Copper accumulation from antifouling paints in five marinas on Puget Sound

Marinas have been shown to contribute elevated levels of metals to marine waters, copper (Cu) in particular. The Cu comes primarily from antifouling paints which are designed to discourage biofouling (barnacles, mussels, and other organisms) of boat hulls. In 2011 the Washington State Legislature passed SSB5436 to phase out Cu in marine antifouling paints. This legislation states that new recreational vessels with Cu-containing bottom paint may not be sold in the state after January 1, 2018. This study provides baseline data for Cu in five marinas of different configuration and size within Puget Sound and assesses potential impacts to marine biota. Four sampling events were conducted between September 2016 and June 2017. Sample media included: water (dissolved and total fractions of metals), sediments (suspended and bottom), and biota (transplanted mussels and biofilms). We found strong evidence, across sample media that Cu accumulate inside marinas to higher levels than outside marinas, regardless of marina configuration. Marinas that are more enclosed, where water is slower to flush in and out, accumulated higher levels of Cu than more open marinas. However, concentrations of Cu were rarely high enough to be above the state water quality criterion for acute impacts to aquatic life. Sediment Cu was also not above the state criteria for the protection of benthic invertebrates. This study provides an adequate baseline dataset to measure progress as a result of recent legislation towards the reduction of Cu to Puget Sound from marinas

Monitoring stormwater contaminants in the Puget Sound nearshore: an active biomonitoring tool using transplanted mussels (Mytilus trossulus)

Stormwater delivers a diverse range of contaminants to receiving waters including Puget Sound. Monitoring stormwater pollutants and their effects on biota is critical to informing best management practices aimed at recovering Puget Sound health. In the winter of 2012/13, the Washington Department of Fish and Wildlife’s Toxics-focused Biological Observation System (TBiOS) team conducted a pilot study using transplanted mussels to characterize the extent and magnitude of contamination in nearshore biota of Puget Sound. Mussels are now a key TBiOS indicator organism for tracking contaminants in the nearshore, and the Stormwater Action Monitoring (SAM) program has adopted mussels for nearshore stormwater monitoring as well. SAM now serves as the primary funder of nearshore mussel monitoring in Puget Sound and the first two SAM mussel monitoring surveys were conducted during the winters of 2015/16 and 2017/18, with future surveys planned on a biennial basis. These mussel surveys utilized native bay mussels (Mytilus trossulus) from a local aquaculture source that were transplanted into anti-predator cages to locations along the Puget Sound shoreline. Monitoring sites covered a broad range of upland land-use types, from rural to highly urban, and concentrations of organic contaminants and metals were measured in the mussels after a two to three-month winter deployment period. Data from the first two years of mussel surveys (2012/13, 2015/16) indicates polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were the most abundant organic contaminants of those tested in the nearshore. Concentrations of both contaminants were significantly higher in the most urbanized areas and were positively correlated with impervious surface in upland watersheds adjacent to the nearshore. Patterns of PAHs (i.e. PAH fingerprints) in mussels from different locations demonstrate how mussels might be useful as indicators of sources for this particular class of stormwater contaminants in Puget Sound

Monitoring metal stress in Puget Sound using metallothionein production in mussels in the nearshore

