2013 A Report of the Regional Monitoring Program for Water Quality in San Francisco Bay

CONTAMINANTS OF EMERGING CONCERN THIS REPORT SHOULD BE CITED AS: San Francisco Estuary Institute (SFEI). 2013. The Pulse of the Bay: Contaminants of Emerging Concern. SFEI Contribution 701. San Francisco Estuary Institute, Richmond, CA. 20132013 A Report of the Regional Monitoring Program for Water Quality in San Francisco Bay

CONTAMINANTS OF EMERGING CONCERN Society enjoys many benefits from our ingenuity in synthesizing chemicals that enhance our health, food, homes, and the products we use. These chemicals are pervasive in our lives CONTAMINANTS and our economy. An estimated $700 billion worth of chemistry products flow through the US economy each OF EMERGING CONCERN year (US Department of Commerce 2013). More than 100,000 chemicals IN SAN FRANCISCO BAY have been registered or approved for commercial use in the US, including more than 84,000 industrial chemicals, 9,000 food additives, 3,000 cosmetics ingredients, 1,000 pesticide active ingredients, and 3,000 pharmaceuticals (Muir and Howard 2006, Benotti et al. 2009, USEPA 2013). Global chemical production is projected to continue growing by about 3% per year, and double every 24 years (Wilson and Schwarzman 2009).

2 OVERVIEW 3 PFOS HBCD PBDEs Fipronil Nanomaterials PBDDs and PBDFs Many, many others Many, Pyrethroids (14 chemicals) Alternative ame retardants No CECs currently in this tier No CECs Pesticides (dozens of chemicals) Short-chain chlorinated parafns Pharmaceuticals (100+ chemicals) Plasticizers (bisphenol A, phthalates) Fluorinated chemicals (17 chemicals) Nonylphenol and nonylphenol ethoxylates Nonylphenol and nonylphenol Personal care product ingredients (10 chemicals) Personal care product ingredients (10 TPhP, TDCPP, TCPP, TCEP, TBEP, TBPP, V6, EBTEBPI, TBECH) TBPP, TBEP, TCEP, TCPP, TDCPP, TPhP, (BEH-TEBP, EH-TBB, DBDPE, PBEB, BTBPE, HBB, Dechlorane Plus, EH-TBB, DBDPE, (BEH-TEBP, OF OF A OF A UNCLEAR MODERATE MODERATE NO IMPACT NO IMPACT IMPACT ON IMPACT LOW IMPACT LOW IMPACT Prioritization Scheme for CECs in San Francisco Bay Francisco in San CECs for Scheme Prioritization WATER QUALITY WATER OR HIGH IMPACT OR HIGH IMPACT HIGH PROBABILITY HIGH PROBABILITY HIGH PROBABILITY HIGH PROBABILITY HIGH PROBABILITY ON WATER QUALITY ON WATER QUALITY ON WATER ON WATER QUALITY ON WATER

LOW HIGH TIER 1 TIER 3 TIER 2 TIER 4 CONCERN CONCERN CONCERN CONCERN POSSIBLE MODERATE Photograph by Tim Davis. Photograph by Tim  Although these chemicals generally enhance our lives in Fortunately, many of the more than 100,000 chemicals in Bay monitoring is also providing documentation of what many ways, they can sometimes have undesired side effects. commerce do not pose threats to water quality. Only a small appears to be a prime example of effective CEC manage- Some chemicals escape and persist beyond their intended percentage of this universe of chemicals fits the description ment. PBDEs are bromine-containing flame retardants uses and enter aquatic ecosystems where they pose health of a CEC. Furthermore, only a handful of CECs rise to a that were practically unheard of in the early 1990s, but threats to aquatic life and to people who consume fish and level of concern corresponding to a real or suspected impact increased rapidly in Bay fish and wildlife over the next shellfish. Aquatic organisms in urban water bodies like San on the quality of the Bay as habitat for aquatic species or as 10 years to become pollutants of concern. The high and Francisco Bay are exposed to a dilute soup of antibiotics, a source of fish and shellfish for human consumption. Early rapidly increasing levels of PBDEs in marine mammals and beta blockers, stimulants, pain relievers, lipid reducers, identification of these problem CECs and quick action to humans from the Bay Area were particularly alarming, and antidepressants, anxiety reducers, hypertension reliev- nip them in the bud is an optimal and cost-effective strategy it seemed that PBDEs could become the next persistent ers, insect repellents, stain repellents, detergents, flame for protecting water quality. This is especially true in an legacy contamination problem for the Bay. In 2004, two of retardants, insecticides, herbicides, fungicides, rodenticides, ecosystem like the Bay, which is a long-term trap for per- three popular commercial PBDE mixtures, PentaBDE and lubricants, polymers, plasticizers, nanomaterials, and many sistent contaminants, with recovery taking decades or even OctaBDE, were voluntarily phased out by the manufacturer, other chemicals, not to mention byproducts and degrada- centuries when the contamination is extensive. slightly preceding a California ban that was to take effect in tion products. For the past decade the Regional Monitoring Program 2006. RMP monitoring over the past 10 years has docu- Assessing the environmental hazard posed by these thou- for Water Quality in San Francisco Bay (RMP) has been mented the success of this management action - dramatic sands of chemicals is a daunting task. It requires informa- making a concerted effort to identify problem CECs. Bay reductions have been observed in PBDE concentrations in PAGE 65 tion on how they move and persist after they are released water quality managers and RMP scientists have developed bivalves, fish, and bird eggs ( ). In addition, under- to the environment, how potent they are as toxicants, and a tiered scheme for prioritizing CECs that is used to guide standing of the toxicity of PBDEs to humans and wildlife measurements of their occurrence in ecosystems of interest. decisions on monitoring (PAGE 48) and management has improved, and Bay concentrations are well below the For many of these chemicals, assessment of their potential (PAGE 3) (PAGE 8). The good news is that, in spite of dili- effect thresholds that are now more firmly established for impacts on Bay water quality is severely hampered by the gent surveillance, no CECs are presently classified as a high birds and for humans; concern remains, however, for some lack of information on the chemicals present in commercial concern, where a severe or moderate impairment of water other Bay species. Through management, monitoring, and products, their movement in the environment, and their quality is considered highly probable. A few CECs have improved understanding, PBDEs have shifted from being toxicity. Screening of chemical properties and toxicity is risen to a level of moderate concern - including the stain a contaminant of emerging concern 10 years ago to a con- currently required for some chemicals, but could be im- repellent PFOS (PAGE 55), the insecticide fipronil PAGE( taminant of diminishing concern today. proved and expanded. Many chemicals enter the market de- 83), the detergent ingredients nonylphenols and nonylphe- Preventing water quality impairment from happening, spite little to no data on toxicity or environmental impacts. nol ethoxylates (PAGE 59), and the flame retardants known rather than waiting to react once environmental degrada- Furthermore, much of the information that does exist is not as PBDEs (PAGE 63) - where there is a high probability of tion has occurred, is the ideal way to protect the health made available to the public. Measuring chemicals in Bay a low degree of impairment of water quality. On the other of the Bay and other aquatic ecosystems. The California samples at the low concentrations that can cause toxicity hand, many CECs have been monitored in the Bay and Department of Toxic Substance Control’s Safer Consumer is challenging and often requires customized and expen- found to be of low concern, where concentrations are well Products Regulations (PAGE 13) are poised to become an sive analytical chemistry methods. When the identities of below known thresholds for adverse effects. A multitude of excellent example of this type of management approach. the potentially problematic chemicals are not known, it is CECs fall into a final category of possible concern, where This edition of the Pulse provides a summary of the current exceptionally challenging. knowledge of occurrence in the Bay or of effect thresholds state of knowledge of CECs in the Bay. Profiles of the CECs When we do have sufficient information on occurrence are not sufficient to allow assignment into the low, moder- of greatest concern summarize information on their use, and toxicity, some of these chemicals can be identified ate, or high concern tiers. properties, recent findings from monitoring in the Bay and as contaminants of emerging concern, or CECs. A CEC CEC studies performed by the RMP have been guided by elsewhere, and developments in management. PAGE can be defined as any chemical that is not regulated or some of the world’s leading experts on this subject ( CEC monitoring is one of the top priorities of the RMP. 51 commonly monitored but that has the potential to enter ), and are chiefly responsible for making the Bay one of The RMP and its partners will continue to strive to protect the environment and cause adverse ecological or human the most thoroughly-monitored aquatic ecosystems in the Bay water quality through vigilant surveillance and manage- health impacts. world with respect to CECs. For some chemicals, such as ment of CECs in the years to come. PFOS (PAGE 55) and PBDEs (PAGE 63), Bay monitoring by the RMP and others has revealed contamination that rivals the highest concentrations observed in the world. 4 TABLE OF CONTENTS 5 TIER 2 TIER 4 TIER 3 TIER 1 Fipronil 83 IN THE BAY IN THE BAY s Perfluorooctane Sulfonate 55 Pyrethroids 79 P N Introduction The RMP Emerging Contaminants Workgroup Contaminants RMPThe Emerging Polybrominated Diphenyl Ethers Ethers Diphenyl Polybrominated Chlorinated Paraffins Paraffins Chlorinated Currently Used Pesticides Pesticides Used Currently On the Lookout for CECs New On Lookout the Furans and Dioxins olybrominated Alkylphenols Alkylphenol and Ethoxylates Alternative Flame Retardants Products Care Personal and Pharmaceuticals Nanomaterials or anoparticles Triclosan Triclosan M BAY FRANCISCO IN SAN CONCERN R REFERENCES C 87 91 92 93 94 51 54 59 63 67 71 75 A GUIDE TO CEC TO A GUIDE OF EMERGING CONTAMINANTS ONITORING ANDREDITS ACKNOWLEDGEMENTS PARTICIPANTS AND MEMBERS COMMITTEE MP

Comments or questions regarding The Pulse or the RMP can be addressed Jay Davis, RMP Lead Scientist, (510) 746-7368, [email protected] to Dr. 95 97 98 54 48 46

Selenium IN SAN FRANCISCO BAY FRANCISCO IN SAN Flows and Loads and Flows Products s 31 41 CM Chlorophyll and Dissolved Oxygen Dissolved and Chlorophyll 39 Climate and Habitat and Habitat Climate PBDEs 43 36 Graph Details Graph 45 Mercury 28 PAHs 34 ith Pathways to San Francisco Bay to Francisco San Pathways ith w R The Turning Tide The Turning Nutrients Populations Populations Nutrients and Sediment Sediment and Nutrients Toxics and Bacteria Bacteria and Toxics PCBs Human Presence Presence Human Biomonitoring California Measures Contaminants in Californians in Contaminants Measures California Biomonitoring

The 303(d) List and Regulatory Status of Pollutants of Concern of Pollutants of Regulatory Status and List 303(d) The Treating CECs in Municipal Wastewater Municipal in CECs Treating Cradle to Cradle Certified Target Organisms and Application Sites of Pesticides Pesticides of Sites Application and Organisms Target California Safer Consumer Products Regulations Products Safer Consumer California Pesticide Management Pesticide Europe in for Safer Chemicals EACH LATEST MONITORING RESULTS MONITORING LATEST 38 40 42 44 26 32 MANAGEMENT OF CEC

23 18 19 20 22 13 14 15 16 WATER QUALITY TRENDS AT A GLANCE AT TRENDS QUALITY WATER

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6 2 24 6 MANAGEMENT UPDATE 7

IN SAN FRANCISCO BAY FRANCISCO IN SAN Products s CM ith Pathways to San Francisco Bay to Francisco San Pathways ith w R The Turning Tide The Turning Biomonitoring California Measures Contaminants in Californians in Contaminants Measures California Biomonitoring

Treating CECs in Municipal Wastewater Municipal in CECs Treating Cradle to Cradle Certified Target Organisms and Application Sites of Pesticides Pesticides of Sites Application and Organisms Target California Safer Consumer Products Regulations Products Safer Consumer California Pesticide Management Pesticide Europe in for Safer Chemicals EACH MANAGEMENT OF CEC

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HIGHLIGHTS MANAGEMENT OF CECs The Bay Area regulatory, scientific, and stakeholder community has been proactive in putting together a framework to guide management and monitoring of contaminants of emerging IN SAN FRANCISCO BAY concern (CECs) in San Francisco Bay The framework is tiered with levels of management and TOM MUMLEY and NAOMI FEGER, LORIEN FONO, monitoring that correlate with the estimated environmental risk San Francisco Bay Regional Water Board Patricia McGovern Engineers posed by a CEC [email protected] KELLY MORAN, KARIN NORTH, TDC Environmental Bay Area agencies have been implementing management City of Palo Alto actions locally and pursuing actions at the federal and state level that are consistent with the framework for more than ten years, including public education and outreach, local ordinances, regulations, and legislation

