beach Water Collection Beach water samples will be collected in approximately knee-deep water by wading into the water and inverting each sample container just above, then sinking the bottle down to approximately three to six inches below the water surface. No specific tidal height or tidal stage are targeted in order to collect samples from a variety of conditions. Samples for dissolved nutrients are filtered in the field using a 60 mL syringe and a 0.45µm syringe filter. Dissolved nutrient bottles are filled to near the shoulder and the filters are changed for every sample collected. The syringes may be rinsed with ambient water thoroughly and used multiple times. The samples should be filtered within 15 minutes of the bottle emerging from the water. Water temperature will be measured in the field using a digital thermometer. Temperature will be measured at approximately the same depth as the bottle samples. Macroalgae can be a nuisance on beaches and produce noxious odors when it decays. Ecology has a Puget Sound macroalgae assessment project to monitor the amount of macroalgae accumulated along the high tide line. On the field sheets, FSU staff will record

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the amount of macroalgae seen during beach sample collection using the protocols developed by Ecology.

3.2.4 Thermosalinograph (TSG) Data Collection TSG data will be collected continuously at the rate of 0.5 Hz (every two seconds) while the vessel is in Puget Sound and the Duwamish River subestuary. Data will be collected with a Sea-Bird SBE 45 MicroThermosalinograph, which includes a Sea-Bird SBE 38 Digital Oceanographic thermometer. The equipment is installed at the water intake on the vessel bow at approximately 0.8m in water depth. The system appends National Marine Electronics Association (NMEA) positional data via the vessel’s navigation system to ensure each data point is associated with time and coordinates.

3.3 Equipment Decontamination KCEL staff will attempt to avoid sampling in waters that contain visibly high levels of contaminants, such as oil spills. If contact with the rosette or sensors is suspected, staff will follow all recommended protocols from instrument manufacturers for cleaning and, if needed, recalibrating sensors. Sample collection and processing equipment is cleaned prior to each sampling event. The rosette, CTD sensor package, and the vessel deck is rinsed with freshwater at the end of each sampling day. Polypropylene containers for bacteria analyses are autoclaved and identified as sterile with autoclave tape before being used for sample collection. Because nutrients, salinity, and organic carbon are analyzed at trace levels and may be prone to carryover contamination, aliquots for these measurements are collected and stored in new, precleaned, high-density polyethylene and/or glass containers. All other sample containers and lids are reused. Multi-use containers have previous labels removed, are cleaned using hot tap water, Detergent 8, and reverse osmosis water with a programmable multi-cycle dishwasher. The washed containers are allowed to dry, are recapped, and then reused.

3.4 Sample Handling Procedures The following section provides information regarding the handling and storage of discrete offshore and beach water samples.

3.4.1 Sample Storage and Holding times The size and type of containers, required preservation, and holding times for parameters analyzed by the KCEL are shown in Table 4. The specifications listed in the table represent the requirements of the reference method most often associated with a particular parameter. For nutrients, the recommended 60 mL, 125 mL, and 250 mL containers are not reused to avoid potential contamination at trace levels. When appropriate, preservatives are added to containers prior to sample collection. The current lab practice is to analyze nutrient samples within two days of collection and filtered samples for ammonia, nitrate/nitrite, and orthophosphate may be stored for up to

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two days at ≤6°C. However, it is possible to extend the holding time to 14 days for all nutrients except silica by freezing the filtered sample aliquots at -20°C when immediate analysis is not feasible. Filtered samples for silica should be held at ≤6°C but never frozen. Silica samples must be brought to room temperature and shaken vigorously before analysis. When samples require silica analysis in addition to other dissolved nutrient parameters, two full sets of sample aliquots must be filtered in order to apply proper storage conditions to maintain sample integrity and holding time.

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Sample storage, preservation, and holding times.

Parameter ContainerStorage

Conditions PreservationAnalysis

hold timeFecal coliform,

Enterococci bacteriasterile 500 ml polypropylene cool to ≤ 10oC none 24 hours

Ammonia-nitrogen

125 or 250 ml clear wide

mouth HDPE* freeze at -20oC field filter within 1 day 14 days

Nitrate/nitrite-nitrogen

125 or 250 ml clear wide

mouth HDPE freeze at -20oC field filter within 1 day 14 days

Total nitrogen

125 or 250 ml clear wide

mouth HDPE freeze at -20oCcool to ≤ 6oC within 2

days 28 days

Silica

125 or 250 ml clear wide

mouth HDPE cool to ≤ 6oC field filter within 1 day 28 days

Orthophosphate-phosphorus

125 or 250 ml clear wide

mouth HDPE freeze at -20oCfield filter within 15

minutes 14 days

Chlorophyll-a and pheophytin

250 ml amber wide mouth

HDPE freeze at -20oCfilter, add magnesium

carbonate within 1 day 28 daysTotal suspended

solids1 L clear wide mouth HDPE cool to ≤ 6oC cool within 15 minutes 7 days

Dissolved organic carbon

125 ml amber glass cool to ≤ 6oC

filter within 1 day, add hydrochloric acid to pH

<2 28 days

Total organic carbon125 ml amber

glass cool to ≤ 6oC

within 1 day, add hydrochloric acid to pH

<2 28 days

Dissolved oxygen (Winkler)

300 ml glass Wheaton with glass stopper

ambient temperature, no direct light, zero

headspace

within 15 minutes, add manganese sulfate &

alkali-iodide-azide 8 hours

Salinity

125 ml clear narrow mouth

HDPE cool to ≤ 6oC none 28 days

* high density polyethylene

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3.4.2 Chain of Custody Procedures Chain of custody (COC) will commence at the time that each sample is collected. While in the field, all samples will be under direct possession and control of King County field staff. For chain of custody purposes, the research vessel will be considered a “controlled area.” Each day, all sample information will be recorded on the field sheet (Figure 6 and Figure 7). This form will be completed in the field and will accompany all samples during transport and delivery to the laboratory each day. Upon arrival at KCEL, the sample delivery person will relinquish all samples to the sample login person. The sample login person will examine the samples, verify that sample-specific information recorded on the field sheets is accurate, verify the sample integrity (containers are sealed and intact), and that field holding temperatures were maintained. The date and time of sample delivery will be recorded and both parties will then sign off in the appropriate sections on the COC portion of the field sheets. The samples will then be logged into the laboratory information management system (LIMS) for tracking throughout the analytical, review, and reporting processes. Samples will be stored in a secure freezer or refrigerator at the temperature conditions required in Table 4. Once completed, original field sheets will be archived in the project file. Samples delivered after regular business hours will be stored in a refrigerator until the next day. Field custody of the electronic CTD profile raw data files will be the responsibility of the Lead Field Scientist. Field custody of electronic data consists of transferring survey data to a network server each day. The network server will be backed up daily.