Toxic metals are common contaminants in sediments near industrial ports and in stormwater from urban areas throughout the Salish Sea. Although pollutant concentrations have been mapped in the sediments, waters and biota of Puget Sound for decades, equating these contaminant levels to biological impacts has been attempted infrequently. Moreover, many of these attempts at studying metal toxicity have not been applied to the ecologically and economically important nearshore area. As part of the Washington Department of Fish and Wildlife’s (WDFW) 2012-2013 MusselWatch Pilot Expansion Project, an effort to develop a nearshore biomonitoring protocol for Puget Sound, mussels of the same age and reared in the same location were transplanted to over 100 locations throughout Puget Sound in November 2012. Mussels were secured in quadruplicate batches in nylon netting suspended in 16x16x16 inch cages and anchored in the low intertidal by volunteers. The mussels were allowed to equilibrate with their surroundings for two months and retrieved in January 2013. All mussels were measured and weighed by WDFW staff and supervised volunteers, shucked and homogenized, and then frozen to await analysis. A portion of each homogenized sample was delivered to the University of Washington Tacoma for analysis of metallothioneins, cysteine-rich proteins used in the metal detoxification mechanism of mussels and other bivalves. Metallothioneins were derivatized with monobromobimane, separated by reverse phase high-pressure liquid chromatography, and analyzed with a fluorescence detector. Our results and correlations with parameters measured by other WDFW collaborators, including metal concentrations and growth characteristics, will be presented. With limited funding available for toxics remediation it is imperative to develop monitoring tools that measure biological impacts specific to metal stress, and to apply those tools to understanding ecological health in the nearshore

Contaminants of emerging concern in bay mussels throughout the Salish Sea

Monitoring of bay mussels (Mytilus trossulus) has been an important part of WDFW’s Toxics-focused Biological Observation System (TBiOS) in the Puget Sound. Traditional monitoring has focused on a suite of priority compounds including PAHs, PCBs, PBDEs, and metals. In order to expand the range of compounds investigated, we undertook a pilot program in 2016 to analyze a select set of tissue samples for contaminants of emerging concern (CECs), utilizing two distinct analytical approaches. One set was analyzed by targeted methods focusing on a suite of over 200 pharmaceuticals, personal care products, and endocrine disrupting compounds. The results supported the notion of widespread exposure of marine organisms to trace levels of organic contaminants, including compounds such as the antidepressant sertraline, and the antibiotic virginiamycin. They also clearly demonstrated the importance of analytical considerations such as matrix effects, variable limits of detection, and quality assurance criteria when expanding and comparing these results across an ecosystem. A second set of tissue samples were analyzed by high resolution mass spectrometry (HRMS) in order to gain a broader understanding of exposures without focusing on a pre-defined list of analytes. This non-targeted approach utilized accurate mass, isotopic ratios, and retention time information for the tentative identification of a wide range of unique compounds for follow up analysis. Additional criteria, such as differential occurrence patterns, potential for biological interactions, and/or compound properties (e.g., halogenation), are then applied to identify a subset for focused identification. In this instance a candidate list of approximately 175 unique compounds was selected for identification based on common occurrence across samples and presence in existing accurate mass databases and libraries. These results again support the notion of a wide range of CEC exposures in the nearshore of Puget Sound, including synthetic hormones such as drospirenone

Assessing the threat of toxic contaminants to early marine survival of Chinook salmon in the Salish Sea

Human development of the Salish Sea has resulted in loss and modification of salmonid habitats, including reduced habitat quality due to contaminant inputs, particularly in the lower reaches of rivers and estuaries of the central Puget Sound. Chemical contaminants released into the Salish Sea from anthropogenic sources can reduce the health and productivity of salmon. Juvenile salmon are exposed to contaminants in freshwater, estuarine, and marine habitats but they are particularly vulnernable as they transition from fresh to saltwater because this life history stage is especially sensitive to stressors that may reduce their early marine survival. Reduced growth and disease resistance have been demonstrated for juvenile Chinook salmon exposed to environmentally relevant contaminant levels; however, synoptic, Puget Sound-wide surveys to assess the extent and magnitude of contaminant exposure are lacking. In this study we measured exposure of juvenile Chinook salmon to chemicals of concern that enter Puget Sound via stormwater, wastewater treatment facilities, atmospheric deposition to marine waters, and groundwater. During the spring and summer of 2013, outmigrating fish were sampled from the river mouthes and two adjacent marine shorelines at each of five Puget Sound river-estuary systems: Skagit, Snohomish, Green/Duwamish, Puyallup/Hylebos, and Nisqually. We (1) report the extent and magnitude of exposure, (2) compare exposure in outmigrants across five major river-estuary systems, and (3) evaluate potential effects on marine survival. Results will be used to establish a time series of contaminant conditions in juvenile Chinook salmon to measure the effectiveness of current toxics reductions strategies and actions, inform future pollution reduction efforts, and enhanced recovery of Chinook salmon

