duwamish river sediment assessment 2019 sampling and

Water and Land Resources Division Department of Natural Resources and Parks King Street Center 201 South Jackson Street, Suite 704 Seattle, WA 98104-3855 206-477-4800 Fax 206-296-0192 TTY Relay: 711

T E C H N I C A L M E M O R A N D U M August 22, 2019 TO: Doug Osterman, Green/Duwamish Watershed Coordinator, Water and Land Resources

Division (WLRD), Department of Natural Resources and Parks (DNRP) FM: Jenée Colton, Water Quality Planner III, Science and Technical Support Section,

WLRD, DNRP RE: Sampling and Analysis Plan (SAP) for CWM project: Assessment of sediment

contamination in restored Duwamish River habitat. This memorandum describes the study design and details of sampling, laboratory analysis and data analysis for the Cooperative Watershed Management Grant Award Exhibit A10, awarded in 2018. This project has two objectives: (1) characterizing the chemical contamination of sediments in three areas with restored habitat to determine if contamination is harmful to benthic invertebrates, and (2) determining if contamination in the restored areas is lower, similar to or higher than other upstream and downstream areas of the Duwamish River. Sediment samples will be collected from each restored area and analyzed for a suite of contaminants. The resulting contaminant concentrations will be compared to Washington State Sediment Management Standards (SMS) for protection of benthic invertebrates and to existing sediment chemistry data from the Duwamish and Lower Green rivers. STUDY DESIGN Surface sediments (10 centimeters [cm] depth) will be sampled and analyzed for contaminants in three restored habitat areas of the Duwamish River. The three areas that will be sampled are Duwamish Garden (DUW-7 in the 2005 Salmon Habitat Plan) at river mile (RM) 6.8, North Winds Weir (DUW-10 in the 2005 Salmon Habitat Plan) at RM 6.3 and Cecil B Moses Park at RM 6.2 (Figure 1). The City of Tukwila led the restoration of Duwamish Gardens, a 2.15 acre site which includes 500 feet of river bank. The restoration project was completed in 2016 and created one acre of intertidal mudflats and marsh and more than an acre of native trees and shrub habitat. King County led restoration of the North Winds Weir which is a similarly sized site (2 acres) as Duwamish Gardens. The restoration project included contaminated soil removal and excavation of an off-channel habitat. This project was completed in 2009–2010.

SAP Memo for CWM Duwamish River Sediment Assessment Study August 22, 2019

Figure 1. Duwamish River restoration sites to be sampled in 2019 (Figure from Duwamish

Blueprint). Restoration work was completed at the 3-acre Cecil B Moses in the early 2000s and included creating a slough and marsh habitat. Today, the park is stewarded by the Duwamish Alive! Coalition. The target depth for collection of sediment samples is 10 cm because this is the biotic zone depth determined for the Lower Duwamish Superfund site and no other biotic zone or sedimentation rate data are known for the areas of interest. Therefore, it is assumed the biotic zone at these restoration sites is equivalent to 10 cm. Three composite sediment samples will be collected from each area and analyzed for the following parameters: total organic carbon (TOC), total solids, particle size distribution, 8 metals, polychlorinated biphenyl (PCB) Aroclors, polycyclic aromatic hydrocarbons (PAHs), phthalates, and other semi-volatile organic compounds (see Laboratory Analysis Section for a complete list). The resulting sediment chemistry data will be compared to Washington State marine SMS to evaluate if contaminants are at levels that would adversely impact the health of the benthic

SAP Memo for CWM Duwamish River Sediment Assessment Study August 22, 2019 invertebrate community present. This evaluation will provide an estimate of the health of this juvenile salmon food source. In addition, existing sediment data from upstream and downstream of the restored areas will be compared to the sediment chemistry results of this study as a relative estimate of contaminant exposure for juvenile salmon. SAMPLE COLLECTION Each restoration area will be divided into three subareas for sampling (Figure 2-4). Three grab samples will be collected from each subarea at each site and mixed together to form a composite sample for laboratory analysis. In total, nine composite samples will be collected from each of the three restoration areas, three from each subarea per site. Grab samples will be collected manually to a depth of 10 cm using stainless steel spoons. Sampling will be scheduled to occur at negative low tides to maximize the accessible area by wading/walking.