Polybrominated diphenyl ether (PBDE) flame retardants are one success story, where a phase-out in 2004 and a state ban in 2006 appear to have caused a marked decline in concentrations in the Bay food web

As CEC science continues to advance, we will refine our efforts and improve our strategy for managing CECs, building upon implementation successes and lessons learned

8 MANAGEMENT UPDATE | MANAGEMENT OF CEC s 9 MODERATE CONCERN LOW CONCERN • • CECs in the Bay and potential sources. Key management Key management sources. potential and in the Bay CECs analytical improved of include: 1) development actions methods; 2) iden- methods bioanalytical and screening 3) determining Bay; to the sources tification of potential toxicity; and 4) identifi- and exposure pathways potential actions pollution prevention low-cost and of easy cation that trends with or market use product for contaminants Bay. in the occurrence possible increasing suggest The Tier 3, Moderate Concern Concern includes Risk Level Moderate 3, Tier The concentra- found at frequently are that contaminants effect an than higher or slightly to equal are tions that will strategy be management and A monitoring threshold. consideration including 3 CEC, Tier for each developed Emerging The actions. regulatory and of non-regulatory pilot will oversee and develop Workgroup Contaminants to and loadings effects, fate, evaluate to studies special and will 3 contaminants All decisions. Tier inform management part of whether they become determine to be evaluated in the RMP. monitoring routine TIER 3 TIER 2 contami- Concern includes Risk 2, Level Tier Low The indicate and available are data occurrence Bay where nants thresholds. effect below is present the contaminant that include no 2 chemicals may for Tier actions Management we that no further and action for contaminants monitoring trend no increasing confidence willhave reasonable have and include easy they may Alternatively, occurrence. in Bay and pollution identification prevention source low-cost pos- suggest with that trends use for contaminants actions the also affect would trends Use in the Bay. sible increases frequency of further in the Bay for occurrence monitoring or runoff. in wastewater trends track or decisions to The goal is to prevent water water is to prevent The goal impairmentquality than rather adverse to react once waiting effects are observed ) provides an ongoing ongoing an ) provides PAGE 51 PAGE POSSIBLE CONCERN • educe loading from controllable sources through through sources controllable from loading educe rack consumer product and use trends, including including trends, use and product consumer rack monitor- CEC international and national, state, rack in the Bay of CECs in occurrence trends rack path- different through of CECs loading the rack new products and new uses for existing uses new and products. products new properties, chemical of their on the basis Rank CECs in and or knownlikely occurrence thresholds, effects the Bay. Identify efforts.CECs potential management and ing support to or preclude strategies management and efforts. local or regional T the RMP. through T or wastewater of municipal as discharge such ways, runoff.urban R control, source pollution prevention, cost-effective strategies. treatment and T T

• • • • • forum to identify and prioritize CECs of potential concern forum concern identify to of potential prioritize and CECs effortsconsumer and international and national tracking by also Workgroup The trends. use product and product of the presence determine to studies oversees and develops Overview of the Risk Tiers Overview Risk the of monitoring riskand associated tiers environmental The described below. are actions management and strategies hierarchy, as a risk-based presented Although the tiers are actions management and strategies monitoring the listed and Strategies tier. each be unique to to not intended are de- be implemented tiers may or lower in higher actions specificcontaminants of of knowledge on the state pending feasibility and the cost and of of contaminants or categories actions. and strategies candidate TIER 1 contami- Concern includes Risk Possible Level 1, Tier The merit but to concern, is sufficient knowledge where nants still impacts exist.Bay about Those uncertainties significant their occurrence about uncertainties include information which at or uncertainty the concentration about in the Bay concern is for The potential impacts. adverse they cause expert or knowledge, in the literature, on information based Emerging The RMP’s locations. geographic other from data ( Workgroup Contaminants ), TABLE 1 ) has been a focal point for a focal point been ) has PAGE 51 PAGE The Golden Gate Bridge. Photograph by Tim Davis. The Golden Gate Bridge. Photograph by Tim developing and adapting this approach. this approach. adapting and developing the high-risk tier reaching from CECs to prevent is goal The actions. cost-effective feasible, the most implementing by the following encompasses strategy This prevention-based within the implemented and be considered to components framework. tiered  A Tiered Framework for for Framework A Tiered Management and Monitoring and lo- Board Water Regional Bay Francisco San The Prevention Pollution Area the Bay (e.g., cal agencies Regional the by generated information using are Group), management inform CEC to (RMP) Program Monitoring Our strategy. monitoring our CEC adapt to and strategies, risk ( on a tiered framework is based approach An Ounce of Prevention of Ounce An con- emerging of contaminants about knowledge Scientific at accumulating been has in the environment (CECs) cern concern is no longer The 1990s. the late since rate a rapid they’ve since find them?” we ubiqui- to be shown been “can scientists, managers, now environment; in the aquatic tous do about “what asking should we are stakeholders and emerging of potential thousands of tens are There them?” with introduced, continually being more contaminants, quality standards water and research toxicological and which are at we up with do not keep the rate development regulatory Additionally, environment. in the them finding for management challenges barriers pose and constraints of CECs. control and com- stakeholder scientific, and regulatory, Area Bay The a framework together in putting proactive munity been has in San of CECs monitoring and guide management to which is the focus of this Thisapproach, Bay. Francisco identify to of CECs screening article, a risk-based provides appropriate an applies then and actors, possible bad quality water to prevent is goal The response. management ef- adverse once react to waiting than rather impairment observed. are fects wherein the type and level of management and monitoring monitoring and the typewherein of management level and environ- of understanding latest with the effortcorrelate Con- Emerging The RMP's risk a CEC. by mental posed ( Workgroup taminants Specific management actions could include aggressive TIER ASSIGNMENTS MANAGEMENT MONITORING pollution prevention measures or low-cost wastewater or runoff treatment controls. Regulatory actions may include permit requirements and development of water quality objectives. The California Department of Toxic TIER 4 303(d) listing Substance Control’s Safer Consumer Products regula- tory program (PAGE 13) is poised to become a viable HIGH No CECs TMDL or alternative Studies to support TMDL action mechanism for source control. Pesticides will be CONCERN currently management plan. or an alternative referred to the US Environmental Protection Agency in this tier Aggressive control actions management plan (USEPA) or the California Department of Pesticide for all controllable sources Regulation for action (PAGE 15). TIER 4 • HIGH CONCERN The Tier 4, High Concern Risk Level includes con- PFOS taminants that occur frequently in the Bay at levels that Action plan or strategy Consider including in TIER 3 Fipronil Status and Trends indicate a high probability of a moderate or high level Aggressive pollution Monitoring effect on aquatic life, wildlife, or people. This would MODERATE Nonylphenol prevention and nonylphenol Special studies of fate, likely result in placing the entire Bay, or any affected Bay CONCERN Low-cost ethoxylates effects, and sources, segments, on the state 303(d) List of impaired waters control actions for these contaminants. Listing would include the devel- PBDEs pathways, and loadings opment of a Total Maximum Daily Load (TMDL) and implementation plan for the contaminant, or an alterna- tive management plan in lieu of a TMDL that would resolve the impairment. Implementation actions would HBCD Low-cost source Discontinue screening, identi cation and control or periodically screen in include aggressive pollution prevention and treatment Pyrethroids TIER 2 water, sediment, or biota control actions for all controllable sources including Low-level pollution Pharmaceuticals wastewater and runoff to the Bay. LOW prevention Periodic screening and personal care in wastewater efuent CONCERN products Track product use or urban runoff and market trends Technical Challenges PBDDs and PBDFs to track trends The biggest challenges in monitoring and manag- ing CECs are: 1) the ever-increasing number of new chemicals in commerce that have the potential to cause adverse environmental impacts, 2) the lack of water Identify and prioritize Alternative quality standards or adverse effects thresholds to allow contaminants of Screening in water, TIER 1 ame retardants for interpretation of exposure levels, and 3) the absence potential concern, sediment, biota, of practical analytical methods to measure many CECs. POSSIBLE Pesticides track international efforts wastewater efuent, urban runoff Thus far, no CECs have been classified in the high CONCERN Plasticizers Develop targeted concern tier. However, this may be partially explained and non-targeted Many, many others by the lack of water quality criteria or thresholds for analytical methods specific chemicals, and a lack of tools to evaluate the potential additive or synergistic effects of multiple contaminants. Consequently, many CECs fall into the possible concern tier, corresponding to an unknown TABLE 1 level of risk for the Bay. Tiered framework for management and monitoring CECs in San Francisco Bay. 10 MANAGEMENT UPDATE MANAGEMENT OF CEC s

| 11 ) enter the sewer system system the sewer ) enter PAGE 71 PAGE , which guides hospitals clinics and on ospital Outreach - The BAPPG created a - The BAPPG created ospital Outreach esidential Outreach - Since 2005, the BAPPG - Since Outreach esidential H R for col- the need promoting actively been has California-specific update to the Hospitals for a to the California-specific update - Pharmaceuti Managing Environment’s Healthy cal Waste handle to (BMPs) practices management best na- a The BAPPG hired waste. pharmaceutical disposal expert pharmaceutical tional provide to Bay the around hospital staff to class a training pharmaceutical for proper on the BMPs Area disposal.

o o harmaceuticals ( harmaceuticals prevent odors and stains, which provides a pathway to to which stains, a pathway odors provides and prevent Nanosil- when washed. articles these the sewer are its fully determine been to not yet has studied ver is It environment. or the health on human impact silver overall though even a CEC, considered being The regulated. already are Bay in the concentrations Sup- Water Area with the Bay BAPPG collaborated the rebate Agency Conservation remove and ply to machine silver ion washing for the Samsung incentive nanosilver Since Area. the Bay in its sale discourage to letters the BAPPG also submitted is has a pesticide, of Department the California and the USEPA to to them encouraging Regulation (DPR) Pesticide in their environment the aquatic to pathways consider track- are BAPPG members of nanosilver. regulation nanoparticles, of these emergence the continuing ing locally marketed products any that ensure to helping for requirements fully with state and comply federal pesticides. antibacterial P from excretion of partially-metabolized medications medications of partially-metabolized excretion from through and who them take patients the human by The or expired medications. of unused flushing statewide and supportingBAPPG been national has Institute Stewardship specificallyProduct groups, the Council, Stewardship Product the California and that laws producer-responsibility pursuing are that for the disposal of pay to manufacturers require sources the two largest Since medications. unwanted system the sewer entering pharmaceuticals of unused BAPPG worked the has hospitals residents, and are the on residents and staff both hospital on educating disposal of pharmaceuticals. proper

• ). The Bay Area Pollution Area Bay ). The PAGE 14 PAGE ) is an antibacterial agent, disin- agent, ) is antibacterial an PAGE 75 PAGE anosilver is currently incorporated into a variety of into incorporated isanosilver currently riclosan ( N is its use growth, and bacterial prevent that products to in sports embedded clothing is often It on the rise. fectant, and fungicide and fectant, found in certain types of liquid deodorants. and cosmetics, toothpaste, soap, hand over substantially increased have of triclosan The uses antibacte- as well as other Triclosan, decade. the past now byproducts, are their degradation and rial agents including in the environment, found ubiquitously soil, The BAPPG fish and tissue. waters, surface on the efficacy of scientific literature reviewed triclosan not effective was that triclosan, determined washing, during hand began and bacteria in reducing agency the public through to message that deliver to BAPPG Many communityevents. and newsletters purchasing example stopped by also and led agencies triclosan. Since contain that soaps hand antibacterial BAPPG members pesticide, triclosan is a registered during the ongoing also comments provided have the US urging review process triclosan registration limit to Agency (USEPA) Protection Environmental products. of triclosan-containing the use T

