Characterization of Toxic Chemicals in Puget Sound and Major Tributaries Tom Gries and David Osterberg Washington State Department of Ecology

Introduction Puget Sound Toxics Loading Analysis –Compiled relevant information, estimated loads, identified data gaps –Developed box model for transport and fate of toxic chemicals (e.g., PCBs) –Estimated loading after land use-based water quality monitoring in two watersheds (Wed 6A) –Estimated loading from ocean exchange and from monitoring near mouths of major rivers –Synthesis (Platform session 1A)

Objectives Measure concentrations of toxic chemicals in and entering Puget Sound –To reduce uncertainty of Box Model outputs → –To calibrate Box Model Assess spatial and temporal variability Estimate loads

Sampling Design: Marine Waters Collected water samples from: 7 stations 2 depths/station 3 seasons

Sampling Design: Marine SPM Collected SPM in sediment traps Moored at 5 sites Trap array at 1-2 depths Nov 2009 to Jan 2010

Sampling Design – Major Rivers Collect depth-integrated samples from 3 quarter points in each channel Collect surface grabs for petroleum-related compounds

TSS, organic carbon, and metals similar to other studies; most organics seldom detected POC, total zinc, and PBDEs most variable Total PCBs < recent Canadian study Total PBDEs often 10X Canadian study Results: Marine Water Column

Results: Spatial Variability DOC, copper, lead, PCBs: PS > OB Cadmium: ocean boundary > Puget Sound

Deep > Surface –Arsenic, total lead –Total PCBs → Surface > Deep –DOC in ocean boundary waters Results: Spatial Variability

Results: Ocean Exchange Net exchange = Mass exported – Mass imported Mass exported = volume out x flow-weighted concentrations of surface layer at Main, Whidbey and Hood Canal basin sites Mass imported = volume into Puget Sound x concentrations of deep layer at Haro Strait and San Juan de Fuca sites Boundaries Admiralty Inlet Deception Pass 2-layer circulation Deep water flows into Puget Sound Surface water flows out of Puget Sound

Based on model-predicted water fluxes and 25 th -75 th percentile concentrations … Most parameters exported Cadmium and lead imported Results: Ocean Exchange

Conclusions General Concentrations of toxics low in marine waters and near mouths of rivers Concentrations of non-halogenated organics seldom detected in whole water Organics detected more frequently in samples of SPM

Marine waters Concentrations of organic carbon, and metals similar to other studies Concentrations of toxics often greater in Puget Sound and at depth (e.g., PCBs) PBDE concentrations high and variable Net export of most toxic chemicals out of Puget Sound (except cadmium and lead) Conclusions (continued)

Marine SPM Sedimentation and flux of toxic chemicals greater in basins with more developed watersheds Chemical fluxes in Hood Canal less than in South Puget Sound (except copper) Rates can be compared to Box Model- predicted losses via sedimentation Conclusions (continued)

River water Concentrations of conventionals, nutrients, and metals in rivers similar to other studies Most measured daily loads from river mouths within ranges estimated from monitoring/modeling Overall? Results improve choice of input values for the Puget Sound Box Model and ability to calibrate it Conclusions (continued)

Recommendations To further improve estimates of external loading, sample more intensively near model boundaries and measure concentrations of most variable toxics (PBDEs) To improve detection frequency of non- polar organic compounds, focus future sampling on collection/analysis of SPM See details:

Acknowledgments Ecology staff: Bruce Barbour, Julia Bos, Randy Coots, Karin Feddersen, Mya Keyzers, Stuart Magoon, Jim Maroncelli, Dean Momohara, Dale Norton, Greg Pelletier, Brian Pickering, Mindy Roberts, Nancy Rosenbower, Dave Serdar, Janice Sloan, John Weakland, Leon Weiks, Jeff Westerlund

Reserved Slides

Parameters Measured Metals (dissolved and total arsenic, cadmium, copper, lead, and zinc) Organic compounds (33 chlorinated pesticides, 55 semivolatile organics, 22 PAHs, 209 PCB congeners, 26 PBDE congeners) Conventional parameters (total suspended solids, dissolved and total organic carbon) Nutrients (nitrogen and phosphorus), hardness, and petroleum-related compounds (TPH and oil and grease) in river water only

Total PCB Concentrations –Range pg/L (mean = 26.3 pg/L) –Puget Sound (30.7 pg/L) > Ocean Boundary (20.4 pg/L) –Ocean boundary < Dangerfield et al, 2007 (42 pg/L) –Deep layer (32.7 pg/L) > surface layer (15.1 pg/L) Total PBDEs –Detection frequency <25% –Range 50-19,000 pg/L (mean = 2900 pg/L) –Measured concentrations highly variable –6/10 detections and two highest concentrations from ocean boundary sites –Results often  10X greater than Dangerfield et al study Results: Marine Water Column

Sampling SPM from Rivers

River SPM Results Detection frequency  20% for petroleum-related compounds, semivolatile organics, and chlorinated pesticides 16 of 22 PAHs measured routinely detected in SPM with µg/Kg TPAH (mean = 120 µg/Kg) Mean PCBs = 410 ng/Kg Mean PBDEs = 1700 ng/Kg