Figure 2. Cecil B Moses Park sampling subareas


Figure 3. North Winds Weir sampling subareas


Figure 4. Duwamish Gardens sampling subareas

Collection Method Subareas will be accessed for sampling on foot. Surface sediment samples will be collected manually using clean stainless steel spoons or spatulas. Three grabs targeting 10 cm depth (3.94 inches) from each subarea will be combined and mixed into one composite sample with a clean stainless steel bowl using sets of spoons or spatulas dedicated for sample collection at each subarea. All sampling equipment will be decontaminated at the King County Environmental Lab (KCEL) prior to sampling using a phosphorus-free detergent and a Reverse Osmosis water rinse.

Sample handling All samples will be collected into pre-cleaned, laboratory-supplied containers affixed with computer-generated labels. Sample containers will be selected based on Puget Sound Protocol guidelines (PSEP, 1996). Information on sample labels will include: a unique sample number; information about the sampling location; collection date; requested analyses; and information about any chemical used in sample preservation. Sample containers are summarized in Table 1.


Sample Containers, Preservation, and Holding Times

Analysis Container Preservation Holding Time PSD 16-oz CWM PP or Glass Refrigerate at 4°C 180 days

Total Solids 4-oz CWM PP or Glass Freeze at -20°C1 180 days TOC 4-oz CWM PP or Glass

(w/Total Solids) Freeze at -20°C1 180 days

Total Metals and Total Mercury

Acid washed 4 or 8 oz PP jar

Freeze at -18°C 2 Years (28 days for Mercury

BNAs 16-oz glass Freeze 1 Year2 Chlorinated Pesticides 16-oz glass (w/ BNAs) Freeze 1 Year2

PCBs 16-oz glass (w/ BNAs) Freeze 1 Year2 Notes:

1Holding time is 14 days if sample is stored at 4°C. 2One year to extraction and then 40 days to analyze. LABORATORY ANALYSIS

Conventional Parameters The conventional parameters to be analyzed, analytical methods and associated Detection Limit Goals (wet weight) are summarized in Table 2. Sample method detection limits (MDLs), reporting detection limits (RDLs), lower limits of quantitation (LLOQ and quantitation limits (QLs) may vary based on the actual mass used for analysis and any required dilutions.

Conventional Analyses

Analysis/Method Method Summary MDL RDL Particle Size Distribution /

ASTM D422 Sieve (Gravel & Sand)

Hydrometer (Silt & Clay) 0.1% dry wt. 0.5% dry wt.

1% 1%

Total Solids / SM2540-G Gravimetric 0.005% 0.01% Analysis/Method Method Summary LLOQ / QL

Total Organic Carbon / SW846 9060 PSEP96

High Temperature Combustion with Infrared

Spectroscopy 500 mg/Kg

Notes: MDL = method detection limit; RDL = reporting detection limit; LLOQ / QL = lower limit of quantitation

Metals Target elements, analytical methods, and associated Detection Limit Goals (wet weight) are summarized in Table 3. All metals analyses will be performed by the KCEL. Mercury will be analyzed by Cold Vapor Atomic Absorption (CVAA).


Total Metal Analyses (mg/Kg wet weight)

Element Digestion Method*Analytical Method LLOQ

Arsenic

SW846 3050B*SW846 6010C

2.50 Cadmium 0.250 Chromium 0.250 Copper 0.500 Lead 2.50 Selenium 2.50 Silver 0.500 Zinc 0.250 Mercury SW846 7471B 0.020

Listed wet weight LLOQ values are approximate. Actual values reported will vary with the exact amount of sample analyzed and may vary based on the presence or absence of matrix interference in the samples. The CVAA detection limit is based upon a nominal sample aliquot of 1 g, wet weight, digested with a final volume of 100 mL. ICP-OES Detection Limit Goals are based upon a nominal sample aliquot of 1 gram, wet wt., digested and made up to a final volume of 50 mL. ICP-MS Detection Limit Goals are based upon a nominal sample aliquot of 1 gram, wet weight, digested and made up to a final volume of 250 mL. LLOQ values for actual samples will be calculated based on exact amount of sample digested and will be reported to three significant figures.