• • Examples of some of these actions at the local and state state the local and at Examples actions of these of some described in the following sections. are level Wastewater Agency Pollution Prevention Efforts Prevention Agency Pollution Wastewater prevent up to teamed have agencies wastewater Area Bay plants treatment Wastewater pollution the source. at CEC as such pollutants conventional remove to designed are and material, organic solids, biodegradable suspended remove to not designed but they are toxicsome pollutants, compounds, synthetic of organic concentrations low pollu- are there Fortunately, which CECs. most includes to successfully used been have that tools tion prevention out therefore and systems, sewer out of CECs some keep costly potentially avoiding environment, of the aquatic ( end-of-pipe treatment Prevention Group (BAPPG – bacwa.org/committees/ (BAPPG Group Prevention a consortium of 43 bay-area-pollution-prevention-group), to messages outreach regional crafts agencies, wastewater As CECs the Bay. enter that of CECs the amount reduce to include messages BAPPG modifies its outreach emerge, examples of BAPPG’s Some of concern. pollutants new described below. are efforts on individualCECs egulations – State agencies that oversee classes of classes oversee that agencies – State egulations egislation – State or federal government may ban a ban may government or federal – State egislation ocal Ordinances – Municipalities and local agencies local agencies and – Municipalities ocal Ordinances ublic Education and Outreach – Government agen- – Government Outreach and ublic Education L a chemical. of using or a way chemical L R that regulations set can as pesticides such products and how sale for available affect are which chemicals or a process alsoestablish They can used. they are for identifying chemicals to requirements alternatives risks the pose and that consumers or products to environment. P local agency and organizations, cies, non-governmental provide informa- can programs pollution prevention voluntary actions influences the public that tion to individuals curtailamong to groups of and the use a risk pose the environment. to may that products their own guidelines set for which can can products be they can how and organizations their by be used product control also They can their workers. by used individuals private by circumstances. use some under

• • • • Taking ActionTaking within actions management implementing been have We state and the federal at actions pursuing and Area the Bay for more with framework the tiered consistent are that level multiple institutional actions include The years. ten than curb or minimize to successfully used been have that tools environment. the aquatic to of CECs discharges In response to the lack of effects thresholds for the vast vast for the thresholds of effects the lack to response In ef- evolving an in participating are we majority of CECs, fort identify to with classes chemicals or chemical similar and developing by action of adverse or mechanisms modes “bioanalytical”testing methods integrate These methods. based the activity a response chemicals into of multiple biological as endocrine mode-of-action,on a single such in be used may methods These disruption or mutagenicity. on based toxicity with bioassays combination conventional survival, organism or inhibited test reproduction, inhibited toolsbioanalytical These extensively. used are growth that for chemical-specific thresholds the need do not supersede if they successful, Rather, quality standards. water and of prioritizing of provide a means chemicals or classes chemicals for further evaluation. lection events and permanent pharmaceutical • DTSC is developing Safer Consumer Products The Future disposal locations for unwanted medications Regulations that will require manufacturers to con- from residents. As a result of BAPPG’s 2006 sider alternatives to a subset of specifically identified As emphasized throughout this article, the goal is to Safe Medicine Disposal Days campaign, more toxic chemicals contained in products (PAGE 13). prevent CECs from reaching levels that can cause adverse than 100 permanent collection locations have However, these regulations exclude products already impacts in San Francisco Bay. As CEC science continues to been established in the Bay Area. The BAPPG regulated by other entities, such as prescription medi- advance, we will refine our efforts and improve our strategy also supported the successful passage in 2012 cations and pesticides. for managing CECs, building upon implementation suc- of Alameda County’s Safe Drug Disposal Ordi- cesses and lessons learned. At a minimum, our actions will Legislation can be an effective means to target CECs when include the following elements. nance, which requires manufacturers to develop the weight of evidence suggests that a particular chemical and fund the collection of unwanted medica- is harmful. However, legislation is challenging, and even • Continuing to implement and improve the San tions from residents. if successful, can take years to enact and additional years Francisco Bay CEC management strategy and work- to go into effect. One success story is that of polybromi- ing proactively to reduce the likelihood that any CEC State Regulatory and Legislative Actions nated diphenyl ether (PBDE) flame retardants, a class of presents a high risk. A key component of the regional CEC management compounds that bioaccumulate in the food web (PAGE • Continuing to proactively identify and investigate strategy is to support state and federal CEC initiatives. 63). Many forms of PBDEs are considered potential endo- possible CECs and collect the necessary informa- Management of CECs is complicated by federal and state crine disruptors and are found throughout San Francisco tion to make informed management decisions about rules and regulations that govern production, sales, and use Bay. Two commercial PBDE mixtures, PentaBDE and CECs of moderate risk. of products. This can result in water quality initiatives being OctaBDE, were banned by the California legislature in stymied by rules set by other agencies. For example, locally 2003. The ban was to take effect in 2006, but manufactur- • Beginning to test and implement bioanalytical tools initiated drug take-back programs have been hampered by ers voluntarily phased these mixtures out by 2004, and we to advance understanding of effects due to CECs and Federal Drug Enforcement Agency regulations related to have since observed decreasing concentrations in the Bay. legacy contaminants in San Francisco Bay. the handling of controlled substances. There are also Euro- However, this good news is tempered by observations of • Working with state and federal agencies to prevent pean Union and Canadian initiatives that address emerging replacement flame retardants in the Bay PAGE( 67), and or limit the use of CECs that could cause harm to the contaminants in products that would have a positive ben- legislative efforts to address them have not been successful. aquatic environment. efit if applied here. For example, the European Union re- A major shortcoming of chemical by chemical legislative quires the submission of environmental risk assessments of bans is that a ban on one chemical can lead to the use of the fate and effects of compounds to gain market approval a potentially harmful replacement chemical. This under- PAGE 19 for new pharmaceuticals ( ). A similar requirement scores the purpose of green chemistry initiatives, like the is under development in Canada. In the United States, DTSC Safer Consumer Products Regulations, to address these types of initiatives have been difficult to implement at this issue by requiring an alternatives assessment as a the federal and state levels. necessary component of phasing out a chemical’s usage. There are, however, two notable State initiatives, by the Also, when regulations drive the use of toxic chemicals, DPR and the Department of Toxic Substances Control as in the case of the flammability standards for household (DTSC), that have key roles in governing use and disposal furnishing (PAGE 66), there is also the opportunity to of products. review those regulations and assess whether they can be • DPR promulgated regulations in 2012 to prevent revised. California is doing just that. The California Bureau surface water contamination by pesticides used in of Home Furnishings has been directed to revise existing outdoor non-agricultural (e.g., urban) settings. This is flammability standards and recommend changes to reduce part of an evolving effort to manage urban pesticides the use of toxic flame retardants while maintaining the fire that can adversely affect water quality PAGE( 15). safety of products.

12 MANAGEMENT UPDATE MANAGEMENT OF CEC s

| 13 The California Regulations (www. Safer Consumer Products CECs should help reduce dtsc.ca.gov/SCPRegulations.cfm) establish a process to These regulations will in the Bay. are safer alternativesevaluate whether there to a chemical of concern in a product, and to allow the Department of Toxic to implement appropriate controls. Substance Control (DTSC) In simple terms, the regulations require a manufacturer contains a chemical of concernwhose consumer product to necessary?ask: Is this ingredient Is there a safer alternative? Is that alternative by listing ingredient feasible? In addition, State will be examining in consumer the chemicals that the will have the opportunityproducts, manufacturers to elimi- chemicals ahead of a regulatorynate the use of those action. Chemicals (ap- The regulations establish a list of Candidate for the California proximately 1,200) and specify a process that exhibit DTSC to identify additional Candidate Chemicals to evaluate one or more hazard traits. They require DTSC combinations and prioritize product/Candidate Chemical which alternato develop a list of “Priority Products” for - Priority Products tives analyses must be conducted. The first 230 Candidate List will be developed using approximately hazard traits Chemicals that have a combination of listed and exposure concerns. Manufacturers (or other responsible must performentities) of a product listed as a Priority Product an alternatives analysis for the product and the chemical(s) of concern in the product to determine how best to limit health and en- exposures to, or the level of adverse public of the chemical or chemicals vironmental impacts posed by, concern in the product. re- the regulations require DTSC to identify and Ultimately, quire implementation of regulatory responses (e.g., product information for consumers, use restrictions, or product sales and the envi- prohibitions) designed to protect public health and feasible ronment, and to maximize the use of acceptable alternatives of least concern. DTSC may require regulatory responses for a Priority Product (if the manufacturer decides to continue using the chemical of concern in its product). r o  Alternatives Analyses Regulatory Response(s) for selected Alternative and/or Priority Product A Candidate is Chemical (CC) a chemical that a candidate is for designation as a Chemical Concern. of Each Candidate Chemical exhibits one or more hazard environmental traits and/or endpoints. toxicological The Candidate Chemicals that will be evaluated for development of thePriority first Products will be List ~230 chemicals that have both listed hazard traits and listed concerns. exposure A Chemical of Concern (COC) a Candidateis Chemical that is the basis for a product-chemical combination being listed as a Priority Product. PRIORITY PRODUCTS PRIORITY PRODUCTS AND THEIR COCs s CC WITH PRODUCTS ) ~1,200 CANDIDATE CANDIDATE CHEMICALS (CCs Source: Department of Substances Toxic Control, January 2013 California Safer Consumer Products Regulations CaliforniaRegulations Products Consumer Safer ALL 100,000+ CHEMICALS Treating CECs in Municipal Wastewater

Many CECs, including pharmaceuticals and personal care products, have been detected at low levels in treated municipal wastewater.

Traditional wastewater treatment processes remove CECs to some degree, depending on their chemical properties (e.g., affinity for particles) and biodegradability. These properties influence whether a CEC will remain in water (like many pharmaceuticals) or be removed with wastewater solids and sludge (e.g., certain antibiotics). Wastewater disinfection processes using chlorine can reduce concentrations of certain CECs. Treatment targeted at nutrient removal (e.g., nitrification) has been shown to enhance the removal of some CECs. Additional removal can be obtained via chemical oxidation (e.g., effluent ozonation), which is a means of enhancing breakdown of the organic matter in wastewater. Engineered treatment wetlands can also remove CECs from wastewater through processes such as microbial degradation and degradation caused by exposure to sunlight. Efforts to implement wastewater treatment improvements to remove CECs must consider various challenges. Obviously, capital and operating costs increase with the level of treatment provided, but there are other consequences of enhanced levels of treatment. For example, advanced treatment approaches can be very energy-intensive and increase carbon dioxide emissions, resulting in carbon footprint and climate change implications. In addition, some treatment processes convert CECs to degradation products whose toxicological prop- erties and environmental persistence are not well known. These ramifications need to be weighed with the desired benefit of keeping CECs out of the Bay. The optimum treatment improvements will be those that remove multiple CECs or remove CECs along with other pollutants. More treatment process research, advances in treatment technology, and improvements in our knowledge of CECs in the Bay and wastewater as a source of CECs are needed to better inform decisions on wastewater treatment of CECs.

14 MANAGEMENT UPDATE MANAGEMENT OF CEC s

| 15 - ). Califor ecosystems in the Bay watershed. harm San Francisco Bay and aquatic harm San Francisco Bay and aquatic goal of ensuring that pesticides do not goal of ensuring that pesticides do not products, and to achieve the ultimate products, and to achieve the ultimate to prevent a transition to other harmful to prevent a transition to other harmful ticide-related toxicity in urban watersheds, ticide-related toxicity in urban watersheds, - additional work will be needed to end pes concentrations of fipronil, a reminder that concentrations of fipronil, a reminder that initiated reviews of all pyrethroids, advanc- initiated reviews of all ing its regularly scheduled periodic reviews in periodic reviews in ing its regularly scheduled nia monitoring data show rapidly increasing nia monitoring data show rapidly increasing water pollution. From 2009 to 2012, USEPA 2009 to 2012, USEPA water pollution. From response to input from California water quality Californiaresponse to input from water quality PAGE 83 ity impacts, such as fipronil (PAGE approach for defining when pesticides are causing when pesticides are causing approach for defining agencies. The reviews now involve generation of now involve generation of agencies. The reviews for other insecticides associated with water qual- for other insecticides associated with water assessment methodology" to establish a consistent to establish a consistent assessment methodology" new aquatic toxicity data, preparation of detailed detailed new aquatic toxicity data, preparation of pest management, but also creating a growing market market pest management, but also creating a growing risk assessments, and decisions as to whether USEPA USEPA risk assessments, and decisions as to whether shifting the market, creating opportunities for less toxic should require nationwide risk mitigation actions (e.g., actions (e.g., should require nationwide risk mitigation Now regulatory actions addressing pyrethroids are again modified product application instructions, discontinuing discontinuing modified product application instructions, selected uses), which would be implemented between 2016 between 2016 selected uses), which would be implemented and 2020. As an interim measure, in 2009, USEPA asked asked USEPA and 2020. As an interim measure, in 2009, pyrethroid manufacturers to voluntarily place user instructions user instructions pyrethroid manufacturers to voluntarily place about water quality protection on product labels. about water quality protection on product There are also improvements at the federal level. Recognizing that a key regula- at the federal level. Recognizing There are also improvements tory its separate Pesti- from programmatic differences between gap stemmed began developing a common "effects USEPA Offices, in 2009, cides and Water ). Pyrethroids ). Pyrethroids ). In many locations toxicity that was ). In many locations toxicity that was caused by organophosphate pesticides (e.g., diazinon and chlorpyrifos, diazinon and chlorpyrifos, caused by organophosphate pesticides (e.g., formerly the most commonly applied insecticides in California urban areas), 79 pyrethroids (PAGE has been replaced by toxicity caused by In recent years, numerous studies have documented the presence of pesticide- studies have documented the presence In recent years, numerous throughout water and sediment in rivers and streams caused toxicity in both California, particularly caused by in urban watersheds, and almost exclusively 79-90 currently used pesticides (PAGE Pesticide Management Pesticide California data have water quality monitoring in unrecognized gaps revealed previously pesticide regulatory review procedures intended pollution. to prevent water in Californiabecame the most commonly applied insecticides areas urban were phased out by the after most urban uses of diazinon and chlorpyrifos and the Both USEPA in 2004. US Environmental Protection Agency (USEPA) California Department (DPR) have responsibility for of Pesticide Regulation effects on the environment regulating pesticides and must consider adverse the procedures used to identify an in their review of pesticides. However, of risks that are not adverse effect under pesticide law allow acceptance Code. Act and the California Water consistent with the Clean Water In response, Bay Area municipal stormwater and management agencies and DPR to work with USEPA wastewater treatment plants joined together water pollution in California. toward the goal of eliminating pesticide-related included professional applicators, This multi-agency collaboration, which also in 2012 that restrict the ways led to landmark regulations enacted by DPR pyrethroid insecticides around professional applicators are allowed to apply - with special restrictions placed on bifenthrin (the most envi buildings. Together regulations are expected to reduce ronmentally persistent pyrethroid), the new 2012, DPR also moved to prevent new pyrethroid-caused toxicity by 80-90%. In gaps in its surfacewater pollution by eliminating procedural water reviews for new pesticides. Target Organisms and Application Sites of Pesticides with Pathways