3.4.3 Sample Documentation Sample information and metadata will be documented using the procedures listed below. Field sheets generated by King County’s LIMS will include information such as:

• sample ID number • station name and locator • sample water depth • date and time of sample collection • space for any comments

LIMS-generated container labels will identify each container with a unique sample number, station and site names, collect date, analyses required, and preservation method. The sampling vessel logbook will contain records of all shipboard activities, destinations, arrival and departure times, general weather, positioning information, and the names of shipboard personnel. The sampling vessel logbooks are archived in the project file when full. Additional sample information is documented on the field observation form (See Figure 3). A daily description of weather, tidal stage, algae observations, equipment used, equipment

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issues, and any other observations that could affect sample quality are included on this form. Once complete, these forms are archived in the project file. A sample of typical field sheets used by the KCEL field staff for offshore and beach stations is included as Figure 6 and Figure 7.

Figure 6. Field sheet for offshore samples.

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Figure 7. Field sheet for beach samples.

Login: T_AM_IT_BN_1 Personnel: _________________ Ambient Intertidal Beaches-North Personnel: _________________ Ambient Intertidal Beaches-North Personnel:______________

Project: 421250BN CHAIN OF CUSTODYRelinquished by Date Time

Received by Date Time

Sample Numbers [All]

Sample Number T_AM_IT_BN_1-1 T_AM_IT_BN_1-2 T_AM_IT_BN_1-3 T_AM_IT_BN_1-4 T_AM_IT_BN_1-5 T_AM_IT_BN_1-6 T_AM_IT_BN_1-7 T_AM_IT_BN_1-8 T_AM_IT_BN_1-9

QC LinkLocator JSVW04 ITCARKEEKP KSHZ03 KSLU03 KSSN04 KSSN05 KSYV02 LTBD27 FFBLANKShort Loc Desc RICHMND BCH CARKEEKPKN CARK PK S GOLD GRD NE WP SE WP MAG PARK SAM SclpPkB FFBLANKLocator Desc RICHMOND BEACH// CARKEEK PK SHORE/100 FT N OF

PEDESTRIAN BRIDGCARKEEK PARK SHORE//SOUTH BOUNDARY OF CARKEEK

GOLDEN GARDENS BEACH//GOLDEN GARDENS

WEST POINT SHORE//WEST POINT, NE OF LIGHTHOUS

WEST POINT SHORE//WEST POINT, SE OF LIGHTHOUS

MAGNOLIA BLUFF SHORE//MAGNOLIA PK FT OF 32ND

SAM SCULPTURE PARK BEACH FIELD FILTER BLANK

Site RICH BCH INTERTID CENT PS INTERTIDAL CARK PK INTERTID WEST PT INTERTID WEST PT INTERTID WEST PT INTERTID WEST PT INTERTID AMBIENT INTERTID METRO

Comments new station at Paramount Plant @100 ft N of overpass Intertidal S of Piper's Ck off Gldn Grdn Comm Cntr NE of WPT Lighthouse - go right SW of WPT Lt Haus - go left Magnolia Park CSO SAM Sculpture Pk Bch Field Filter Blank

Start Date/Time

End Date/Time

Time Span

Sample Depth

ALGAE COVER * * * * * * * * * *

PERSONNEL

SAMP INFO * * * * * * * * * *

SAMP METH

SAMP TEMP * * * * * * * * * *

STORM/NON * * * * * * * * * *

SWIMMERS * * * * * * * * * *

Dept, Matrix, Prod3 LL NH3 3 LL NH3 3 LL NH3 3 LL NH3 3 LL NH3 3 LL NH3 3 LL NH3 3 LL NH3 3 LN NH33 LL NO23 3 LL NO23 3 LL NO23 3 LL NO23 3 LL NO23 3 LL NO23 3 LL NO23 3 LL NO23 3 LN NO233 LL ORTHOP 3 LL ORTHOP 3 LL ORTHOP 3 LL ORTHOP 3 LL ORTHOP 3 LL ORTHOP 3 LL ORTHOP 3 LL ORTHOP 3 LN ORTHOP3 LL SAL 3 LL SAL 3 LL SAL 3 LL SAL 3 LL SAL 3 LL SAL 3 LL SAL 3 LL SAL 3 LL TOTN 5 LL ENT-MF 3 LL TOTN 5 LL ENT-MF 5 LL ENT-MF 5 LL ENT-MF 5 LL ENT-MF 5 LL ENT-MF 5 LL ENT-MF 5 LL FC-MF 5 LL ENT-MF 5 LL FC-MF 5 LL FC-MF 5 LL FC-MF 5 LL FC-MF 5 LL FC-MF 5 LL FC-MF 5 LL FC-MF

# birds: * * * * * * * * * *

# dogs: * * * * * * * * * *

water clarity (clear or murky): * * * * * * * * * *

breaking waves (yes or no): * * * * * * * * * *

algae in water (yes or no): * * * * * * * * * *

algae wrack odor (yes or no): * * * * * * * * * *algae condition (fresh or decaying): * * * * * * * * * *

algae color: * * * * * * * * * *

Ambient Intertidal Beaches-North

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4.0 LABORATORY PROCEDURES The comparability of a data set may be increased by following a standard set of protocols for analyzing samples. This section describes the laboratory analytical methods currently in use. Methods have changed over the sampling record as both analytical procedures and instrumentation have improved over time. To ensure data comparability over time, side-by-side analyses are run concurrently with the existing and proposed new instrumentation and/or methods. Once the side-by-side data are assessed statistically by staff, the laboratory QA officer, and unit supervisor and deemed comparable, the new instrument and/or method is implemented. All instrument and method changes are documented and archived. All parameters described below are analyzed at the KCEL using various analytical methods described in Table 5. Detailed method information is provided in the SOPs for each parameter. Due to the length of some SOPs, only the cover page for applicable SOPs are included in Appendix B. However, all SOPs are available upon request. Quality assurance/quality control procedures for laboratory methods are described in Section 5.0.

4.1 Quantitation Limits The terms MDL and RDL refer to the method detection limit and reporting detection limit, respectively. The MDL is defined as the minimum concentration of a chemical, biological, or physical constituent that can be reliably detected by a particular method. The RDL is defined as the minimum concentration of a chemical, biological, or physical constituent that can be reliably quantified by a given method. The detection limits for laboratory parameters are provided in Table 5 as well as analytical methods.

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Quantitation limits for laboratory parameters.