Effects of polycyclic aromatic hydrocarbons (PAHs) on Pacific herring (Clupea pallasii) embryos exposed to creosote-treated pilings related to a piling removal project in Quilcene Bay, Washington

Fish embryos spawned in Puget Sound nearshore marine habitats face a risk of exposure to a wide variety of toxic chemical pollutants during their incubation. Of particular concern are polycyclic aromatic hydrocarbons (PAHs), chemicals originating from oil spills, combusted fossil fuels, and creosote-treated pilings (CTPs). Removal of CTPs and prohibiting their use in marine waters are two recovery practices aimed at reducing PAHs and other creosote-related chemicals in marine waters. We used manually spawned and field-deployed Pacific herring embryos as a sensitive indicator of PAH exposure from CTPs, to test the efficacy of a CTP removal project in Quilcene Bay Washington. Embryos were deployed near CTPs in a 100-year-old derelict CTP field (1) before the CTPs were removed, (2) just after the removal process, to evaluate whether PAHs were released during removal, and (3) one year later, to evaluate whether PAHs lingered after CTP removal. Embryos incubated in the undisturbed CTP field prior to CTP removal exhibited PAH body burdens approximately five times higher than at reference areas, though total PAHs in the CTP-field embryos were below health effects thresholds. The CTP removal project was not fully completed during this study; CTP debris remained in the piling field and many CTPs were cut at the seafloor, resulting in freshly exposed CTP surfaces after the removal project ended. PAH concentrations in embryos sampled during and after CTP removal were 25x to 83x higher than reference embryos, and many exceeded health effects thresholds. PAH concentrations in embryos after CTP removal correlated with distance from former CTP locations. In addition, expression of cyp1a, a gene involved in PAH-detoxification, was correlated with PAH body burden. These results link embryo health with toxic contaminants associated with CTPs and illustrate the importance of fastidious adherence to appropriate CTP removal protocols to avoid contaminant risks to biota

Factors influencing Puget Sound nearshore sediment chemistry: results from the Stormwater Action Monitoring (SAM) program

In an effort to assess the status of current nearshore sediment chemical concentrations and the effectiveness of stormwater management overtime, the Stormwater Action Monitoring (SAM) program initiated a spatially balanced randomized sediment sampling study design in the Puget Sound. Forty one randomly selected sites were chosen in the nearshore adjacent to Urban Growth Areas (UGA). During summer 2016, sediment was collected at the sites six feet below the mean low low water (MLLW) line and was sieved to 2mm and less. All samples were analyzed for organic carbon, metals, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyl (PCB) congeners, and polybrominated diphenyl ethers (PBDEs). Concentrations were generally low and typically below sediment criteria, but exhibited a wide range often exceeding 2 orders of magnitude. Only two sites exhibited substantially elevated levels of PAH and/or total PCBs. These two sites were located adjacent to a rail line and industrial area. A number of statistical tests were performed, but we were unable to discover any significant relationships between land cover attributes in the watersheds adjacent to the sampling sites and sediment chemical concentrations. However, sediment chemical concentrations were significantly related to the type of drift cell in which the sampling site was located. Puget Sound drift cell types are characterized by the direction and amount of sediment movement along a shoreline. For this study, sediment chemical concentrations were significantly lower in sites located in actively moving drift cells. These results suggest a resorting and dilution of nearshore sediment chemical concentrations is occurring, but is dependent on the type of drift cell the site is located in. Future efforts designed to assess how changes in watershed stormwater management may influence nearshore sediment chemistry will need to consider the role drift cells play in nearshore sediment dynamics

Biomagnification, oceanographic processes, and the distribution of toxic contaminants in Puget Sound’s pelagic food web