to San Francisco Bay INSECT INDOOR REPELLENT PESTS AND LICE BIOCIDAL AND FABRICS SCABIES DISPOSAL, SPILL, OR CLEANUP CLOTHES WASHER CLEANING PET PARASITES

SWIMMING POOLS Indoor Drains

ROOTS IN SEWER LINES COOLING TOWERS Wastewater Collection System

UNDERGROUND TERMITES

Potential Groundwater Infiltration CECs in the Bay are derived from a wide MARINE variety of sources and pathways. Pesticides, COATINGS for example, are used in many applications. PIERS They enter wastewater and stormwater collec- Wastewater AND tion systems through multiple pathways, are Treatment PILINGS removed from wastewater to varying degrees Plant by wastewater treatment (stormwater does not undergo treatment), and then discharged to the Bay. Some uses of pesticides also lead to direct entry into creeks and the Bay.

16 SAN FRAN CISCO BAY MANAGEMENT UPDATE | MANAGEMENT OF CEC s 17 AGRICULTURAL AGRICULTURAL RUNOFF AGRICULTURE

Creeks FENCES DECKS AND and Riversand ATMOSPHERIC DEPOSITION MOSQUITOES BUILDING BUILDING MATERIALS

LANDSCAPE PESTS Stormwater Urban RunoffUrban Drainage System Drainage

PESTS AROUND BUILDINGS AQUATIC AND RIPARIAN WEEDS

CISCO BAY N SAN FRA CM Cradle To Cradle Certified Products SUSAN KLOSTERHAUS, [email protected], Cradle to Cradle Products Innovation Institute One solution for the continued accumulation of hazardous chemicals in the environment and people is adoption of the Cradle To Cradle CertifiedCM Product Standard, a systematic approach to product innovation that is spurring a global paradigm shift in the way products are made. By committing to meet the requirements for certification, designers and manufacturers are making products that not only contain chemicals that are safer for people and the environment, but products that can also be recycled for future uses and are manufactured using responsible practices.

The product certification standard is based on the design principles outlined in the 2002 book, ‘Cradle to Cradle: Remaking the Way We Make Things’ by William McDonough and Michael Braungart: eliminate the concept of waste, Cradle to Cradle CertifiedCM is a certification use renewable energy, and celebrate diversity. mark licensed exclusively for the Cradle to Cradle Products Innovation Institute.

Product certification is awarded at five levels in version 3.0 of the standard The materials and manufacturing (Basic, Bronze, Silver, Gold, Platinum), with each higher level addressing a practices of each product more rigorous set of requirements. Continued participation in the program requires that manufacturers commit to meeting higher and higher levels of certi- are assessed in five categories fication over time, thus committing to continuous improvement of their products and manufacturing processes. By providing this pathway for improvement, the SOCIAL FAIRNESS MATERIAL HEALTH certification standard encourages innovation and the design of products that Company opera- Product ingredients are effectively and positively impact people and the environment. tions are designed to inventoried throughout the celebrate all people supply chain and evaluated for Products that meet the requirements of the standard are awarded use of the and natural systems impacts to human and ecological and build towards health. The criteria build towards Cradle to Cradle certification mark, indicating their commitment to sustainability. having a wholly posi- the goal of eliminating all toxic tive impact on their and unidentified chemicals and The Cradle to Cradle design framework was originally created by McDonough communities. becoming nutrients for safe, Braungart Design Chemistry, LLC (MBDC) in cooperation with EPEA Interna- continuous cycling. tionale Umweltforschung GmbH, and has been developed and practiced over the past 20 years. Since product certification began in 2005, more than 125 WATER STEWARDSHIP MATERIAL REUTILIZATION companies have adopted the Cradle to Cradle approach. Over 400 product Processes are Products are designed to certifications (both individual products and product lines representing several designed to regard either biodegrade safely as products) have been issued in product categories including building materials, water as a precious a biological nutrient or to be interior design, textiles and fabrics, paper and packaging, and personal and recycled into new products as resource for all living RENEWABLE ENERGY homecare. Participating companies include Puma, Steelcase, Herman Miller, things and facilities AND CARBON MANAGEMENT a technical nutrient. Progress Shaw Industries, Aveda, Method, and a government leader, the United States strive towards the Energy use and carbon emissions are must be made towards goal of all effluent calculated in order to strive towards the recovering materials and Postal Service. being clean enough goal of powering all operations with keeping them in continuous to drink. 100% renewable energy. reuse cycles. The Cradle to Cradle Products Innovation Institute, an international non-profit organization co-founded by William McDonough and Michael Braungart in San Francisco, is working to scale up the adoption of the Cradle to Cradle Certified Product Standard by manufacturers and designers. For more information, please The Cradle to CradleCM Products Program rates products across five critical quality categories and recognizes achievement and a commitment to continual improvement with five award levels. visit http://www.c2ccertified.org/ 18 MANAGEMENT UPDATE MANAGEMENT OF CEC s

| 19 Bifenox Dicofol BANNED Terbutryn Aclonifen Cybutryne Dichlorvos Diclofenac Heptachlor Quinoxyfen Cypermethrin (paint additive) (paint additive) BBP (phthalates) DIBP (phthalates) DBP (phthalates) ADDED (2012) DEHP (phthalates) and their oligomers 2,4-DNT (plasticizer) TCEP (flame retardant) 17 beta-estradiol (E2) HBCD (flame retardant) musk xylene (fragrance) Sodium dichromate (dye) Potassium chromate (dye) Trichloroethylene (solvent) Trichloroethylene TO BE BANNED BY 2017 Diarsenic pentaoxide (dye) Potassium dichromate (dye) Ammonium dichromate (dye) MDA (epoxy resin-hardener) Dioxin and Dioxin-Like PCBs 17 alpha-ethinylestradiol (EE2) Perfluorooctane sulfonate (PFOS) Chromium trioxide (electroplating) Lead chromate molybdate sulfate red Lead chromate molybdate sulfate red Sodium chromate (corrosion inhibitor) Hexabromocyclododecane (HBCDD) Hexabromocyclododecane Diarsenic trioxide (decolorizing agent) Acids generated from chromium trioxide Lead sulfochromate yellow (paint additive) Diuron Alachlor Atrazine Benzene Trifluralin Simazine Endosulfan Isoproturon Anthracene Chlorpyrifos Fluoranthene Naphthalene Octylphenols: Chlorfenvinphos Dichloromethane Trichlorobenzenes Pentachlorophenol (congener numbers 1,2-Dichloroethane Hexachlorobenzene Pentachlorobenzene Hexachlorobutadiene Chloroalkanes, C10-13 Hexachlorocyclohexane NICOLE DAVID, San Francisco Estuary San Institute ([email protected]) NICOLE DAVID, Lead and its compounds Nickel and its compounds Pentabromodiphenyl ether Pentabromodiphenyl ether Brominated diphenyl ether: Brominated diphenyl ether: Mercury and its compounds Cadmium and its compounds WATER WATCH LIST (2009) WATCH WATER Nonylphenols (4-nonylphenol) Trichloromethane (Chloroform) Trichloromethane thene, Indeno(1,2,3-cd)pyrene Bis(2-ethylhexyl)phthalate (DEHP) Bis(2-ethylhexyl)phthalate 28, 47, 99, 100, 153, and 154) 28, 47, 99, 100, 153, and Polycyclic aromatic hydrocarbons: (4-(1,1',3,3'-tetramethylbutyl)-phenol) Benzo(g,h,i)perylene, Benzo(k)fluoran- Benzo(a)pyrene, Benzo(b)fluoranthene, Tributyltin compounds (Tributyltin-cation) Tributyltin Link for REACH introduction: http:// ec.europa.eu/environment/chemicals/ reach/reach_en.htm Link for priority substances in the field of water policy: http://ec.europa.eu/ environment/water/water-framework/ priority_substances.htm REACH for Safer Chemicals in Europe in Chemicals for Safer REACH of to improve the protection a regulation European Union adopted In 2006, the can be posed by chemicals. from the risk that and the environment human health of chemicals and restriction evaluation, authorization, for registration, REACH stands information framework for the disclosure of detailed and provides the legislative on chemical sales in the European Union use of chemicals. With the safe handling and chemical sales) this $460 billion in 2007 (about 30% of global amounting to nearly was extremely important.change in regulation It gave rise to one of the most intense historylobbying battles in the green campaign man- of the European Union, pitting of REACH are gradu- But the benefits agers against the powerful chemical industry. and chemicals more and more chemicals are being regulated ally being realized as environment. The assessed and controlled, resulting in a safer are being effectively safer for workers, already considers chemicals significantly European Commission due to new informationconsumers, and the environment on uses and properties of the costs associated that are placed on the market. Despite the chemical substances has been reported of REACH, a positive economic effect with the implementation in the chemical industry. due to innovation and enhanced competition and importers.REACH places the burden of proof on manufacturers These companies are required to submit information on the properties of each chemical and chemi- cal mixture they produce. The information run by the is stored in a central database Finland. ECHA coordinates in-depth European Chemicals Agency (ECHA) in Helsinki, a public database with hazard infor- evaluations of the chemical data and maintains number of ‘substances of verymation. The first goal was to evaluate a smaller high concern’ reproductive that are suspected of causing cancer or disturbing the human chemicals is enforced, and risk man- system. A progressive substitution of dangerous are communicated. Until 2018, when agement measures for the safe use of chemicals the regulatory phase-in of substances (registration windows for chemicals according completed, REACH seeks to improve the to their production volume) is expected to be early identification of harmful chemicals and the integration with international efforts. In 2010, the ministryvery of environmental protection in China brought into force a that will facilitate importsimilar regulation, also known as ‘China REACH’, and export agreements between the EU and China. proposed to add 15 chemicals As a result of REACH, the European Commission and controlled in European List of 33 chemicals that are monitored to the Watch surface on this priority substances list are regularly monitored to waters. Chemicals (effect levels for aquatic life) and emis- assure concentrations stay below standards next 20 years. For the first time, three sions into water will be phased out over the pharmaceuticals were included on the priority substances list. The popular pain-killer six chemicals have been banned, and unless diclofenac is one of them. Additionally, a specific exemption is obtained, companies are not able to sell items containing banned chemicals. This approach is an important advance in improving water qual- ity in rivers, lakes, and coastal waters in the European Union. Biomonitoring California Measures Contaminants in Californians

By measuring chemicals in body fluids, such as • some chemicals found in personal care products (PAGE 71), including phthalates, parabens, and cyclosiloxanes; blood or urine, scientists can determine the levels of • some chemicals in other consumer products, such as bisphenol A (PAGE 71) and contaminants that get into people from all sources related compounds (e.g., air, soil, water, dust, and food) combined. These “biomonitoring” investigations can provide • the antibacterial chemical triclosan (PAGE 75), and useful information on exposure to toxic chemicals. • pyrethroids (PAGE 79) and many other pesticides (PAGE 87).