4.2 Fecal Indicator Bacteria Fecal coliform bacteria analysis is performed according to Standard Method (SM) 9222 D (APHA 2017) and KCEL SOP #506 . Enterococci bacteria analysis is conducted according to method SM9230 C (APHA 2017) and KCEL SOP #512. The MDL for both fecal coliform and enterococci bacteria is 1 colony forming unit per 100 milliliters (CFU/100 ml). There is no reporting limit for these two parameters. For fecal coliforms, appropriate dilutions, if necessary, are prepared using buffered water as the diluent. The sample and its dilutions are filtered through a sterile 0.45 µm nitrocellulose membrane. The membrane is then applied to a plate with the appropriate agar media. After incubation at 44.5 ± 0.2oC for 24 ± 2 hours, all colonies with a characteristic blue color are counted. The number of colonies per 100 mL of sample is calculated based on the colonies counted and the dilutions used per plate. The method is similar for enterococci, however, once transferred to the appropriate agar media plate, the plate is incubated at 41 ± 0.5oC for 48 ± 3 hours. After the 48 hour incubation, the filter is transferred to the EIA medium and incubated at 41 ± 0.5°C for an additional 20–30 minutes. All colonies that have a red to pink color with a black or reddish-brown precipitate are counted and the number of colonies is based on the colonies counted and the dilutions used per plate.

ParameterMethod

detection limitReported

detection limit Units MethodFecal coliform 1 -- cfu/100 ml SM 9222 D

Enterococci 1 -- cfu/100 ml SM 9230 C

Ammonia-nitrogen 0.002 0.01 mg/L Kerouel & Aminot 1997

Nitrate/nitrite-nitrogen 0.01 0.04 mg/L SM 4500 NO3-F-S

Total nitrogen 0.05 0.1 mg/L SM 4500 N-C-S

Silica 0.05 0.1 mg/L Whitledge 1981

Orthophosphate-phosphorus 0.005 0.01 mg/L SM 4500 P-F-S

Chlorophyll-a 0.05 0.1 ug/L EPA 445.0

Pheophytin-a 0.1 0.2 ug/L EPA 445.0

Total suspended solids 0.5 10 mg/L SM 2540 D

Dissolved organic carbon 0.5 1 mg/L SM 5310 B

Total organic carbon 0.5 1 mg/L SM 5310 B

Dissolved oxygen (Winkler) 0.1 0.5 mg/L SM 4500 O-C

Salinity 2 3 PSS SM 2520 B

cfu = colony forming unitsPSS = practical salinity scale

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4.3 Water Clarity and Salinity Total suspended solids analysis is performed according to SM 2540 D (APHA 2017) and KCEL SOP#309. The MDL and RDL for this analysis are 0.5 and 10 mg/L, respectively. For the determination of total suspended solids, a measured volume of a well-mixed water sample is filtered through a 2 µm glass fiber filter. The residue retained on the filter is dried to a constant weight at 103 to 105°C. The resulting net weight represents the total suspended solids contained in the sample. Salinity analysis is determined according to SM 2520 B (APHA 2017) and KCEL SOP #316. The MDL and RDL for this analysis is 2 and 3 PSU (Practical Salinity Unit), respectively. Salinity is determined by measuring the conductance of an electrical current through the sample kept at constant temperature of 25°C (set at 2°C above mean ambient room temperature) and comparing the measurement to the conductivity of a certified and calibrated Standard Seawater. The relative measurement can be displayed as a conductivity ratio or practical salinity. The control and measurement conversion is performed by a microprocessor in the instrument to calculate salinity corrected for the bath temperature to give the equivalent salinity relative to Standard Seawater at 15°C.

4.4 Nutrients Dissolved nutrients are measured in samples that have been filtered through a 0.45 µm syringe filter in the field. Concentrations are determined fluorometrically or colorimetrically using an automated analysis (Astoria2 segmented flow analyzer) for the simultaneous assessment of ammonia-nitrogen, nitrite/nitrate-nitrogen, orthophosphate-phosphorus, and silica. Analyses are conducted according to Standard Methods (APHA 2017) and KCEL SOP# 330. The detection limits for each analyte are summarized in Table 5.

Dissolved inorganic nutrients. An ammonia sample is mixed with o-phthaldialdehyde and sodium sulfite in a borate-buffered solution at 75°C. After sufficient mixing, the concentration is measured by fluorescence spectroscopy using 350nm excitation and 420–470nm emission wavelengths. The increase in fluorescence is directly proportional to the ammonia concentration. For nitrate/nitrite, nitrate is converted to nitrite by cadmium reduction. Nitrite is determined by diazotizing with sulfanilamide and coupling with N-(1-naphthyl)-ethylenediamine dihydrochloride to form a highly colored azo dye. The absorbance is measured at 540nm. Orthophosphate reacts with molybdenum VI and antimony III in an acidic medium to form a complex. This complex is subsequently reduced with ascorbic acid to form a blue color and the reaction accelerated by heating. The absorbance is then measured at 880 nm. Silica in solution as silicic acid or silicate reacts with molybdate reagent in aqueous acid media to form molybdosilicic acid, making this method specific for molybdate-reactive silica. Tartaric acid is added to the complex to reduce the phosphorus interference. The complex is reduced by stannous chloride to form a heteropoly blue complex acid and the absorbance measured at 820 nm.

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Total nitrogen analysis, which includes both organic and inorganic forms of nitrogen, is performed according to SM 4500 N-C-S (APHA 2017) and KCEL SOP #331. Most forms of nitrogen are oxidized to nitrate using high temperature and potassium persulfate as the oxidizing agent. The condition for optimal oxidation efficiency is highly pH sensitive, with the most effective oxidation occurring at a pH >10. The nitrate is then converted to nitrite by cadmium reduction, pH adjusted, and analyzed using an Astoria2 segmented flow analyzer following the nitrate method described above.

4.5 Phytoplankton Pigments Chlorophyll-a and pheophytin-a analyses are performed according to EPA method 445.0 and KCEL SOP #314. The sample is concentrated by filtering a measured volume through a glass fiber filter under a low vacuum. The pigments are extracted from the phytoplankton by ultrasonic disruption of the cells in an acetone medium. The concentration of chlorophyll-a is then determined fluorometrically using a Turner Designs Trilogy Fluorometer. As pheophytin-a is a positive interferent, chlorophyll-a is converted to pheophytin-a by acidification. The extract is then remeasured and the concentration of pheophytin-a determined by calculating the difference from the first measurement.

4.6 Organic Carbon Both total and dissolved organic carbon are analyzed in the Duwamish River subestuary samples according to SM 5310 B (APHA 2017) and KCEL SOP #314. Addition of hydrochloric acid and sparging by the instrument (O-I Analytical Combustion Total Organic Carbon Analyzer) removes inorganic and volatile carbon from the sample. The non-purgeable organic carbon (NPOC) remaining is converted to carbon dioxide by catalytic conversion in a heated combustion chamber packed with platinum catalyst. The carbon dioxide formed is measured directly by a non-dispersive infrared detector. The value provides a measure of non-purgeable organic carbon in the sample. In practice, the purgeable organic carbon is negligible, and therefore the NPOC equals total organic carbon.