Organics Base/Neutral/Acid (BNA) Extractables The detection limits for the target BNA compounds are summarized in Table 4. These Laboratory Information Management System (LIMS) MDLs and RDLs are presented on a wet-weight basis and are based on a 30 g extraction concentrated to a final volume of 1.0 ml for analysis. The LIMS RDL is equal to the LLOQ, which in LIMS will be referred to as the QL. The LIMs MDL column in Table 4 is a value that is at most one-half of the LLOQ, and could be lower if the qualitative requirements of the method are fulfilled (defined as the concentration of a low standard that meets the qualitative requirements for the reference method). The samples are sonicated in 1:1 methylene chloride:acetone (3550C) and then undergo a gel permeation chromatography cleanup. Note that detection limits can vary if limited sample mass is available for extraction (less than 30 g) or if dilutions are required due to elevated analyte concentration(s). BNA analysis will be performed according to EPA method 8270D (SW-846), using analysis by gas chromatography/mass spectroscopy (GC/MS).


BNA target analytes and detection limits (µg/Kg wet weight).

Analyte MDL RDL/QL* Analyte MDL RDL/QL* 1,2,4-Trichlorobenzene 1.7 3.33 Dibenzo(a,h)anthracene 3.3 6.67 1,2-Dichlorobenzene 1.7 3.33 Dibenzofuran 1.7 3.33 1,4-Dichlorobenzene 1.7 5.00 Diethyl Phthalate 3.3 33.3 2,4-Dimethylphenola 8.3 167 Dimethyl Phthalatea 17 33.3 2-Methylnaphthalene 1.7 3.33 Di-N-Butyl Phthalate 1.7 3.33

2-Methylphenol 8.3 16.7 Di-N-Octyl Phthalate 1.7 6.67 3-,4-Methylphenol 8.3 16.7 Fluoranthene 1.7 3.33

Acenaphthene 1.7 3.33 Fluorene 1.7 3.33 Acenaphthylene 1.7 3.33 Hexachlorobenzenea 1.7 3.33

Anthracene 1.7 3.33 Hexachlorobutadienea 17 33.3 Benzo(a)anthracene 3.3 8.33 Indeno(1,2,3-Cd)Pyrene 1.7 3.33

Benzo(a)pyrene 1.7 3.33 Naphthalene 1.7 3.33 Benzo(b,j,k)fluoranthene 2.0 3.33 N-Nitrosodiphenylaminea 8.3 16.7

Benzo(g,h,i)perylene 1.7 3.33 Pentachlorophenola 33 66.7 Benzoic Acida 33 667 Phenanthrene 3.3 6.67

Benzyl Alcohola 17 33.3 Phenol 8.3 16.7 Benzyl Butyl Phthalate 1.7 5.00 Pyrene 1.7 3.33

Bis(2-Ethylhexyl) Phthalate 1.7 6.67 Chrysene 1.7 3.33

*QL refers to the Lower Limit of Quantitation (LLOQ) and is equal to the LIMS RDL. a Soxhlet extraction and selected ion monitoring method can be used to optimize recoveries and potentially lower QLs for these analytes

For several target analytes, using the standard methodology presented above, QLs are likely to be above the SMS criteria. For these analytes, KCEL may include a separate Soxhlet extraction (EPA Method 3540) to optimize the acidic and phenolic sample recoveries. Analysis for these chemicals may be completed using a selected ion monitoring (SIM) scanning mode of the mass spectrometer optimized for early eluting acid compounds. The combination of these two steps may reduce the QLs for the following analytes:

• 2,4-Dimethylphenol • Benzoic Acid • Benzyl Alcohol • Dimethyl Phthalate • Hexachlorobenzene • Hexachlorobutadiene • N-Nitrosodiphenylamine • Pentachlorophenol