The California Environmental Contaminant Biomonitoring Program (also known as Other priority chemicals include: Biomonitoring California) was established in 2006 by Senate Bill 1379 (Perata • diglycidyl ethers of bisphenols (used to line food cans); and Ortiz). The legislation set forth three main goals: a) determine levels of environmental chemicals in a representative sample of Californians; b) establish • polychlorinated biphenyls (PCBs; legacy contaminants once widely used in the trends in the levels of these chemicals over time; and c) help assess the effective- electrical industry and banned in 1979) (PAGE 32); ness of public health efforts and regulatory programs to decrease exposures to specific chemicals. • polycyclic aromatic hydrocarbons (PAHs; air pollutants typically produced by burn- ing fossil fuels) (PAGE 34); The Program is a collaboration among three state departments: The California Department of Public Health (CDPH), the Office of Environmental Health Hazard • perchlorate (rocket fuel component and drinking water contaminant); Assessment (OEHHA) and the Department of Toxic Substances Control (DTSC). CDPH is the lead department for the Program. • diesel exhaust;

A panel of experts, the Scientific Guidance Panel (SGP), helps guide the Program's • tobacco smoke; and design and implementation. The SGP recommends which chemicals to prioritize for biomonitoring in California, based on concerns for potential human exposure and • metals like arsenic, cadmium, lead, and mercury (PAGE 28). adverse health effects. While California’s budget woes have prevented full implementation of Biomonitor- Biomonitoring California’s priority chemicals list, updated in May 2013, ing California’s goal of analyzing contaminant levels in a representative sample of includes a number of Bay CECs: Californians, the Program’s scientists have developed analytical methods for detect- ing a large number of environmental contaminants in blood and urine. Biomonitor- • PFOS and other perfluorochemicals (PAGE 55); ing California has undertaken several collaborative biomonitoring projects.

• PBDE flame etardantsr (PAGE 63) and their metabolites; • The Maternal Infant Environmental Exposure Project (MIEEP) – This project is measuring environmental chemical exposures in 65 maternal-infant pairs and an • many alternative flame retardants PAGE( 67); additional 27 pregnant women, recruited from San Francisco General Hospital. The study is being conducted in collaboration with the University of California (UC)

20 MANAGEMENT UPDATE MANAGEMENT OF CEC s

| 21 For more information about Biomonitoring For more information about Biomonitoring California, visit www.biomonitoring.ca.gov 

o regulatory efforts, including o regulatory efforts, including re the levels of chemicals changing over time? over of chemicals changing the levels re or populations groups there re he Biomonitoring Exposures Study (BEST) Study adults in is a pilot study of 112 Exposures he Biomonitoring This – irefighter Occupational Exposures (FOX) – This study is measuring environmental This study is measuring environmental – (FOX) Exposures Occupational irefighter T Northern with Kaiser conducted in collaboration Permanente Valley, the Central collectto study samples from California is the first Biomonitoring This California. and location. race/ethnicity, age, participants gender, selected randomly across San Francisco’s Program on Reproductive Health and the Environment and the and the and the Environment Health on Reproductive Program San Francisco’s of the project goals include identifying The Health. UC Berkeley School of Public biomoni- communicating methods for and developing exposures of toxic sources participants. to results toring F conducted col- It is being in firefighters. County in 101 Orange chemical exposures Health and and Environmental Occupational for Center with UC Irvine’s laboration Authority. Fire County the Orange A A D W among Californians? among Californians? actually reduce exposures exposures actually reduce exposures to certain to chemicals? exposures bans or phase-outs of chemicals, in California that have higher higher have that in California

Photograph courtesy of Biomonitoring California. REBECCA SUTTON, San Francisco EstuaryREBECCA SUTTON, Institute, ([email protected]) • • • • Even with the currently limited funding, these Biomonitoring California projects are Biomonitoring CaliforniaEven with the currently limited funding, these projects are answer such questions as: already helping scientists and policymakers • thelevels? are high bodiesandhow inpeople’s hich chemicalsare • Biomonitoring CaliforniaBiomonitoring Californians in Contaminants Measures THE RV TURNING TIDE For the last two years, the USGS Water Center in Sacramento, CA has assisted in the collection of RMP water and sediment samples using their re- search vessel, the RV Turning Tide. This 52-ft vessel is under the capable command of the Captain Chris Vallee and his first mates, Norbert Vandenbranden (“Nubbs”) and Trevor Violette. When Chris and his crew are not assisting the RMP, they are collecting real-time flow and water quality data at roughly 40 sites, trawling for Delta smelt and tracking juvenile salmon outmigrants through acoustic telemetry. Dr. Roger Fujii is Bay/Delta Program Chief; Jon Burau is the Bay/Delta Hydrodynamics Project Chief. The RMP is extremely grateful to have this opportunity to work with the USGS and looks forward to many fu- ture sampling cruises. More information regarding the USGS Water Center can be found at http:// ca.water.usgs.gov/index.html.

 Photograph by Don Yee.

22 MANAGEMENT UPDATE THE 303(D) LIST AND THE REGULATORY STATUS OF POLLUTANTS OF CONCERN

| 23

Photograph by Elaine Bond.  ATUS ST in 2002 Bay TMDL and site-specific objectives approved in 2008 TMDL Guadalupe River Watershed approved in 2010 Richardson Bay TMDL adopted in 2008 Bay beaches (multiple listings); TMDL in early development stage TMDL approved in 2009 TMDL in development – completion projected for 2014/2015 Central and South Bay shorelines added to the 2010 303(d) List Site-specific objectives approved for entire Bay Site-specific objectives from 303(d) List San Francisco Bay removed stage TMDL in early development Under consideration for delisting

y Approved: State Water Board and USEPA approval Board and USEPA Approved: State Water Copper Dioxins / Furans Pathogens PCBs Selenium Trash Legacy Pesticides (Chlordane, Dieldrin, and DDT) Mercur POLLUTANT REGULATORY STATUS STATUS REGULATORY OF POLLUTANTS OF CONCERN Section 303(d) of the 1972 Federal Clean Act Water requires thatSection states of the 1972 303(d) develop of water a list bodies that do not meet water quality standards, establish priority rankings for waters on and the develop List, action plans, called Maximum Total Daily Loads (TMDLs), to water improve quality. The of impairedlist water bodies revised is periodically (typically every two The RMP years). one is of many entities that provide data to the State BoardWater to compile and List to develop the 303(d) TMDLs. Theprimary pollutants/stressors for the Estuary and its major tributaries on the current List 303(d) include: Elements Trace Mercury and Selenium Pesticides Chlordane, andDieldrin, DDT Compounds Chlorinated Other Compounds and Furan PCBs, Dioxin Others andExotic Polycyclic Aromatic Species, Hydrocarbons Trash, (PAHs) THE 303(D) LIST 303(D) THE 24 STATUS AND TRENDS UPDATE 25 Selenium Flows and Loads and Flows 31 41 Chlorophyll and Dissolved Oxygen Dissolved and Chlorophyll 39 Climate and Habitat and Habitat Climate PBDEs 43 36 Graph Details Graph 45 Mercury 28 PAHs 34 Nutrients Populations Populations Nutrients and Sediment Sediment and Nutrients Toxics and Bacteria Bacteria and Toxics PCBs Human Presence Presence Human LATEST MONITORING RESULTS MONITORING LATEST 26 32 38 40 42 44 WATER QUALITY TRENDS AT A GLANCE AT TRENDS QUALITY WATER

38 8 LATEST MONITORING RESULTS Nutrients DISSOLVED OXYGEN (mg/L) 4 7 There is a growing body of 3 Dissolved oxygen evidence, including increases reaches a daily minimum in phytoplankton biomass and 2 6 at lowest tide declines in dissolved oxygen, that Depth (m) suggests the historic resilience of 1 the Bay to the harmful effects of nutrient enrichment is weakening. 5 0 The complexity of the ecosystem, 7/3/13 7/4/13 7/5/13 7/6/13 7/7/13 7/8/13 7/9/13 7/10/13 uncertainty about future conditions, CHLOROPHYLL (RFU) and the potentially great cost of 3 reducing nutrient inputs underlie 4 Chlorophyll fluctuates the importance of nutrient and with the tides due 2 3 to the movement of phytoplankton monitoring, different water masses

research, and modeling. 2 past the sensor Depth (m) 1 1

0 0 7/3/13 7/4/13 7/5/13 7/6/13 7/7/13 7/8/13 7/9/13 7/10/13

A New Chapter in the report’s recommendations was to develop a network of temperature, salinity, dissolved oxygen, pH, turbidity, continuous monitoring stations at key locations in the Bay fluorescent dissolved organic matter (a surrogate for RMP Water Monitoring to complement the current ship-based monitoring program. chlorophyll, and therefore phytoplankton, abundance), and Concerns about high nutrient loads to San Francisco These stations can provide high temporal resolution water nitrate. Real-time data are transmitted via cell phone, and a Bay, and recent observations of the Bay’s changing quality data to: 1) identify the onset of events (e.g., large public website is being developed for viewing and down- response to nutrients (see PAGE 48 of the 2011 PULSE), phytoplankton blooms); 2) improve understanding about loading data. While these sensors are providing valuable have led regulators and stakeholders to collaboratively the processes that influence phytoplankton blooms and new information, the approach is not without its problems develop a Nutrient Strategy (http://bayareanutrients. other nutrient-related responses; 3) assess oxygen budgets; - biofouling is a major issue that needs to be managed at the aquaticscience.org/) for San Francisco Bay to inform and 4) provide high temporal resolution data to calibrate Dumbarton site (photo PAGE 45). Two more continuous important and potentially costly management decisions water quality models. monitoring stations will be added in South Bay and Lower related to prevention of problematic levels of phytoplankton San Francisco Estuary Institute staff collaborated with South Bay in 2014. Prior to that, effort will be directed growth. As an early step in implementation of the Nutrient USGS staff from Menlo Park and Sacramento to install toward field studies for calibration and testing of sensor Strategy, the RMP funded a nutrient conceptual model a RMP-funded continuous monitoring station at the accuracy and precision, developing protocols for sensor report (Senn et al. 2013) that described the current state Dumbarton Bridge on July 3, 2013. Water quality sensors maintenance and minimizing biofouling, pilot field deploy- 26 of the science and identified priority science needs. One of at the Dumbarton station measure multiple parameters: ments to inform future site selection, and data analysis. STATUS AND TRENDS UPDATE LATEST MONITORING RESULTS

| 27 - - Temperature (ºC) Temperature The graphs show results for two algal toxins, microcys for algal results two show The graphs cruises during monthly tin domoic acid, and measured likely derived toxins are during 2011. Both of these with microcystin proper, Bay outside of the algae from from domoic coming acid and the Delta from originating a wide over varied range; concentration Toxin the ocean. during all cruises, in detected toxins both were however, of tempera a wide range across and all subembayments, While- note of the toxins was salinity. and detection ture concentrations of these significance the ecological worthy, efforts, inform future monitoring known. To is not yet the RMP measure funded in 2013, both to study a special to cruises attempt toxins during monthly to algal and from concentrations water of estimating a way establish results. SPATT Domoic Acid 8 10 12 14 16 18 20 22 24 26 5 0

-5 35 30 25 20 15 10

- Salinity (ppt) Salinity Temperature (ºC) Temperature Color corresponds to Bay regions HAB toxins detected in Bay during 2011 Bubble size = toxin concentration Bars represent 1 SD for Salinity and Temperature In 2011, researchers from UC Santa Cruz collaborated Cruz collaborated UC Santa from 2011, researchers In toxins in algal with measure the RMP and to the USGS packet small deploying a involved approach The the Bay. adsorption phase (solid – SPATT resin of toxin-binding continuously water of Bay toxin tracking) – in a stream the into and the surface below 1 meter from pumped - sam during monthly transects Bay as it travelled lab ship’s toxins chemically algal adsorbs cruises.SPATT pling The Cruz, the algal Santa at UC Back it. past flows water Bay as analyzed. One and the resin from extracted toxins were provid subembayment, each for was used packet SPATT measure spatially-integrated inexpensive, a relatively ing of toxin abundance. Microcystins - 8 10 12 14 16 18 20 22 24 26 5 0 -5 35 30 25 20 15 10

Salinity (ppt) Salinity (cont) Source: R Kudela, UCSC Footnote: Circle size denotes toxin relative concentration, and color represents the subembayment (see map). in the Bay in the toxic produce species algae) (or phytoplankton Some harm in food webs, bioaccumulate can compounds that in humans illness or death severe biota, cause and aquatic or seafood who tainted animals or domestic consume toxin concentra Algal water. swim in contaminated typicallytions are during so-called highest harmful algal toxin production HABs associated and (HABs). blooms are and waters, in coastal globally problem a growing are re- until However, efforts. research the focusof numerous monitored not been had toxin concentrations algal cently, Bay. Francisco in San Nutrients Nutrients Ubiquitous Toxins Algal LATEST MONITORING RESULTS Mercury, Methyl in Water (Total), 2006 to 2011