4.7 Dissolved Oxygen Dissolved oxygen is analyzed by the Winkler titration method according to SM 4500 O-C (APHA 2017) and KCEL SOP #325. The sample is transferred from the Niskin into a Wheaton BOD bottle, then fixed in the field by adding two mL of manganous sulfate (MnSO4) solution and two mL of alkali-iodide-azide (AIA) solution. Dissolved oxygen rapidly oxidizes an equivalent amount of the dispersed divalent manganous hydroxide to form a brown precipitate, Mn(OH)2. Upon acidification with sulfuric acid, manganic hydroxide forms manganic sulfate, which then acts as an oxidizing agent to liberate free iodine from the alkali-iodide. The iodine, which is stoichiometrically equivalent to the dissolved oxygen in the sample, is then titrated with a standard solution of sodium thiosulfate. The titration end point is either determined electronically with an autotitrator instrument or visually with a starch indicator.

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5.0 QUALITY CONTROL The following sections describe the procedures used to ensure the data collected in the field and analyzed by the KCEL are of the highest quality in order to meet the monitoring program objectives.

5.1 Field Instrument Calibration and Maintenance Proper maintenance and calibration of field hydrographic profile and TSG sensors is described in the operating manuals and application notes for each sensor. Sensor information and application notes can be found at the manufacture’s website at https://www.seabird.com/. Instrument maintenance and calibration will be in accordance with the manufacturers' recommendations. Maintenance and repair logs for instruments and equipment will be stored in the files maintained by the KCEL. Most equipment used for acquiring CTD profiles is factory calibrated initially and returned to the manufacturer for annual recalibration. Calibration records are maintained in the field equipment maintenance and calibration files. After return from the manufacturer for annual calibration or repair, a designated KCEL Field Science Unit (FSU) staff person will verify that the offsets and calibration factors for each piece of equipment have been entered into the data set-up files. The set-up and verification will be documented in the logbook. In addition to providing a new set of calibration factors, the manufacturer also reports on drift and loss of sensitivity relative to the previous calibration. This information will also be documented in the logbook and is useful for tracking performance over each sensor’s operational lifetime. The conductivity sensor, used to calculate salinity, incorporates a fixed precision resistor in parallel with the cell. When the cell is dry and in air, the sensor outputs a frequency representative of the fixed resistor. This frequency is recorded on the calibration certificate and should remain stable, within 1 Hz, over time. The primary cause for calibration drift in the conductivity sensor is fouling of the cell by biological or chemical residues. Fouling changes the cell geometry resulting in a shift in cell constant; therefore, the cleanliness of the cell is important for long-term sensor accuracy. Conductivity or salinity values will be evaluated on a regular basis, bi-monthly at a minimum, based on expected values and best professional judgment. If large drifts in conductivity readings are observed, the sensor will be sent to the manufacturer to be cleaned and recalibrated. In addition to annual factory calibration, the DO sensor is calibrated by comparing samples collected and analyzed in the laboratory using Winkler titration methodology. DO sensor data are then corrected using the Winkler DO data. The surface solar irradiance sensor is deployed above the vessel deck and measures ambient solar radiation in air. It is used in conjunction with the profiling irradiance sensor on the CTD package to assess the amount of available surface sunlight penetrating the water column. The surface solar irradiance sensor is calibrated bi-annually by Biospherical

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Instruments Inc. (http://www.biospherical.com/ ). If the instrument’s calibration is in question for any reason, the instrument will be returned to Biospherical Instruments for recalibration and examination. The collector sphere of the sensor may become dirty during normal use. Any attempt to rotate, tighten, or pull on the small white sensor ball will compromise the calibration and it must be sent to the manufacturer for repair and recalibration. The sphere may be gently cleaned with soap and warm water, or a solvent such as alcohol, by using a soft tissue or towel. Acids, abrasive cleaners or brushes cannot be used as this will mar the surface of the sphere and compromise the calibration. If the sphere becomes damaged or heavily soiled, the instrument will be returned to the manufacturer for cleaning and recalibration and recorded in the logbook. The irradiance shield will be kept as clean as possible by periodically wiping with a damp cloth with care to avoid touching the collector sphere. In addition to bi-annual calibration by the manufacturer, the LI-COR underwater irradiance sensor will be checked periodically against the surface Biospherical sensor readings. If it is evident based upon best professional judgement that the instrument calibration has drifted over time and no longer appropriate, the sensor will be returned to the manufacturer for maintenance and recalibration. The o-rings will be replaced annually when the instrument is returned to the manufacturer for calibration. The thermometer used to determine beach water temperatures will be evaluated annually using an ice-bath to ensure a 32°F (0°C) reading. If the reading is greater than +/- 0.5°C, the probe will be sent back to the manufacturer for calibration. All temperature probe maintenance and evaluation will be kept in the log book. The Niskin bottles are maintained by conducting annual visual inspections and replacing any worn or damaged components. The Niskin bottles are placed in the open position prior to the rosette deployment at each station. The bottles are “rinsed” during the downcast by the flushing of sample water through the bottles and the bottles are closed at the specified depth on the upcast.

5.1.1 Laboratory Equipment Calibration and Maintenance For optimal instrument performance, routine preventative maintenance will be performed according to the manufacturer’s recommendations. Instrument calibration will be done according to the procedures outlined in the SOPs for each parameter. In general, to prevent contamination and/or buildup in the instruments, Chemwash rinses should occur regularly after every run and vendor specific cleaning solutions should also be followed. For those instruments that use tubing, it is also important to change the tubing regularly.

5.2 Field Blanks and Replicates Field quality control (QC) samples are collected to assess any bias that may be introduced to an environmental sample through sampling and sample handling techniques, as well as

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environmental variability at a sampling location. Field QC samples will include field filtration blanks and field replicates.

5.2.1 Field Filtration Blank A field filtration blank is a sample of reagent water supplied by the laboratory, which is transported to the field, poured into a syringe and filtered in a manner similar to a typical sample. Analysis of field filtration blanks is used to measure and document any sample contamination resulting from the filtration process. Field filtration blanks will be analyzed for dissolved nutrients and will be collected at the rate of one per ≤20 samples or per batch, whichever is less.

5.2.2 Field Replicate A field replicate sample consists of a second sample collected at a sampling location using the exact collection methodology that was used to obtain the first sample. The field replicate is collected at the same sampling location and as soon after the original sample as possible. The field replicate sample is generally analyzed for all the analytes for which the sample was analyzed. Analysis of the field replicate sample is used to measure and document the precision of field sampling methodologies and the environmental variability at the sample site. Field replicates will be collected at the rate of one per sampling event for both offshore and beach samples and will be analyzed for nutrients and fecal indicator bacteria. As marine waters are in constant motion due to tides, currents and/or winds, conducting a field replicate for a CTD cast does not provide a good measure of the precision of field sampling methodologies as the field replicate data would be collected minutes after the initial sample. Therefore, it is possible a different water mass could be sampled during the second cast. Replicate CTD casts provide a measure of field variability rather than a measure of precision and accuracy. For this reason, data results from samples collected with the Niskin bottles are used to assess the CTD sensor performance rather than conducting a replicate cast.