SAP Memo for CWM Duwamish River Sediment Assessment Study August 22, 2019 Chlorinated Pesticides and PCBs The detection limits for the target chlorinated pesticides and PCB Aroclors® are summarized in Table 5. For each Aroclor and Pesticide, the LIMs MDL and RDL are equal to the LLOQ, which in LIMS is referred to as the QL. These limits are presented on a wet-weight basis and are based on a 30 g extraction, which is concentrated to a final volume of 1.0 ml for analysis. These samples are sonicated in 1:1 hexane:acetone (3550C), and then undergo a gel permeation chromatography, TBA, and sulfuric acid cleanups. Note that detection limits can vary if sample mass is limited (less than 30 g) or if a dilution is required due to elevated analyte concentration(s) or interferences. Chlorinated pesticide/PCB analysis will be performed according to EPA methods 8081B/8082A (SW-846), gas chromatography/electron capture detector (GC/ECD) with dual column confirmation.

Chlorinated pesticide and PCB target analytes and sample detection limit goals (µg/Kg wet weight).

Analyte MDL/RDL/QL* Analyte MDL/RDL/QL* 4,4'-DDD 0.167 Endosulfan II 0.167 4,4'-DDE 0.167 Endosulfan Sulfate 0.167 4,4'-DDT 0.167 Endrin 0.167

Aldrin 0.167 Endrin Aldehyde 0.167 Alpha-BHC 0.167 Gamma-BHC (Lindane) 0.167

Alpha-Chlordane 0.167 Trans-Chlordane 0.167 Beta-BHC 0.167 Heptachlor 0.167 Delta-BHC 0.167 Heptachlor Epoxide 0.167

Dieldrin 0.167 Methoxychlor 0.167 Endosulfan I 0.167 Toxaphene 0.167 Aroclor 1016 0.833 Aroclor 1248 0.833 Aroclor 1221 2.50 Aroclor 1254 0.833 Aroclor 1232 2.50 Aroclor 1260 0.833 Aroclor 1242 0.833

*QL refers to the Lower Limit of Quantitation (LLOQ) and is equal to the LIMS MDL and RDL.

Quality Assurance and Quality Control Practices The QC samples that will be analyzed in association with sediment chemical testing are summarized in Table 6.


Chemistry QC Samples for Sediment Analysis

Parameter Blank1 Replicate2 Matrix Spike SRM3 Surrogates Spiked Blank

PSD No

1 Per Batch

No No No No Total Solids

1 Per Batch

No No No No

TOC 1 Per Batch 1 Per Batch4 No Yes

Mercury 1 Per Batch No4 No Yes Other Metals 1 Per Batch No4 No Yes

BNAs 1 Per Batch Yes Yes Yes Chlorinated Pest./PCBs 1 Per Batch No Yes Yes

1Batch - A group of samples analyzed together for QC purposes containing a maximum of 20 samples. 2Replicate - Triplicate analysis for all conventional parameters, duplicate analysis for metal and organic parameters. May be a Lab Duplicate or Matrix Spike Duplicate depending upon the analysis. 3SRM - Standard reference material (must be certified by NIST or NRCC). 4 A Laboratory Control Sample (LCS) will be prepared and analyzed in lieu of an SRM.

The recommended QC limits associated with sediment chemistry testing are summarized in Table 7.

Recommended Chemistry QC Limits for Sediment Samples

Parameter Blank1 Replicate2 Matrix Spike3, 5 SRM4, 5 Surrogates5 Spiked Blank5

PSD N/A < 20% N/A N/A N/A N/A Total Solids < MDL < 20% N/A N/A N/A N/A

TOC < QL < 20% 75 – 125% 80 – 120% N/A 80-120% Mercury < MDL < 20% 75 - 125% 80 to 120% N/A 85-115%

Other Metals < MDL < 20% 75 - 125% varies by analyte N/A 85-115%

BNAs < MDL < 35% varies by analyte

varies by analyte

varies by surrogate

varies by analyte

Chlorinated Pesticides < MDL < 35% varies by

analyte N/A varies by surrogate

varies by analyte

PCBs < MDL < 35% varies by analyte N/A varies by

surrogate varies by analyte

1Concentration of all analytes should be less than the method detection limit (< MDL) or <QL. 2Relative percent difference (RPD) for duplicate analysis and percent relative standard deviation (%RSD) for triplicate analysis. 3Percent recovery for matrix spike, standard reference material, and surrogates. 4If SRM is available, otherwise LCS. 5Compounds that have variable control limits are control charted and updated annually.