LATEST MONITORING RESULTS Mercury

Mercury contamination is one of the Methylmercury in Water top water quality concerns in the Bay and mercury clean-up is a high San Pablo Bay priority for the Water Board. Mercury Rivers is a problem because it accumulates Suisun Bay in the form of methylmercury to high concentrations and poses risks to some 0.100 fish and wildlife species. Humans and 0.080 0.060 wildlife that consume fish face the ng/L 0.040 greatest health risks from mercury. Central Bay 0.020

0.000 2001 2003 2005 2007 2009 2011

South Bay Lower South Bay

0 Miles 20

<0.02 0.04 0.07 0.09 0.12 0.14 >0.17

Water from Lower South Bay had the highest average concentration of methylmer- cury by far (0.11 ng/L) of any segment from 2006 to 2011. South Bay had the next highest average (0.07 ng/L). Methylmercury typically represents only about 1% of the to- tal of all forms of mercury in water or sediment, but is the form that is readily accumulated in the food web and poses a toxicological threat to highly exposed species. Methylmercury has a complex cycle in the Bay, influenced by many processes that vary in space and time. No regulatory guideline exists for methylmercury in Bay water . The Bay-wide average in 2011 was 0.03 ng/L. The Bay-wide average for the six-year period was 0.04 ng/L. The Bay- wide averages for 2008-2011 were lower than those observed in 2006 and 2007. Footnote: Water is sampled only in the dry season, and was not sampled in 2012. Colored symbols on map show results for samples collected in 2011: circles represent random sites; diamonds represent historic fixed stations. Contour plot based on 111 RMP random station data points from 2006-2011. Trend plot shows annual Bay-wide random station means with error bars indicating the 95% confidence intervals of the means. Earlier years not included because a less sensitive method was employed. The maximum concentration was 0.28 ng/L at a site in Lower South Bay in 2011. Data are for total methylmercury (dissolved plus particulate).

 Photograph by Meg Sedlak. 28 STATUS AND TRENDS UPDATE LATEST MONITORING RESULTS

| 29 - Aver 2011 2009 2007 2005 2003 2005 2007 2009 2011 Rivers Lower South Bay 2001 Suisun Bay 0.1 0.0 0.3 0.2 0.4 ppm 20 Mercury in Sediment, 2002 to 2011 to 2002 in Sediment, Mercury 2012)** years (2010, wet **excluding South Bay Miles Central Bay San Pablo Bay 0 Footnote: Colored symbols on map show results for wet season samples circles collected represent in 2012: random sites; diamonds represent historic fixed stations. Contour plot based 360on RMP data points from random stationscollected over nine rounds of dry season sampling (data from from wet 2002-2009 season and 2011 sampling in are excluded). Trend plot and 2012 shows annual2010 Bay-wide random station means with error bars indicating confidence95% intervals of the means.Red circles on trend plot indicate wet season samples; blue diamonds dryindicate season samples. The maximum dry season concentration ppm in Central was Concentrations Bay 0.94 in 2009. presented on a dry weight basis. Incontrast to methylmercury, long-term average total mercury concentrations in sediment during the dry season have been highest in San Pablo Bay (0.27 ppm). age concentrations have been slightly lower in Lower South Bay and Central Bay (both Bay Central and Bay South in Lower lower slightly been have concentrations age Bay-wide The (0.17 ppm). Bay in Suisun lowest and ppm), (0.22 Bay South and 0.26 ppm) to Also 0.25 ppm. of dry was in contrast for the nine rounds sampling season average shown mercury have of total in sediment concentrations average Bay-wide methylmercury, to a of 0.19 ppm in 2005 variability little a low thisfrom period,ranging over relatively season roundswet for the of two averages Bay-wide annual of 0.30 ppm in 2009. The high guideline regulatory exists for the dry No for season. the averages similar to were sampling mercurytotal in sediment. Mercury in Sediment <0.02 0.1 0.18 0.25 0.33 0.41 >0.49 2011 2009 2007 2005 2003 2005 2007 2009 2011 Methylmercury Methylmercury Rivers Lower South Bay 2001 Suisun Bay 0.2 0.0 0.6 0.4 1.0 0.8 ppb 20 (cont) IDW Output Surface Outliers Reset Output Surface IDW South Bay Miles Central Bay San Pablo Bay Mercury LATEST MONITORING RESULTS Footnote: Colored symbols on map show results for wet season samples circles collected represent in 2012: random sites; diamonds represent historic fixed stations. Contour plot based 360on RMP data points from random stations over nine rounds of dry season sampling (data from from wet 2002-2009 season and 2011 are excluded). Trend plot and 2012 sampling shows annual in 2010 Bay-wide random station means with error bars indicating confidence 95% intervals of the means.Red circles on trend plot indicate wet season samples;blue diamonds indicate dry season samples. The maximum dry season concentration at a random2.4 ppb station at a site in Central was Bay in 2002. Concentrations presented on a dry weight basis. Concentrations of methylmercury in sediment south of the Bay Bridge have been consistently higher than those in the northern Estuary. Methylmercury in Sediment production can vary tremendously over small distances and over short time over and periods, small distances vary over can production tremendously “snapshots” of several shown should be viewed as the result contours the colored so in the dry collected season the time were of the surveys. at conditions Samples of Bay data season 2012 (wet in 2010 and season in the wet 2011, and in 2002-2009 and Long-term follow). that the averages and on the map the contours from excluded are and Bay in South highest been have dry concentrations season (2002-2011) average (0.20 Bay in Suisun lowest and respectively), 0.68 ppb, (0.72 and Bay South Lower wet for the concentration average Bay-wide The (0.27 ppb). Bay Pablo San and ppb) period. The the 11-year over average annual the lowest was in 2012 (0.28 ppb) season relatively were sampling season for the two of wet rounds averages Bay-wide annual guideline regulatory exists for the dry No for season. the averages to compared low sediment. methylmercury in Bay 0 <0.03 0.28 0.53 0.78 1.03 1.28 >1.53 LATEST MONITORING RESULTS Mercury (cont)

Statewide Survey Underscores The San Francisco Estuary is the only coastal ecosystem in California where striped bass occur. Results for shiner surfperch, a species with a more widespread distribution along High Mercury in Bay Food Web the coast and that is a valuable indicator of spatial patterns, also documented elevated mercury concentrations in the Bay food web (data not shown). The five locations sampled In 2012 the State Water Resources Control Board’s Surface Water Ambient Monitoring in the Bay (out of 17 total across the state) accounted for the five highest concentrations Program (SWAMP) published results from a 2009-2010 survey of contaminants in fish on for this species statewide. the California coast. The survey was performed in close collaboration with the RMP and the Southern California Bight Regional Monitoring Program. The survey was the largest of While the mercury concentrations in the Bay food web stood out when comparisons its kind ever conducted, analyzing 3,483 fish from 46 species at 68 coastal locations. could be made within single species, the survey also showed that mercury accumulation in fish is of high concern along much of the California coast. Long-lived predator species The survey summary included a comparison of Bay striped bass mercury concentrations that are common along the coast, such as various rockfish and shark species, generally had with those in other US estuaries. Striped bass are a relevant and useful indicator species high concentrations. for comparing mercury contamination across US estuaries due to several factors: their popularity for consumption; their dependence on estuaries; their broad spatial integra- The public can access results for individual fishing locations from the Coast Survey and tion across the estuaries in which they reside due to their variable use of fresh, brackish, other statewide SWAMP fish surveys through the California Water Quality Monitoring and saline habitat; and their wide distribution on the east, west, and Gulf coasts. Striped Council’s “My Water Quality” web portal at: www.CaWaterQuality.net bass from San Francisco Bay had the highest average mercury concentration (0.44 ppm, estimated for a 60 cm fish) among the six estuaries with data. The New Jersey coast had the second highest average concentration (0.39 ppm, but based primarily on fish greater The Coast Survey Report ("Contaminants in Fish from the California than 84 cm). Average mercury concentrations in striped bass from other US coastal areas Coast, 2009-2010") is available on the SWAMP website at: were much lower, ranging from 0.12 to 0.23 ppm. www.waterboards.ca.gov/water_issues/programs/swamp/coast_study.shtml

Mercury in Striped Bass in US Estuaries

San Francisco Bay * New Jersey

South Carolina

Chesapeake Bay

Narragansett Bay

Louisiana

0 0.1 0.2 0.3 0.4 0.5 Mercury (ppm wet weight)

* The median size of striped bass sampled in New Jersey was 84 cm, substantially larger than the Bay average for a 60 cm fish. The larger size of the New Jersey fish would inflate the mercury concentrations measured.

30 STATUS AND TRENDS UPDATE LATEST MONITORING RESULTS

| 31

- 2011 2009 The highest concentration concentration The highest 2007 Rivers 2005 2003 Lower South Bay 2001 0.0 0.20 0.40 0.30 0.10 Suisun Bay µg/L 20 South Bay Miles Central Bay San Pablo Bay ide random station means with error bars indicating the confidence 95% intervals of the means. The maximum Selenium in Water Selenium observed in water at random stations from 2002 to 2011 was 0.63 µg/L, much lower than than 0.63 µg/L, lower 2011 was much 2002 to from stations random at observed in water concentration average a higher had Bay South The Lower (5 µg/L). objective the CTR aver- which very had segments, consistent Bay the other than this period (0.25 µg/L) over Bay-wide The 0.14 µg/L). 0.12 and between were averages other (all concentrations age Bay-wide the long-term than lower slightly was in 2011 (0.10 µg/L) concentration average (0.13 µg/L). average Footnote: Water is sampled only in the dry season, and Colored was not sampled symbols in 2012. on map show results for circles samples represent collected random sites; in diamonds 2011: represent historic fixed stations. µg/Lconcentration at a historical fixed wasstation 1.15 in the Southern Sloughs2002. in Data are for total selenium particulate). plus (dissolved Selenium concentrations in water are well below the water quality objective es Contour plot RMP based random on 210 Trend plot station shows annual data points Bay- from 2002-2011. w tablished by the California Toxics Rule but (CTR), concerns still exist for wildlife exposure as indicated by studies on early life-stages of fish. 0 <0.04 0.09 0.14 0.2 0.25 0.3 >0.36 Photograph by Meg Sedlak.  Selenium is a contamination Selenium concerncontinuing in the Bay. in diving accumulates Selenium that pose ducks to concentrations risk to human a potential health concentrations consumers. Selenium to wildlife. also pose a threat suggest that selenium Recent studies may be high enough concentrations to cause deformities, growth impairment, and mortality in early life-stages of Sacramento splittail and white sturgeon. LATEST MONITORING RESULTS LATEST MONITORING RESULTS PCBs

PCB contamination remains 1000 one of the greatest water ppb quality concerns in the Bay, 500 250 and PCB cleanup is a primary focus of the Water Board. Mississippi Silverside PCBs are a problem because targeted Mississippi Silverside they accumulate to high non-targeted concentrations in some Bay fish and pose health risks to Topsmelt targeted consumers of those fish. SAN PABLO BAY Topsmelt non-targeted SUISUN BAY

FIGURE 1 PCB concentrations CENTRAL Stege Marsh (ppb wet weight) BAY in small fish in 2010.