5.3 CTD Hydrocast Quality Control Samples analyzed in the laboratory to compare results with the CTD casts are collected with Niskin bottles in the field and are used to indicate sensor accuracy and/or drift. Laboratory samples for DO and salinity are collected during each event to compare with sensor values and verify CTD sensor performance. DO and salinity comparison samples are collected from near bottom or mid-water column depths in order to capture the natural range of oxygen levels. If the CTD and Niskin values differ substantially, appropriate data qualifiers are applied and stored in the database.

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5.4 Laboratory Quality Control Samples Laboratory QC will include the analysis of several types of QC samples that measure accuracy, precision, and bias. Laboratory QC samples will be analyzed at the rate of one per analytical batch or every 20 samples, whichever is less. All laboratory parameters with the exception of Winkler DO will include analysis of method blanks, laboratory control samples/check standards, and laboratory duplicates to assess quality control. Bacteria analyses also include the use of negative and positive controls and nutrient, dissolved organic carbon, and total organic carbon analyses include the use of matrix spike samples. Check standards are also used during analysis of chlorophyll-a. No method blanks are analyzed for salinity. A short description of these types of laboratory QC samples is provided in the following sections. Method Blank A method blank is an aliquot of reverse osmosis water that is processed through the entire analytical procedure. Analysis of the method blank is used to evaluate the levels of contamination that might be associated with the processing and analysis of samples and any introduced bias to sample results. All method blank results should be less than the MDL. If an analyte is detected in the method blank, reanalysis of the method blank is performed. If the analyte concentration in the method blank is still greater than the MDL, all associated samples with values less than 10 times the method blank value may be affected and will be given a data quality flag by the analyst. In addition, a data anomaly form (DAF) will be completed providing details on the quality control results and the potential effect on the sample data quality. For dissolved nutrient analysis, method blanks should be spaced approximately every 20 samples for batches greater than 20 samples. For batches less than 20 samples, method blanks should be prepared at some point after the start of sample filtration (i.e. not just at the beginning of the filtration batch) so that the potential for contamination can be evaluated. Spike Blank Spike blanks are prepared by filtering an aliquot of reagent water and is normally prepared concurrent with the method blank. Spike blanks are prepared by adding a known concentration of the analyte being measured and analyzed as a check on the analyst’s spiking technique. They are also used in conjunction with sample and matrix spike data to check for possible sample matrix interferences. Matrix Spike A matrix spike is similar to a spike blank; however, the known concentration of the analyte being measured is added to an analytical sample rather than reagent water to assess the potential for matrix interference. Matrix spike QC samples are used for nutrient, dissolved

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organic carbon, and total organic carbon analyses. If the result is outside of established control limits, the data associated with the batch are given a data quality flag by the analyst and a DAF will be completed providing details on the quality control results and the potential effect on the sample data quality. Laboratory Control Sample/Check Standard A laboratory control sample or check standard is used as an indicator of instrument and/or method accuracy and analyst proficiency. A control sample of a known concentration of the analyte being measured is included with every sample batch. The resulting value is compared to the known value. If the result is outside of established control limits, the data associated with the batch are given a data quality flag by the analyst and a DAF will be completed providing details on the quality control results and the potential effect on the sample data quality. Laboratory Duplicate A laboratory duplicate is a second aliquot of an analytical sample taken from the same sample container. It is processed concurrently and in an identical manner with the original sample. Analysis of the laboratory duplicate is used as an indicator of method precision and laboratory sub-sampling procedures. The laboratory duplicate can also be used to provide information regarding the homogeneity of the sample matrix. The relative percent difference (RPD) between the sample and duplicate results should be within established control limits. If outside the control limits, a DAF will be completed providing details on the quality control results and the potential effect on data quality. Continuing Calibration Verification (CCV) A calibration standard of known concentration is prepared and analyzed at the beginning, end, and every ten samples throughout each analytical batch for nutrient, dissolved organic carbon, and total organic carbon analyses to assess instrument calibration performance. The calculated value for the CCV should be within 10% of the true value. If the value is not within the acceptance limits after preparation and analysis of a second CCV, appropriate corrective action will be taken (see Section 5.5). Negative Control For fecal coliform and Enterococci analyses, a negative control is used to assess the occurrence of false positives. The media is streaked with a non-target organism and analyzed using the same procedure as the samples. The negative control is expected to show no detectable target organisms, thereby evaluating the specificity of the method. Positive Control A positive control is a QC sample prepared or obtained by the lab which is known or expected to yield a positive response for the target organism. A positive control can be either a sample of water known to contain fecal bacteria, such as Lake Washington Ship Canal Water, or media streaked with the target organism. The positive control is analyzed in the same manner as the samples.

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Established quality control limits for laboratory duplicates, matrix spikes, laboratory control samples, and spike blanks are periodically assessed and updated as necessary or are specified by the method. As such, the most current limits for the various QC samples are provided in the SOP for each parameter and not provided in this document.

5.5 Corrective Action Procedures QC results may indicate a problem with sample collection, preparation, or analysis at some point(s) during the sample handling procedure. Corrective action procedures for field and laboratory analyses are provided in the SOP for each parameter and may include measures such as:

• collecting an additional hydrographic profile and/or Niskin sample if a sample collection problem was detected in the field;

• retrieving missing information not included on the sample login sheet; • recalibrating analytical instruments; • sending sensors to the manufacturer for repair or recalibration; • reanalyzing the sample if sufficient quantity remains and the re-analysis is within

the specified parameter hold time; • collecting additional samples or field measurements on a different day following a

discussion with the Water Quality Project Manager; • applying a data qualifier; or • completing a DAF.

A DAF is completed if any data were qualified. In addition, laboratory sample log-in staff document on the Sample Receipt Record any instances where anomalies were observed upon sample receipt and corrective action steps were taken prior to sample analysis. If a suspected data error is observed in either LIMS or the CTD database by a Water Quality Project Manager, the LPM will be contacted. If the data error is confirmed based upon the results from an investigation into the potential problem, the LPM will complete a data change request form and the error corrected and/or data assigned a QC qualifier.

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6.0 DATA MANAGEMENT AND REPORTING Data management and reporting are essential for sustaining and organizing the large amount of data generated from a long-term, on-going monitoring program. Information regarding the quality and usability of the data, systematic and consistent storage systems, and the ability for users to access the data are all critical for meeting project objectives. The offshore and beach monitoring programs comprise multiple data management elements including:

• laboratory and field/CTD databases for finalized data storage and retrieval; • electronic data file management (raw CTD sensor data); • document management (field observation forms, SOPs, SAPs, data validation

packages, DAFs); and • analytical and QC information management (calibration and instrument

maintenance logs, equations for processing raw data, MDL studies, and other analytical information).

