Refocusing Mussel Watch on contaminants of emerging concern (CECs): The California Pilot Study (2009-10) Keith A. Maruya1, Nathan G. Dodder1, Rebecca A. Schaffner1, Stephen B. Weisberg1, Dominic Gregorio2, Susan Klosterhaus3,*, David A. Alvarez4, Edward T. Furlong5, Kimani L. Kimbrough6, Gunnar G. Lauenstein6 and John D. Christensen6 ecosystems, while serving as a model for monitoring ABSTRACT CECs within the region and across the nation. To expand the utility of the Mussel Watch Program, local, regional and state agencies in California partnered with NOAA to design a INTRODUCTION pilot study that targeted contaminants of emerging To characterize the spatial extent and temporal concern (CECs). Native mussels (Mytilus spp.) trends in contaminant levels in the coastal ocean and from 68 stations, stratified by land use and discharge Great Lakes, the National Oceanic and Atmospheric scenario, were collected in 2009-10 and analyzed Administration’s National Centers for Coastal Ocean for 167 individual pharmaceuticals, industrial and Science Mussel Watch Program (“Mussel Watch”) commercial chemicals and current use pesticides. has collected and analyzed bivalves and sediments since 1986 (http://ccma.nos.noaa.gov/stressors/ Passive sampling devices (PSDs) and caged Mytilus pollution/nsandt). Representative samples of locally were co-deployed to expand the list of CECs, and to abundant bivalve species have been collected from assess the ability of PSDs to mimic bioaccumulation more than 200 stations across the nation on a fixed, by Mytilus. A performance-based quality assurance/ biennial schedule, e.g., during the winter months in quality control (QA/QC) approach was developed California. To date, bivalve tissue samples have been to ensure a high degree of data quality, consistency analyzed for more than 100 trace metal and semi- and comparability. Data management and analysis volatile organic constituents and for overall condition were streamlined and standardized using automated using histopathology. After more than 20 years of software tools. This pioneering study will help shape assessment, a downward trend in levels of persistent future monitoring efforts in California’s coastal organic pollutants (POPs) that have been phased 1Southern California Coastal Water Research Project, Costa Mesa, CA 2California State Water Resources Control Board, Sacramento, CA 3San Francisco Estuary Institute, Richmond, CA 4US Geological Survey, Columbia, MO 5US Geological Survey, Denver Federal Center, Denver, CO 6National Oceanic and Atmospheric Administration, Silver Spring, MD *Currently at: Cradle to Cradle Products Innovation Institute, San Francisco, CA Refocusing Mussel Watch on CECs: The California Pilot Study (2009-2010) - 27 out or severely restricted, such as polychlorinated surface waters (Boreen et al. 2003, Guo and Krasner biphenyls (PCBs), dichlorodiphenyltrichloroethane 2009). Whereas bivalves or other aquatic species and its derivatives (DDTs) and chlordanes, is appar- may be appropriate monitoring sentinels for bioaccu- ent nationwide (Kimbrough et al. 2008a). No such mulative CECs, alternative approaches including the trend is discernable for other contaminant classes use of passive sampling devices (PSDs) that target whose usage and discharge into the environment water soluble compounds (Petty et al. 2004) as well continues, such as total polycyclic aromatic hydro- as hydrophobic pollutants (Zeng et al. 2004) show carbons (PAHs), a product of fossil fuel combustion, promise for monitoring of CECs in natural waters. and trace metals such as arsenic, copper, nickel, lead A consortium of research, monitoring and and zinc. regulatory agencies in California seized the op- Since most of the currently targeted POPs have portunity to serve as an initial test bed to facilitate been banned for use in the US, these trends are this transformation. During the 2007-08 Mussel expected to continue into the foreseeable future. Watch collection cycle, the Southern California Thus, the value of continuing to analyze these Coastal Water Research Project (SCCWRP), the contaminant classes via Mussel Watch is decreasing Multi-Agency Rocky Intertidal Network (MARINe) from the perspective of local and regional aquatic and the Ocean Unit of the State Water Resources resource managers. In response to a waning demand Control Board (SWRCB) teamed with NOAA to for legacy contaminant data, NOAA held a workshop increase spatial coverage of Mussel Watch by dou- in 2009 with personnel from local, state, regional and bling the number of existing Mussel Watch stations federal agencies to identify the most relevant infor- in California. In contrast to the original, overarching mation emanating from the Mussel Watch Program. Mussel Watch strategy of