Oakland Harbor

Hunters Point

SOUTH BAY

32 STATUS AND TRENDS UPDATE LATEST MONITORING RESULTS

| 33 40 20 SPORT FISH SPORT SMALL FISH PCB Concentration (ppm lipid)

0 FIGURE 2 PCB concentrations in small fish (even when expressed on a lipid weight basis) are comparable and often greater than concentrations in large sport fish species. Topsmelt Jacksmelt Striped Bass Leopard Shark White Croaker White Sturgeon Shiner Surfperch California Halibut Northern Anchovy Mississippi Silverside ). The consistently high concentrations concentrations high consistently ). The FIGURE 2 ). (cont) FIGURE 1 in anchovy are noteworthy, as this is the most abundant fish species in the Bay and an and Bay fish in the species as this is abundant the most noteworthy, in anchovy are important wildlife item. prey smallby fish spe- accumulated PCBs the is that explainA hypothesis patterns to these hotspots legacy at a “bathtub from derived ring”cies are contamination of sediment sport by fish higher species while accumulated the PCBs of the Bay, the margins along Bay in open sediment primarily derived less-contaminated from are in the food chain in elevated remain contaminants legacy other and of PCBs Concentrations habitat. low times in these residence long transport and reduced hotspots due to the margin in the small fish in thissurvey found were concentrations PCB energy environments. supporting sediment, this hypothesis. in nearby well with concentrations correlate to observed smalluptake of the in linkage PCB fishThe high an important element is in concentrations PCB food web. in the Bay accumulation and sources PCB between and and exposure risk contamination web of food an important indicator small fishare utility with for identifying great and of concern areas margin in the Bay, piscivores to recovery. for tracking Little Fish, Big PCBs Big Little Fish, RMP of small fish from has monitoring obtained fundamentally information New potential and food web of the Bay contamination of PCB our understanding altered The con- seals. RMP and as birds such piscivores of exposure of sensitive pathways and Allen (Greenfield in small fishand 2010 in 2007 pilot of PCBs monitoring ducted RMP of methylmercury study in multi-year 2013), piggybacking extensive more on a small fish. surprisinglysmallwere in the fish concentrations pilotearlier studies, Confirming than higher much small in ppb, was 216 fish in 2010 concentration average The high. (shiner sport in 2009 fishsampled species contaminated for the most the average a maximum Hunters at of 1100 ppb reached Concentrations surfperch 121 ppb). – ( Point These high concentrations in small fish were unexpected because PCBs are among the the among are PCBs because unexpected smallwere in fish concentrations high These up the food with step each increase biomagnify: that concentrations contaminants such as small species web, food same to the belonging for species Therefore, chain. concentrations lower should have plankton eat anchovy that and topsmelt, silverside, fishand eat that bass striped and white sturgeon, as white croaker, such species than invertebrates. larger (or fat) of lipid gram per expressed concentrations to apply comparisons These tis- and species among varies in lipid, lipid and content accumulate PCBs because anchovy When all and silverside, sues. topsmelt, basis, on a lipid weight expressed as such in the food chain higher species than greater were that concentrations had ( bass striped and white sturgeon PCBs PCBs LATEST MONITORING RESULTS LATEST MONITORING RESULTS PAHs

PAHs (polycyclic aromatic PAHs in Sediment hydrocarbons) are included on the 303(d) List for several Bay locations. San Pablo Bay Concentrations tend to be higher Rivers near the Bay margins, due to Suisun Bay proximity to anthropogenic sources. 10 Increasing population and motor vehicle use in the Bay Area suggest 8 6 that PAH concentrations could ppm 4 increase due to deposition from the Central Bay air directly into the Bay and from the 2 air to urban runoff and into the Bay 0 2001 2003 2005 2007 2009 2011 via stormwater. South Bay Lower South Bay

0 Miles 20

0 1.7 3.4 5 6.7 8.3 10

Average dry season PAH concentrations in sediment have been highest along the southwestern shoreline of Central Bay. Central Bay has had the highest average dry season concentration (4.0 ppm) of any Bay segment. South Bay had the next highest average concentration (2.4 ppm), followed by Lower South Bay (1.9 ppm), San Pablo Bay (1.0 ppm), and Suisun Bay (0.5 ppm). The Bay-wide average in 2012 (wet season) was 1.7 ppm - the lowest annual average observed over the 11 years of sampling. The high annual average dry season concentrations observed in 2008 and 2009 were largely driven by a few unusually contaminated sites sampled in those years, including the maximum concentra- tion of 43 ppm at a site on the southwestern Central Bay shoreline in 2009. Seven of the 10 highest samples in the 11 year period were from Central Bay. Footnote: Colored symbols on map show results for wet season samples collected in 2012: circles represent random sites; diamonds represent historic fixed stations. Contour plot based on 360 RMP data points from random stations collected over nine rounds of dry season sampling from 2002-2009 and 2011 (data from wet season sampling in 2010 and 2012 are excluded). Trend plot shows annual Bay-wide random station means with error bars indicating 95% confidence intervals of the means. Red circles on trend plot indicate wet season samples; blue diamonds indicate dry season samples. Concentrations presented on a dry weight basis.

34  Photograph by Emily Novick. STATUS AND TRENDS UPDATE LATEST MONITORING RESULTS

| 35

on PAHs in Mussels on PAHs References: Report Brodberg on the et al. safety 2007. of consuming fish and shellfish from areas impacted by the M/V Cosco Busan oil spill in San Francisco California. Bay, California Office of Environmental Health http://oehha.ca.gov/fish/pdf/SF%20 CA. Sacramento, Assessment, Hazard BayFishShell112907.pdf of the Cosco Busan Oil Spill Spill Busan Oil Cosco of the Large But Fleeting Impact But Fleeting Large its gouged oil tanker Busan 2007, the Cosco November In 54,000 gal- releasing support Bridge tower, hull on a Bay in a brief resulted This fuel the Bay. of bunker oillons into high extremely were concentrations period in which PAH a Fortuitously, by the spill. affected in the parts of the Bay including in mussels, accumulation of contaminant study the spill, shortly after Island was Buena Yerba at sampling partwas of monitoring mussel The time. that underway at the Na- and Board Water the State between a collaboration (NOAA) Atmospheric Administration and Oceanic tional in mussels contaminants other and PAHs measured that coast. the California along Yerba at observed mussels in concentrations PAH The very the spill station to close a sampling Island, Buena the spill 2008 after dry ppb (48,000 in early weight) site, from in the state measured others any than higher far were in Island Buena Yerba at concentration 2007-2009. The the next than highest 18 times higher 2007 was December Beach). State Carpinteria at (2,700 ppb measurement 2008. in December again sampled was Island Buena Yerba 1,900 fell down to concentration the PAH time, that By Bay typical more Francisco for San a concentration ppb, with in California. Consistent bays enclosed other and in a temporary advi- observations,these the spill resulted two from of mussels no consumption sory recommending impacted Rodeo and Beach) Marina (Berkeley areas nearby al. et 2007). the spillby (Brodberg in Island Buena observed Yerba at concentrations PAH end the higher at were locations Bay the other at 2009 and 10 in California, about and bays for enclosed of the range typical open concentrations for other than times higher locations. coast percentile

th Enclosed Bay Open Coastal Median 85 Concentration (ppb dry weight) 10 100 1,000 10,0000 100,000 1 Morro Bay Oceanside Dana Point Long Beach Point Arena Cardiff Reef Tomales Bay Tomales Palos Verdes Crescent City Anaheim Bay Arroyo Hondo Pudding Creek Imperial Beach Marina Del Rey Redondo Beach Eureka Samoa Br. Eureka Samoa SF Bay Emeryville San Pedro Harbor Santa Monica Bay TOTAL PAH CONCENTRATION PAH TOTAL Point Santa Barbara Tijuana River EstuaryTijuana San Simeon Pt. 2009 San Simeon Pt. 2008 SD Bay Harbor Island Agua hedionda lagoon Carpinteria State Beach Lost Angeles Rivermouth SD Bay Coronado Bridge Newport bay PCH Bridge SF Bay San Mateo Bridge SF Bay Dumbarton Bridge (cont) Eureka-Humboldt Bay jetty SF Bay Yerba Buena 2009 SF Bay Yerba Buena 2008 SF Bay Yerba Monterey Bay - Santa Cruz San Luis Obispo Bay 2009 San Luis Obispo Bay 2008 Ventura Bridge Mission Bay Ventura Monterey Bay - Moss Landing South South North North PAHs PAHs LATEST MONITORING RESULTS LATEST MONITORING RESULTS PBDEs

Polybrominated diphenyl ethers BDE-47 in Water (PBDEs), bromine-containing flame retardants that were practically San Pablo Bay unknown to water quality managers in Rivers the early 1990s, increased rapidly in Suisun Bay the Bay through the 1990s to become pollutants of concern. The California 160 Legislature banned the use of two 120

PBDE mixtures in 2006; the third will pg/L 80 be phased out in 2013. Declining Central Bay trends in these chemicals indicate 40 that the bans have been effective in 0 2001 2003 2005 2007 2009 2011 reducing accumulation in the Bay. South Bay Lower South Bay

0 Miles 20

<14.53 37.51 60.48 83.45 106.42 129.4 >152.3

Concentrations of BDE-47 in water (one of the most abundant PBDEs and an index of the banned PentaBDE mixture) appear to be on the decline, though this trend was obscured by one outlier value in 2011. The average BDE-47 concentration in Bay water in 2011 (43 pg/L) was higher than the averages for 2008-2010 (ranging from 18 to 23 pg/L), but this was largely due to one high value measured in Central Bay (117 pg/L). The Bay-wide average concentration for the 10 year period was 45 pg/L. The three lowest annual average concentrations were measured in 2008-2010. Suisun Bay had the highest long-term average concentration of BDE-47 from 2002-2011 (65 pg/L), suggesting the presence of PBDE inputs into the northern Estuary. The maximum concentrations, two samples greater than 300 pg/L, were observed at locations in Suisun Bay and San Pablo Bay, both in 2004. Footnote: Water is sampled only in the dry season, and was not sampled in 2012. Colored symbols on map show results for samples collected in 2011: circles represent random sites; diamonds represent historic fixed stations. Contour plot based on 201 RMP random station data points from 2002-2011. Trend plot shows annual Bay-wide random station means with error bars indicating the 95% confidence intervals of the means. The maximum concentration was 337 pg/L at a site in Suisun Bay in 2004. Data are for total BDE-47 (dissolved plus particulate).

36  Photograph by Meg Sedlak. STATUS AND TRENDS UPDATE LATEST MONITORING RESULTS

| 37 - In contrast to to contrast In 2011 2009 2007 2005 2003 2005 2007 2009 2011 Rivers Lower South Bay 2 2001 0 6 4ppb 8 Suisun Bay 20 South Bay Miles PBDE 209 in Sediment, 2002 to 2011 to 2002 Sediment, in 209 PBDE 2012)** (2010, years wet **excluding Central Bay San Pablo Bay 0 BDE-209 in Sediment BDE-209 BDE-47, Bay-wide average concentrations of BDE-209 in sediment do not appear to be to do not appear of BDE-209 in sediment concentrations average BDE-47, Bay-wide was ppb) of 2012 (1.8 sampling season wet in the concentration average The declining. BDE-47 to in sediment, Similar of 1.9 ppb. dry average the long-term season below slightly in highest of BDE-209 2004-2009 were from dry concentrations season average long-term Central (2.0 ppb), Bay Pablo San and Bay South by followed (5.4 ppb), Bay South Lower (0.8 ppb). Bay Suisun and (1.8 ppb), Bay Footnote: BDE-209 shown as an index of the DecaBDE mixture. Colored symbols on map show results for wet seasonsamples circles collected represent in 2012: random sites; diamonds represent historic fixed stations. Contour plot RMPbased data on points 310 from random stations collected over eight rounds of dry season sampling from (data 2002- from are excluded).2004, wet season 2006-2009, Data and and 2011 2012 sampling from 2005 are in 2010 not available. Trend plot shows annual Bay-wide random station means with error bars indicating confidence 95% intervals of the means. Red circles on trend plot indicate wet season samples; blue diamonds indicate drysamples. season The maximum concentration by far ppb was 52 in San Pablo Bay in 2007 (the next highest concentration ppb was in South19 Bay in 2006). Concentrations presented on a dry weight basis. BDE-209 (also known as decabromodiphenyl ether) represents the one remain ing PBDE mixture (“DecaBDE”) that is still being used in California. <0.1 1.94 3.78 5.62 7.45 9.29 >11.13 2011 2009 2007 2005 2003 2005 2007 2009 2011 Rivers Lower South Bay The Bay-wide average for 2012 (0.26 ppb, a wet wet a ppb, for 2012 (0.26 average Bay-wide The 2001 Suisun Bay 0.2 0.0 0.6 0.4 0.8 ppb 20 (cont) South Bay Miles ), appear), to be on the decline. Central Bay San Pablo Bay PAGE 63 PAGE 0 PBDEs PBDEs LATEST MONITORING RESULTS Footnote: BDE-47 is one of the most abundant PBDEs and was consistently quantified by the lab. Colored symbolsmap show resultson for wet season samples circles collected represent in 2012: random sites; diamonds represent historic fixed stations. Contour plot based 357 on RMP data points from random stations collected over nine roundsseason of dry sampling (data from are from excluded). wet 2002-2009 season Trend and and 2011 2012 sampling in 2010 plot shows annual Bay-wide random station means with error bars indicating confidence 95% intervals Redof circlesthe means. on trend plot indicate wet season samples; blue diamonds indicate dry season samples. Theconcentration, maximum ppb was 3.8 in by Lower far, South Bay in 2005. Concentrations presented on a dry weight basis. Concentrations of BDE-47 in sediment, consistent with the data for water and biota ( BDE-47 in Sediment BDE-47 season value) was the lowest observed in the 11 years of sampling, and 50% lower than the than of sampling, observed 50% lower and in the 11 years the lowest was value) season monitoring, long- water from obtained the results to contrast observed in 2002. In average far, by highest, been have of BDE-47 in sediment dry concentrations season average term from ranged segments in the other concentrations Average (0.71 ppb). Bay South in Lower Bay. in Central 0.46 ppb to Bay in South 0.36 ppb <0.06 0.22 0.38 0.54 0.7 0.86 >1.02 WATER QUALITY TRENDS AT A GLANCE