6.1 CTD Hydrocast Data CTD data (electronic files) for each cast are acquired and stored on a laptop in the field. Raw (unprocessed) data files are named with a sequential-value name following collection. Data files are transferred to a network server by FSU staff once back at the lab. Processing of the raw data is typically conducted within two weeks of data collection using software provided by Sea-Bird Electronics. The processing software is based upon standardized oceanographic methods (UNESCO, 1994). The data processing procedures are detailed in the SBE 25-Plus Sealogger CTD SOP (SOP # 220) and involve applying a correction to the DO profile data based upon laboratory Winker DO data. Once processed, a QC assessment of each hydrocast is performed using profile plots generated for each CTD parameter. Any data failing the QC assessment or comments affecting data quality are qualified/added at this point before the data are loaded into the CTD database by FSU staff.

6.2 Data Storage Collection of CTD water column profile data generates a very large electronic data set for each sampling event and precludes inclusion of these data in LIMS. A subset of the upcast CTD data that are averaged at the discrete depths where Niskin bottle data are collected will be stored in LIMS. However, all hydrocast (both the upcast and downcast) data will be maintained and stored in a separate internal, web-accessible database located on a network server that is backed up on a daily basis. A software application accesses the internal database and allows the data to be viewed and downloaded via a public-accessible webpage. Field observation forms from each offshore and beach sampling event are reviewed and uploaded to LIMS for storage. All laboratory-generated data that have been reviewed and finalized are stored in LIMS in perpetuity. The LIMS database is backed up on a daily basis.

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Field instrument calibration/maintenance records, raw analytical data, and any other hard copy project information will be stored onsite at the KCEL according to standard practices for a period of about two years. After this time, the hard copies are sent to the King County Archives for the remaining portion of the required storage period of 10 years.

6.3 Data Validation and Usability Data verification and validation are critical in the evaluation of how well analytical and field data meet project DQOs. Data verification is performed, at some level, during several steps in the process of sample collection and analysis. All laboratory analytical data and field measurements are entered into KCEL’s Laboratory Information Management System (LIMS). Field data, such as in situ data measurements or recorded environmental observations, are peer reviewed prior to entry into LIMS. Laboratory analytical data are reviewed, first by the analyst and then by a senior peer reviewer, prior to approval of the data in LIMS. Throughout field sampling at offshore stations, the boat captain and lead FSU scientist are responsible for carrying out station-positioning. All sampling crew are responsible for ensuring sample containers are properly labeled and filled according to standard protocols. For beach sampling, the lead FSU scientist is responsible for ensuring samples are collected at the prescribed location and ensuring sample containers are properly labeled and filled according to standard protocols.

• Data verification and review of field and laboratory-generated data is conducted by the Laboratory Project Manager (LPM) to confirm:

• collection and analytical protocols were followed, • data are complete, with no errors or omissions, • established criteria for QC and analytical handling were met, and • data qualifiers were properly assigned.

The LPM will report any QC failures or anomalies to the Water Quality Project Manager (non-laboratory staff). The Water Quality Project Manager will provide a final data validation process to ensure the data meet the project DQOs. CTD data should be reviewed at three-month intervals at a maximum and laboratory-generated data reviewed at six-month intervals at a maximum. Laboratory QC, field replicates, and sensor performance/checks are reviewed during this final validation process as well as assessing if the data are within expected ranges. If DQOs were met, the quality of the data is considered usable for meeting project objectives. If DQOs were not met, Water Quality Project Manager will determine whether the data are still usable based upon the reason DQOs were not met. Laboratory analytical data may be stored with data qualifier flags indicating QC failures. The following are laboratory qualifiers applied to water data and their use.

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FAIL is used in conjunction with microbiological QC samples (positive and negative controls). A FAIL is applied when the results are unacceptable (Failing).

PASS is used in conjunction with microbiological QC samples (positive and negative controls), PASS is applied when the results are acceptable (Passing).

TNTC (too numerous to count) is used for microbiological parameters when the number of target colonies exceeds the countable range and no reliable estimate is available. Once the data is approved, TNTC will be converted to >#### (used when the calculated value is greater than the maximum value possible).

C (confluent growth) is used for microbiological parameters when the bacteria colonies overlap and preclude the counting of individual colonies.

SH (sample handling) indicates that a sample handling criterion was not met in some manner prior to analysis. The sample may have been compromised during the sampling procedure or may not comply with storage conditions or preservation requirements.

B is used to indicate possible laboratory contamination of a sample and is applied when the parameter of interest is also detected in the method blank. Sample results that are less than or equal to five times the concentration detected in the method blank and are greater than the MDL will be given a “B” qualifier. Sample results that are greater than five times the concentration detected in the method blank and less than ten times the concentration detected in the method blank will be given a “B3” qualifier.

J is applied to a parameter result when the reported value is an estimated value. The J qualifier should be used whenever the magnitude of a QC failure or observed interference, unacceptable qualitative response or compromised analysis conditions, would indicate the measured response was outside the expected accuracy of the method. A “JL” qualifier indicates possible high-biased data and a “JG” qualifier indicates possible low-biased data.

R (rejected) indicates that the numerical result for the parameter, based on the professional judgment of the laboratory, is neither scientifically defensible nor representative of the true value for a sample. Indefensible and non-representative data occur whenever sample collection, sample handling, critical analysis conditions or other system failures occur that would prevent the use of the result for any purpose other than an approximate minimum or maximum value. The “R” qualifier may be combined with other applicable flags (B or H) to indicate the magnitude of the original qualifier(s). A text comment must be added to each parameter with an “R” qualifier to indicate the specific reason for the qualifier.

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TA (text available) is used when a lab error has occurred or any other relevant observation has been made. An explanation will be given in the “Comments” field in LIMS.

<MDL (less than method detection limit) is used when the calculated value of an analyte is less than the minimum value possible based on dilution and lowest reliable detection the method can achieve.

<RDL (less than reporting detection limit) is the lowest concentration at which an analyte can be detected in a sample and be reported with a realistic degree of accuracy and precision. If a sample requires dilution, the RDL value is raised corresponding to the dilution factor.

6.4 Data Reports The long-term marine offshore and beach monitoring programs have generated extensive datasets over the 25+ years of sampling. Analyzing and interpreting data results requires a team approach by Water Quality Planners in the Marine and Sediment Assessment Group. The project manager for each monitoring component leads the data reporting, with other group members assisting. The Marine and Sediment Assessment Group generates a variety of reporting products for internal customers as well as for other scientists and the public. Data reports and presentations are produced for internal customers, meetings, regional reports, regional and national conferences, and by request of management and other public entities. Water Quality Planners use various methods to analyze and present the data. The analytical approaches are chosen based on the assessment and product needs, such as evaluation of current conditions or long-term trends. The analysis methods used are generally accepted and appropriate practices for evaluating marine water data in the context of trends, influence of local and large-scale climate patterns, anthropogenic input, and estuarine circulation. Data are summarized and displayed using a variety of standard scientific graphical methods and are appropriate for the intended audience and product needs. Data products are available on the Marine Monitoring Webpage at https://green2.kingcounty.gov/marine/.