selecting stations with no The workshop participants concluded that informa- obvious anthropogenic perturbation, the new stations tion on chemicals that are expected to increase in were selected to address differences in land use and production and usage, whose discharge and fate the impact of point and non-point source discharge, characteristics favor environmental “persistence”, including several that were located in Areas of and that are currently not routinely monitored for Special Biological Significance (ASBS), defined and/or regulated, so-called “contaminants of emerg- by State law as those areas devoid of permitted or ing concern” (or CECs), was lacking (California regulated discharge (http://www.waterboards.ca.gov/ Ocean Science Trust 2009). The recommendation water_issues/programs/ocean/). was made that Mussel Watch would be an excellent A steering committee was established for this platform for examining CECs. “California pilot study”, with representatives from A wide variety of chemicals including pharma- SCCWRP, the SWRCB, the San Francisco Estuary ceuticals and personal care products (PPCPs), flame Institute (SFEI), NOAA and the US Geological retardants, contemporary use pesticides (CUPs) and Survey (USGS), to design a two-year pilot study that even food additives (e.g., caffeine) are considered addressed the following questions: CECs. Except for those most recently formulated, 1. What is the occurrence (frequency of detec- many of these chemicals have likely been present in tion, concentration) of CECs in the coastal aquatic ecosystems for years and perhaps decades, California environment? but were not previously targeted or detectable using available monitoring methods. Public awareness and 2. How does CEC occurrence vary with land recent advances in analytical chemistry have since use? resulted in widespread detection of many CECs in 3. How does CEC occurrence vary with the environment. Moreover, CECs possess a wide proximity to discharge of treated municipal range of physicochemical properties, and thus exhibit wastewater effluent and stormwater runoff? differential behavior once discharged into the aquatic 4. Which CECs are detectable in the water environment. Some, like polybrominated diphenyl column using passive sampling devices ether (PBDE) flame retardants, are hydrophobic and (PSDs)? display persistence and bioaccumulative potential (Kimbrough et al. 2008b, Meng et al. 2009). Others, 5. What is the relationship between CEC such as DEET, sulfamethoxazole and other PPCPs accumulation by PSDs and bivalve tissue? are water soluble and are rapidly transformed in Refocusing Mussel Watch on CECs: The California Pilot Study (2009-2010) - 28 The steering committee identified a list of high priority CEC classes based on the state of the science and availability of robust analytical methods, and designed a field study to address the above questions. This paper describes the process used to select target CECs, the field sampling design, analytical require- ments including data quality objectives and quality assurance/quality control (QA/QC) provisions and strategies for data management and analysis. The results of the pilot study will provide the basis for development of a robust comprehensive monitoring and assessment program for contaminants that will inform future management decisions concerning the quality of the California coastal environment. APPROACH Sampling Locations A total of 68 stations were identified for this study (Figure 1). From 1986-2006, NOAA established 36 Mussel Watch stations in California, with 21 located in southern California (south of Point Conception) and the remainder in central and north- ern California, including San Francisco Bay (SFB) Figure 1. Mussels (Mytilus spp.) were collected at 68 stations for the 2009-10 CEC pilot study along the (Lauenstein et al. 1997). To increase coverage and California (USA) coastline. Passive sampling devices to include stations that are subject to discharge from (PSDs) were deployed at 11 stations. different and/or changing land uses, 32 new stations were identified in collaboration with MARINe, a Stratification by Land Use and Proximity to consortium of local, State, and federal agencies, Known Discharges universities and private organizations whose Land Use members perform long term monitoring of rocky Land cover surrounding each station was deter- intertidal habitat along the California coast, including mined by a GIS-based analysis with four classifica- the Channel Islands. Ten new stations were located tions (http://www.mrlc.gov/nlcd_definitions.php):1) in ASBS, whereas five new stations were located in urban; 2) low density; 3) undeveloped (open space urbanized and/or agriculturally-impacted embay- characterized by barren, grass and