The data qualification flags for this project are presented in Table 8. These data qualifiers address situations that require qualification and generally conform to QA1 guidance (PTI, 1989). The KCEL qualifiers indicating <MDL and <RDL have been used as replacements for the T and U qualifier flags specified under QA1 guidance.


Summary of Sediment Data Qualifiers

Condition to Qualify Flag Comment Applied when reported value is an estimated value with a probable low bias, which may be identified by low matrix spike, LCS, surrogate or SRM recovery

JG

Applied when reported value is an estimated value with a probable high bias, which may be identified by high matrix spike, LCS, surrogate or SRM recovery

JL

Applied when reported value is an estimated value; should be used whenever direction of bias is unknown. J

Applied when a target analyte is detected at a concentration greater than or equal to the associated LIMS MDL but less than the associated LIMS reporting detection limit (LIMS RDL). The LIMS RDL is defined as the lowest concentration at which an analyte can reliably be quantified

<RDL

Applied when a target analyte is not detected or detected at a concentration less than the associated LIMS method detection limit (MDL). MDL is defined as the lowest concentration at which an analyte can be reliably detected

<MDL

Applied when a target analyte is detected at a concentration less than associated Lower Limit of Quantitation or LLOQ or when a parameter is not detected

<QL

Applied to all parameters if associated method blank is ≥ the MDL and sample result is ≥ MDL but ≤ 5 times the blank B >MDL and <5 times

detected MB result

Applied to all parameters if associated method blank is ≥ MDL and sample result is > 5 and ≤ 10 times the blank B3

All parameters between 5 and 10 times detected

MB result Indicates that numerical result for parameter, based on the professional judgment of the laboratory, is not scientifically defensible nor representative of true value for a sample

R

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.

SH container, preservation

Indicates that a holding time criterion (filtration, preparation, or analytical) was not met prior to completion of analysis H

SAP Memo for CWM Duwamish River Sediment Assessment Study August 22, 2019 DATA ANALYSIS, RECORD KEEPING, AND REPORTING Sampling information and sample metadata will be documented using the methods noted below.

• Field sheets generated by the KCEL Laboratory Information Management System (LIMS) that will include information such as:

1. sample ID number 2. locator name 3. locator bottom depth 4. sediment depth 5. physical sediment characteristics 6. date and time of sample collection 7. condition and height of tide 8. name of recorder

• LIMS-generated container labels will identify each container with a unique sample number, station and site names, collect date, analyses required, and preservation method.

• A field observation sheet will contain records destinations, sample numbers, general weather and tidal condition, equipment used, and the names of field personnel.

• Electronic coordinate data will be electronically logged for each grab sample using a survey-grade SBAS GPS unit.

• Chain-of-Custody (COC) documentation will consist of the KCEL’s standard COC form, which is used to track release and receipt of each sample from collection to arrival at the lab.

A sample of a typical field sheet used by the KCEL is included as Attachment 1. COMPARISON TO WASHINGTON STATE MARINE SEDIMENT STANDARDS Chemical concentrations will be normalized as necessary to TOC or solids content and compared to the Sediment Quality Standards (SQS) and Cleanup Screening Levels (CSLs) of the Washington State SMS (WAC 173-204-320 and WAC 173-204-562, respectively). SQS values are no effect levels and the CSL values are minor effects levels protective of the benthic community (i.e., not individuals). Adverse effects are expected when concentrations exceed the CSL.