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7.0 TRAINING AND SAFETY PROTOCOLS All technical personnel involved in conducting field and laboratory work must be qualified to perform their assigned activity and that training be documented. Staff who have the education and/or experience needed to perform an assigned task are considered qualified. Continual professional development through applied training and providing opportunities for professional growth is encouraged at the KCEL as well as at the department level. Technical training encompasses all aspects of specific procedures and requirements. All personnel that perform technical activities must be trained to perform their assigned activities prior to conducting those procedures independently. All KCEL personnel will have documented training, with the QA Officer maintaining the training records for each staff member. General safety training is provided to each employee. Specific safety training sessions are conducted with staff whose responsibilities expose him or her to potential risk or hazard (e.g., boating and chemical safety). The QA Officer and the Unit Supervisor(s) are responsible for identifying and documenting the need for specific safety training. In addition to boat safety training, all staff responsible for participating in the operation of the large research vessel, R/V SoundGuardian, must have completed internal deckhand training. In order to operate the boat in capacity of Captain, the individual must have a current Merchant Mariner Credential of at least OUPV (Operator of Uninspected Passenger Vehicle), but preferably 50 or 100 ton Masters.

7.1 Field Safety Procedures The following general field safety guidelines will be read and understood by all field personnel and is applicable to both offshore and beach water sampling:

• all crew of the research vessel will follow all aspects of the KCEL Vessel Safety Plan, • samplers will wear chemical-resistant gloves when collecting a sample and/or

adding preservative, • no eating or drinking by sampling personnel will be allowed during active sampling

operations, • all sampling operations will be conducted during daylight hours, • all accidents will be reported to a supervisor within 24 hours of occurrence, and • all crew members will be aware of the potential hazards associated with any

chemicals used during the sampling effort. To help prevent accidents and ensure adequate preparation for potential emergencies, the following safety equipment will be required on the R/V SoundGuardian:

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Marine Offshore and Beach Water Monitoring: Sampling and Analysis Plan

King County Science and Technical Support Section 45 May 2020

• one personal floatation device (PFD) for each crew member and one throwable PFD, • an accessible, clearly labeled, fully stocked first-aid/CPR kit, • an accessible and clearly-labeled eye wash, • one (preferably two) VHF marine radio(s) with weather channel, • a cellular telephone, • a horn, • navigation lights, • an emergency life raft, • an anchor and suitable line, • signal flares, and • a reach pole or shepherd's hook.

Personal protective equipment will be selected and used that will protect crew members from the potential hazards likely to be encountered when operating the winch and CTD rosette, such as its suspension above the vessel deck and the heavy weight of the frame. Prior to each sampling event, all cabling, shackles, pins, housings, and swivels will be inspected to ensure the integrity of all points along the sampling assembly. The winch drum, blocks, A-frame, any area between the CTD rosette and railings, and heavy equipment all represent significant pinching and crushing hazards. Only trained and experienced crew members will operate the winch or A-frame during a sampling event. Other crew members will exercise care to avoid these potentially hazardous areas. Required personal protective equipment when working on the back deck of the vessel includes a hard hat, steel-toe rubber boots, and safety glasses. Required personal protective equipment when beach sampling includes waterproof waders. Recommended additional personal protective equipment will include rain gear and hearing protection when the vessel is under way and an orange safety vest when beach sampling.

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Marine Offshore and Beach Water Monitoring: Sampling and Analysis Plan

King County Science and Technical Support Section 46 May 2020

8.0 REFERENCES APHA (American Public Health Association). 2017. American Water Works Association,

Water Environment Federation. Standard Methods for the Examination of Water and Wastewater, 23rd Edition.

EPA (Environmental Protection Agency). 1997. In Vitro Determination of Chlorophyll a and Phaeophytin a in marine and freshwater algae by flourescence. Revision 1.2. USEPA, Office of Research and Development, Cincinnatti, Ohio.

Kerouel, R. and A. Aminot, 1997. Fluorometric Determination of Ammonia in Sea and Estuarine Waters by Direct Segmented Flow Analysis. Marine Chemistry 57 (1997) 265–275.

King County. 2009. Water Quality Status Report for Marine Waters 2005–2007. Prepared by Kimberle Stark, S. Mickelson, and S. Keever. King County Department of Natural Resources and Parks, Seattle, WA.

King County. 2014. Report on an Inter-Laboratory Marine Nutrient Comparison Study Between the King County Environmental Laboratory and University of Washington Marine Chemistry Laboratory. Prepared by Scott Mickelson, King County Department of Natural Resources and Parks, Seattle, WA, and Julia Bos, Washington Department of Ecology, Lacey, WA.

King County. 2016. Marine Phytoplankton Monitoring Program Sampling and Analysis Plan. Prepared by Amelia Kolb, G. Hannach, and L. Swanson. King County Department of Natural Resources and Parks, Seattle, WA.

PSEP (Puget Sound Estuary Program). 1991. Recommended Guidelines for Measuring Conventional Marine Water Column Variables in Puget Sound. Prepared for U.S. EPA and Puget Sound Water Quality Authority.

PSEP (Puget Sound Estuary Program). 1997. Recommended guidelines for sampling marine sediment, water column, and tissue in Puget Sound. Prepared for U.S. Environmental Protection Agency, Region 10, Office of Puget Sound, Seattle, WA and Puget Sound Water Quality Authority, Olympia, WA.

UNESCO. 1994. Protocols for the Joint Global Ocean Flux Study (JGOFS) core measurements. pp. 104–118.

Whitledge, T. E., S. C. Malloy, C. J. Patten, and C. D. Wirick, 1981. Automated Nutrient Analyses in Seawater. Technical Report, Brookhaven National Laboratory. Upton, NY.

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King County Science and Technical Support Section A-1 May 2020

Appendix A: Station Parameters and Depths

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Marine Offshore and Beach Water Monitoring: Sampling and Analysis Plan

King County Science and Technical Support Section A-2 May 2020

Table A-1 Offshore station semimonthly/monthly sampling

1 Sample collected 1m above the bottom (depth variable with tide height). 2 Phytoplankton and zooplankton are not included in this SAP, but are included in the table for reference. Note: CTD profiles are collected from the surface to near bottom at 0.5m intervals

Phyto

Station Depth (m) Ente

roco

ccus

Feca

l Col

iform

Amm

onia

Nitr

ogen

Nitr

ite +

Nitr

ate

Nitr

ogen

Tota

l Nitr

ogen

Ort

hoph

osph

orus

Silic

a

Chlo

roph

yll-a

Phae

ophy

tin

Tota

l Sus

pend

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olid

s

Salin

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Chlo

roph

yll,

Fiel

d

Den

sity

, Fie

ld

Dis

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ield

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t Int

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ty (P

AR),

Fiel

d

Salin

ity, F

ield

Sam

ple

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pera

ture

, Fie

ld

Surf

ace

Ligh

t Int

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ty (P

AR),

Fiel

d

Tran

smis

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ield

Dis

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ield

Sam

ple

Dep

th

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ple

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Sam

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2

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ique

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2

JSUR01 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1chlorophyl l max 1 1 1 1 1 1 1 1 1 1