Long-term monitoring of toxic contaminants in fish has shown that Puget Sound’s pelagic food web is a regional hot spot of persistent, bioaccumulative, and toxic chemicals. Chemicals such as polychlorinated biphenyls (PCBs) are accumulated in and magnified by the pelagic food web, resulting in high concentrations in resident piscivorous fishes, salmon, and apex predators including killer whales. In this talk we underscore the importance of biomagnification of PCBs in the lowest trophic levels of the pelagic food web, and compare PCB biomagnification patterns across four of Puget Sound’s oceanographic basins. PCB data from phytoplankton, primary consumers, and resident fish predators lend credence to the hypothesis that PCBs concentrate in the pelagic food web as they enter surface waters, challenging the paradigm of preferential accumulation in sediments. Four potentially contributing factors are considered: Puget Sound’s microbial food web and abundant micro-grazers promote remineralization and recycling of organic material in surface waters, reducing the intensity of the benthic-pelagic coupling, Puget Sound’s fjord-like basins are deep enough to support vertically migrating zooplankton such as krill, which intercept and feed on sinking particles; krill feeding behavior mechanically breaks up particles and reduces their sinking rate, promoting retention of particle-bound PCBs in mid- and surface waters, a long pelagic food chain including vertically migrating zooplankton and a complex microbial community increases biomagnification potential, and sinking particles aggregate at the pycnocline in stratified waters, where they are processed by micro-grazers, and particulate PCBs are recycled by micro-grazers into the pelagic food web. These factors are discussed, using Elliott Bay as an example representing one of Puget Sound’s greatest sources of PCB contamination. Elliott Bay also has a history of large blooms of micro-grazers (Noctiluca sp.), it is deep enough to support vertically migrating zooplankton such as krill (Euphausia pacifica), and its waters can be strongly stratified

A broad-scale assessment of toxic contaminants in Dungeness crabs (Metacarcinus magister) and spot prawns (Pandalus platyceros) from Puget Sound, Washington

Dungeness crab (Metacarcinus magister) and spot prawn (Pandalus platyceros) are two common, abundant, and ecologically important benthic crustaceans that support valuable recreational, subsistence, and commercial fisheries in Puget Sound. The purpose of this study was to evaluate the geographic extent and magnitude of toxic contaminants in these two species throughout eight Puget Sound basins and three urbanized embayments as sub-locations; Elliott Bay (Seattle), Sinclair Inlet (Bremerton), and Commencement Bay (Tacoma). Data generated from this study were also provided to the Washington Department of Health for their human health risk assessment of these species. Two hundred forty Dungeness crabs were collected at 54 stations, generating 56 crab muscle and 19 crab hepatopancreas composites while 777 spot prawns were collected at 42 stations, generating 43 spot prawn muscle and 16 spot prawn head-tissue composites. Persistent organic pollutants (POPs) including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), and organochlorine pesticides as well as six metals (mercury, arsenic, cadmium, copper, lead and zinc) were analyzed in the crab and prawn tissues. Generally, the highest concentrations of POPs were observed in urban areas while most metals were found at varying levels in Dungeness crab and spot prawn muscle throughout Puget Sound. Total PCBs in muscle tissue from both species ranged from the limit of quantitation (roughly 0.85 ng/g ww) to 12 ng/g ww in non urban locations and from 14 to 180 ng/g ww in the three urban areas. PBDEs (sum of 11 congeners) and PAHs (sum of 37 analytes) in muscle tissue were low overall with all concentrations less than 6 ng/g ww. With the exception of a few metals, contaminant concentrations in the hepatopancreas of Dungeness crab and head tissue of spot prawn were as much as 36 times higher than the concentrations reported in corresponding muscle samples, suggesting POPs were being concentrated in the primary detoxifying organ in these species. This first time broad-scale Puget Sound wide assessment of these two crustaceans provides vital information into how contaminants are geographically distributed throughout the area and how they accumulate in these two important species of the Puget Sound food web