Washington State Marine Sediment Management Standard Values (Ecology 2017)

Parameter SQS CSL Units Arsenic 57 93 mg/kg dw Cadmium 5.1 6.7 mg/kg dw Chromium 260 270 mg/kg dw Copper 390 390 mg/kg dw Lead 450 530 mg/kg dw Mercury 0.41 0.59 mg/kg dw Silver 6.1 6.1 mg/kg dw Zinc 410 960 mg/kg dw 1,2,4-Trichlorobenzene 0.81 1.8 mg/kg OC 1,2-Dichlorobenzene 2.3 2.3 mg/kg OC 1,4-Dichlorobenzene 3.1 9 mg/kg OC 2,4-Dimethylphenol 29 29 ug/kg dw 2-Methylnaphthalene 38 64 mg/kg OC 2-Methylphenol 63 63 ug/kg dw 4-Methylphenol 670 670 ug/kg dw Acenaphthene 16 57 mg/kg OC Acenaphthylene 66 66 mg/kg OC Anthracene 220 1200 mg/kg OC Benzo(a)anthracene 110 270 mg/kg OC Benzo(a)pyrene 99 210 mg/kg OC Benzo(g,h,i)perylene 31 78 mg/kg OC Benzoic Acid 650 650 ug/kg dw Benzyl Alcohol 57 73 ug/kg dw Benzyl Butyl Phthalate 4.9 64 mg/kg OC Bis(2-Ethylhexyl)Phthalate 47 78 mg/kg OC Chrysene 110 460 mg/kg OC Dibenzo(a,h)anthracene 12 33 mg/kg OC Dibenzofuran 15 58 mg/kg OC Diethylphthalate 61 110 mg/kg OC Dimethylphthalate 53 53 mg/kg OC Di-N-Butylphthalate 220 1700 mg/kg OC Di-N-Octylphthalate 58 4500 mg/kg OC Fluoranthene 160 1200 mg/kg OC Fluorene 23 79 mg/kg OC Hexachlorobenzene 0.38 2.3 mg/kg OC Hexachlorobutadiene 3.9 6.2 mg/kg OC Indeno(1,2,3-Cd)Pyrene 34 88 mg/kg OC Naphthalene 99 170 mg/kg OC N-Nitroso-di-phenylamine 11 11 mg/kg OC Pentachlorophenol 360 690 ug/kg dw Phenanthrene 100 480 mg/kg OC


Parameter SQS CSL Units Phenol 420 1200 ug/kg dw Pyrene 1000 1400 mg/kg OC Total Benzofluoranthenes 230 450 mg/kg OC Total HPAHs 960 5300 mg/kg OC Total LPAHs 370 780 mg/kg OC Total PCBs 12 65 mg/kg OC SQS = sediment quality standard CSL = cleanup screening level dw = normalized to dry weight OC = normalized by organic carbon content For OC-normalized values, TOC content must be between 0.5 and 3.5% or the dry-weight normalized value should be used instead, as provided in SCUM II (Ecology 2017)

The most recently collected existing surface sediment chemistry data from upstream and downstream of the restoration areas (Lower Duwamish Waterway Data Evaluation Report) will be compared to the restoration sites’ sediment chemistry results to evaluate the relative level of influence sediment transport may have on sediment contamination at the restoration sites.

Findings from the comparison of restoration site sediment chemistry to SMS and upstream/downstream sediments will be summarized in a technical memorandum.

REFERENCES Ecology. 2017. Sediment Cleanup User Manual II (SCUM II). Published by the Toxics Cleanup

Program, Washington Department of Ecology, Olympia, WA. Pub. No. 12-09-057. https://fortress.wa.gov/ecy/publications/documents/1209057.pdf

PTI Environmental Services. 1989. Data Validation Guidance Manual for Selected Sediment Variables. Washington State Department of Ecology. Olympia, WA.

PSEP. 1996. Puget Sound Protocols. Recommended guidelines for sampling marine sediment, water column, and tissue in Puget Sound. U.S. Environmental Protection Agency. Seattle WA.

cc: Deb Lester, Supervisor, Toxics and Contaminant Assessment Unit, Water and Land Resources Division, Department of Natural Resources and Parks

SAP Memo for CWM Duwamish River Sediment Assessment Study – Attachment 1 August 22, 2019

Attachment 1: Field Observation Form

SAP Memo for CWM Duwamish River Sediment Assessment Study – Attachment 1 August 22, 2019

duwamish river sediment assessment 2019 sampling and

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