15 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 125 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 135 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 155 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

100 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1175 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

KSBP01 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1chlorophyl l max 1 1 1 1 1 1 1 1 1 1 1 1

15 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 125 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 130 135 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 155 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

100 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1200 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

CK200P 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 115 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 125 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 135 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 155 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

KSSK02 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1chlorophyl l max 1 1 1 1 1 1 1 1 1 1

15 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 125 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 135 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 155 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

LTBC43 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 115 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

LTED04 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1chlorophyl l max 1 1 1 1 1 1 1 1 1 1

15 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 125 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 135 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 155 1 1 1 1 1 1 1 1 1 1 1 1 1 1 175 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

LSEP01 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1chlorophyl l max 1 1 1 1 1 1 1 1 1 1

15 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 125 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 135 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 155 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

100 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1180 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

LSKQ06 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 115 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 125 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 135 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

LSNT01 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1chlorophyl l max 1 1 1 1 1 1 1 1 1 1

15 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 125 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 130 1 1 1 1 1 1 1 1 1 1 135 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 155 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

100 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1180 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

CTDLaboratoryBacteria Field ZooPl

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King County Science and Technical Support Section A-3 May 2020

Table A-1 Offshore stations (cont.)

Note: CTD profiles are collected from the surface to near bottom at 0.5m intervals Table A-2 Duwamish River Subestuary stations

Note: CTD profiles are collected from the surface to near bottom at 0.5m intervals Table A-3 Beach stations

Phyto

Station Depth (m) Ente

roco

ccus

Feca

l Col

iform

Amm

onia

Nitr

ogen

Nitr

ite +

Nitr

ate

Nitr

ogen

Tota

l Nitr

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Ort

hoph

osph

orus

Silic

a

Chlo

roph

yll-a

Phae

ophy

tin

Tota

l Sus

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s

Salin

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Chlo

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Fiel

d

Den

sity

, Fie

ld

Dis

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ed O

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ield

Ligh

t Int

ensi

ty (P

AR),

Fiel

d

Salin

ity, F

ield

Sam

ple

Tem

pera

ture

, Fie

ld

Surf

ace

Ligh

t Int

ensi

ty (P

AR),

Fiel

d

Tran

smis

sivi

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ield

Dis

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ed O

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n, F

ield

Sam

ple

Dep

th

Sam

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Star

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Sam

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LSVV01 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 15 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

MSJN02 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 115 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 125 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 135 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 155 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

MSWH01 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

variable1 1 1 1 1 1 1 1 1 1 1 1 1 1

NSAJ02 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

variable1 1 1 1 1 1 1 1 1 1 1 1 1 1NSEX01 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

chlorophyl l max 1 1 1 1 1 1 1 1 1 1 1 115 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 125 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 13035 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 155 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

100 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1170 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

1 Sample col lected 1m above the bottom (depth variable with tide height).2 Phytoplankton and zooplankton are not included in this SAP, but are included in the table for reference.

CTDLaboratoryBacteria Field ZooPl

Station Depth (m) Ent

eroc

occu

s

Fec

al C

olifo

rm

Am

mon

ia N

itrog

en

Nitr

ite +

Nitr

ate

Nitr

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osph

orus

Sili

ca

Tot

al S

uspe

nded

Sol

ids

Dis

solv

ed O

rgan

ic C

arbo

n

Tot

al O

rgan

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arbo

n

Dis

solv

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n - W

inkl

er

Sal

inity

Chl

orop

hyll,

Fie

ld

Den

sity

, Fie

ld

Dis

solv

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xyge

n, F

ield

Lig

ht In

tens

ity (P

AR),

Fiel

d

Sal

inity

, Fie

ld

Sam

ple

Tem

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ture

, Fie

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Sur

face

Lig

ht In

tens

ity (P

AR),

Fiel

d

Tra

nsm

issi

vity

, Fie

ld

Dis

solv

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n, F

ield

Sam

ple

Dep

th

Sam

ple

Star

t Tim

e

LTKE03 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

variable1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1LTUM03 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

variable1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1HNFD01 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

variable1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1LTXQ012 1 1 1 1 1 1 1 1 1 1 1

1 Sample col lected one meter above the bottom (depth variable with tida l height).2 This s tation i s sampled from land.

Bacteria Laboratory CTD Field

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Field

Locator Station Description Ente

roco

ccus

Feca

l Col

iform

Amm

onia

Nitr

ogen

Nitr

ite +

Nitr

ate

Nitr

ogen

Tota

l Nitr

ogen

Ort

hoph

osph

orus

Salin

ity

Sam

ple

Tem

pera

ture

, Fie

ld

JSVW04 Richmond Beach 1 1 1 1 1 1 1 1

ITCARKEEKP Carkeek Park - North 1 1 1 1 1 1 1

KSHZ03 Carkeek Park - Piper's Creek Mouth 1 1 1 1 1 1 1 1

KTHA01 Carkeek Park - Piper's Creek Upstream 1 1 1 1 1 1

KSLU03 Golden Gardens 1 1 1 1 1 1 1

KSSN04 West Point - North 1 1 1 1 1 1 1

KSSN05 West Point - South 1 1 1 1 1 1 1

KSYV02 South Magnol ia CSO 1 1 1 1 1 1 1

LTBD27 SAM Sculpture Park Beach 1 1 1 1 1 1 1

LSGY01 Seacrest Park 1 1 1 1 1 1 1

LSHV01 Alki Beach 1 1 1 1 1 1 1

LSKR01 Alki Beach - Alki Plant 1 1 1 1 1 1 1

LSKS01 Richey Viewpoint 1 1 1 1 1 1 1

LSVW01 Fauntleroy Cove 1 1 1 1 1 1 1 1

MTLD03 Normandy Park 1 1 1 1 1 1 1

MTUJ01 Des Moines Creek Park 1 1 1 1 1 1 1

NTFK01 Redondo Beach 1 1 1 1 1 1 1 1

NSJY01 Dumas Bay Park 1 1 1 1 1 1 1 1

MSJL01 Vashon Is land - Gorsuch Road 1 1 1 1 1 1 1

MSSM05 Vashon Is land - Tramp Harbor 1 1 1 1 1 1 1

MSXK01 Vashon Is land - Burton Acres Park 1 1 1 1 1 1 1 1

Bacteria Laboratory conventionalsWater

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Appendix B: Standard Operating Procedures (SOPs)

Cover pages for the King County Environmental Laboratory SOPs relevant to marine offshore and beach waters.

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