SEE PAGE 45 Toxics and Bacteria FOR GRAPH DETAILS

1. Methylmercury in Sport Fish 2. PCBs in Sport Fish 3. Dioxins in Sport Fish

No trend in striped 0.7 bass since 1971 500 NO APPARENT TREND 3.00 0.6 450 2.50 400 Switch 0.5 0.44 2.00 to croaker OEHHA no 350 Switch 0.4 without consumption to croaker 1.50 threshold 300 skin 0.3 without 250 1.00 skin 0.2 200 Sum of TEQs (ppt)

PCBs (ppb) 0.50

Methylmercury (ppm) 0.1 0.07 150 120 0.14 OEHHA OEHHA no 0.00 100 2 meal/wk consumption 1994 1997 2000 2003 2006 2009 0.0 threshold threshold 1994 1997 2000 2003 2006 2009 50 21 OEHHA 0 2 meal/wk California Halibut Striped Bass 1994 1997 2000 2003 2006 2009 threshold Jack Smelt White Croaker White Sturgeon Shiner Surfperch White Croaker

4. Percent Toxic Sediment Samples 5. Beach Report Card Grades

Sediment Toxicity (1993-2012) 100 NO APPARENT TREND 4 90 80 3 70 60 50 2 NO APPARENT TREND 40 GPA 30 Samples Toxic (%) Samples Toxic 1 20 10 0 0 2012 2011 2010 2009 2008 2007 2006 2005 2004 2005 2006 2007 2008 2009 2010 2011 2012 1995 2000 2005 2010 2011 2012

38 STATUS AND TRENDS UPDATE WATER QUALITY TRENDS AT A GLANCE

| 39

105% increase 105% increase since 1993 2010 SEE PAGE 45 45 PAGE SEE 2000 4% decrease since 1993 FOR GRAPHFOR DETAILS 1990 2010 1980

Chlorophyll in South Bay Bay South in Chlorophyll

10 0 25 20 30 15 5 2005 3. (µg/L) a Chlorophyll 2000 1995

2010

40 100 90 60 80 70 50

Bottom Dissolved Oxygen in South Bay South Oxygen in Bottom Dissolved 2000 saturation) (% Oxygen Dissolved 5. 1990

1980

72% increase 72% increase since 1993

10 2010 0 25 20 30 15 5

Chlorophyll in San Pablo Bay Bay Pablo San in Chlorophyll Chlorophyll a (µg/L) a Chlorophyll 2. 2000 1990 2010

300% increase in 2000 warm season 1980 since 1990

8 7 6 5 3 4 2 Summer Chlorophyll in South Bay Bay South in Chlorophyll Summer

1990 Chlorophyll a (µg/L) a Chlorophyll 4.

1980

10 0 25 20 30 15 5

Chlorophyll in Suisun Bay Chlorophyll a (µg/L) a Chlorophyll

1. Chlorophyll and Dissolved Oxygen Dissolved and Chlorophyll WATER QUALITYTRENDS A GLANCE AT WATER QUALITY TRENDS AT A GLANCE SEE PAGE 45 Nutrients and Sediments FOR GRAPH DETAILS

1. Ammonium 2. Nitrate and Nitrite

14 NO APPARENT TREND – INCOMPLETE TIME SERIES 50 NO APPARENT TREND – INCOMPLETE TIME SERIES 12 40 10

8 30

6 20 4 10 Ammonium (µmol/L) 2 Nitrate + Nitrite (µmol/L) 0 0 1980 1990 2000 2010 1980 1990 2000 2010

Suisun Bay San Pablo Bay South Bay

3. Suspended Sediment 4. In-Bay Disposal of Dredged Material

350 2,500,000 Met a limit of 1.5 36% decrease million cubic yards 300 Bay-wide between by 2012 1998 and 1999 2,000,000 250

200 1,500,000

150 1,000,000 100 Volume (cubic yards) Volume 50 500,000

0

Suspended-sediment Concentration (mg/L) 1992 1994 1996 1998 2000 2002 2004 2006 2008 2010 0 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Suisun Bay Alcatraz Island San Pablo Bay Carquinez Strait

40 WATER QUALITY TRENDS AT A GLANCE SEE PAGE 45 Flows and Loads FOR GRAPH DETAILS 41

3. Delta Outflow High ows 60,000 of 2006 1. Guadalupe River Flow 50,000

40,000 250 30,000 200 26 mcm in 2012 20,000 150 Delta Out ow 10,000 (million cubic meters) 100 0 1995 2000 2005 2010 2012 50 4. Delta Sediment Load

Flow (million cubic meters) 0 1930 1940 1950 1960 1970 1980 1990 2000 2010 3.0

2.5

2.0 STATUS AND TRENDS UPDATE UPDATE TRENDS AND STATUS

1.5 2. Guadalupe River Mercury Load 1.0 0.5 120 Sediment (million tonnes) 0.0 100 1995 2000 2005 2010 2012 Variation 80 driven by rainfall 60 5. Delta Mercury Load

40 2 kg

700 Large mercury | WATER QUALITY TRENDS AT A GLANCE TRENDS QUALITY WATER 20 600 loads from rivers and Yolo Bypass 500 0 due to high ow Wet Season Total Mercury (kg) Season Total Wet 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 400 and sediment load 300

Mercury (kg) 200 78 kg 100 0 1995 2000 2005 2010 2012

41 WATER QUALITY TRENDS AT A GLANCE SEE PAGE 45 Human Presence FOR GRAPH DETAILS

1. Bay Area Population 7.2 million 8 Population has increased Sonoma Napa 7 every decade Solano Marin since 1850 6 Santa Clara Contra Costa

5 San Mateo Alameda San Francisco 4

3

2 Population (Millions) 1

0 1850 1860 1870 1880 1890 1900 1910 1920 1930 1940 1950 1960 1970 1980 1990 2000 2010

2. Bay Area Vehicles Miles Traveled 3. Flows from Top Ten Wastewater Treatment Plants

12% 600 70 179% decrease increase since 1997 60 1980-2010 500 50 400

40 300 30 200 20 100 10 Average Daily Flow (MGD) Average 0 Vehicle Miles Travelled (billions) Miles Travelled Vehicle 0 19971998 1990 2000 2001 2002 2003 2004 2005 2006 2007 2007 2009 2010 1980 1985 1990 1995 2000 2005 2010

42 STATUS AND TRENDS UPDATE WATER QUALITY TRENDS AT A GLANCE 43 43 |

2020 6.4 inch increase 1920-2013 2010 2000 SEE PAGE 45 45 PAGE SEE 14,709 acres restored since 1986. Goal is 100,000 by 2100. 2005 1980 FOR GRAPHFOR DETAILS 20 Year Rolling Average Rolling Average 20 Year 1960 2000 1940 1995 1920 Annual Average Annual Average 1995 1900

3.8 3.6 3.4 3.2 3.0 2.8 2.6 2.4 2.2 2.0

Sea Level at Golden at Gate Sea Level Gate Golden the at Mean Sea Level (feet relative to MLLW) to relative (feet Level Sea Mean 0 1986 2. 8,000 6,000 4,000 2,000

18,000 16,000 14,000 12,000 10,000

Restored Wetland Opened to Tidal Action Opened to Tidal Wetland Restored Acres Restored Acres 5. 2000 2010 19901980 201220102008200620042002200019981996199419921990 201220102008200620042002200019981996199419921990 1970 NO TREND – 7 INCHES IN 2012 NO TREND – NO TREND – VARIABILITY DRIVEN BY FRESHWATER INFLOW DRIVEN BY FRESHWATER NO TREND – VARIABILITY NO TREND – SHORT TIME SERIES AND LARGE SEASONAL VARIABILITY TIME SERIES AND LARGE SEASONAL NO TREND – SHORT

1880 1900 1920 1940 1960

24 22 20 18 16 32 30 28 26 21 20 19 18 17 16 15 14 13 12 11

Salinity (ppt) Salinity Water Temperature (degrees C) (degrees Temperature Water 1870 1890 1910 1930 1950

Salinity Water Temperature Temperature Water Rainfall in the Bay Area Bay the Area in Rainfall 5 0

35 30 25 20 15 10 Rainfall (inches) (inches) Rainfall 4. 3. 1. Climate and Habitat and Climate WATER QUALITYTRENDS A GLANCE AT WATER QUALITY TRENDS AT A GLANCE SEE PAGE 45 Populations FOR GRAPH DETAILS

Pelagic Organism Decline

Delta Smelt Striped Bass

1,800 20,000 1,600 16,000 1,400 1,200 12,000 1,000 800 8,000 Abundance Abundance 600 400 4,000 200 0 0 1970 1976 1982 1988 1994 2000 2006 2012 1970 1976 1982 1988 1994 2000 2006 2012

All species have been near record lows since 2002

Long n Smelt Thread n Shad 90,000 16,000

70,000 12,000

50,000 8,000 Abundance Abundance 30,000 4,000 10,000 0 0 1970 1976 1982 1988 1994 2000 2006 2012 1970 1976 1982 1988 1994 2000 2006 2012

44 STATUS AND TRENDS UPDATE WATER QUALITY TRENDS AT A GLANCE

| 45 

. Salinity reflects Data from National Oceanic Data from National Oceanic Data from Water year median water Water Same information 3) Annual rainfall measured at San Jose Annual rainfall

the California Portal (www. Wetlands californiawetlands.net/ tracker/). and Atmospheric Administration: and Atmospheric Administration: http://tidesandcurrents.noaa.gov/ data_menu.shtml?bdate=19000520 &edate=20110521&wl_sensor_hist= W5&relative=&datum=6&unit=1&shi ft=g&stn=9414290+San+Francisco% 2C+CA&type=Historic+Tide+Data&fo rmat=View+Data 2) 3) 4) All data from: Baxter, R. All data from: Baxter, et al. 2010. Interagency Ecological Program 2010 Pelagic Plan Organism Decline Work and Synthesis of Results. http:// www.water.ca.gov/iep/docs FinalPOD2010Workplan12610.pdf 5) PAGE 44 temperature and interquartile feet range, San Mateo Bridge, 4 From below mean lower low water. 15-minute data collected by the U.S. Geological Survey (Buchanan 2009). 1999-2000 not shown because data were temporarily not collected during bridge construction. Some variation is caused by different periods of missing data. freshwater inflow to the Bay with lower values for higher inflows. Ocean water has a salinity of 35 ppt. as shown as index for Bay Area rainfall. shown as index for climatic years (July 1 These data are the year corresponding to to June 30 with Source: Jan Null, Golden the end date). Services Gate Weather PAGE 43 1) Data from USGS: sfbay.wr.usgs. Data from USGS: ) 2 Daily average Delta outflow from Water year median and interquartile Water Data from the U.S. Army Corps of Total loads for each water year. loads for each water year. Total Data from the U.S. Geological Survey. Survey. Data from the U.S. Geological and Data provided by the ten largest Total sediment loads for each water sediment Total Data from Caltrans: http://traffic- Data from the Association of Bay Area ) Total loads for each water year. Loads for each water year. loads ) Total gov/access/wqdata municipal wastewater dischargers to the Bay: San Jose, East Bay Dischargers, East Bay MUD, San Francisco, Central Contra Costa, Palo Alto, Fairfield-Suisun, South San Mateo, Bayside System Authority, Vallejo.

PAGE 42 1) 2) counts.dot.ca.gov/ 3) 2) 3) 4) 5 PAGE 40 1 3) 4) PAGE 41 1) from 2002–2006 are based on field data. Loads for earlier and later years are estimated from relationships observed between suspended sediment and mercury in 2002–2006. year. Loads based on continuous Loads based on continuous year. measurements taken at Mallard Island by USGS (http://sfbay.wr.usgs.gov/ sediment/cont_monitoring/). DAYFLOW. DAYFLOW data are available data are DAYFLOW DAYFLOW. from the California Department of Water Resources (www.water.ca.gov/dayflow/). range suspended-sediment concentration, concentration, range suspended-sediment Dumbarton Bridge, 20 feet below mean Based on 15-minute data lower low water. Surveycollected by the U.S. Geological Water (Buchanan and Morgan 2010). data. years 2008-2010 are provisional Governments U.S. Census Bureau. and http://census.abag.ca.gov/counties/ counties.htm Additional matching funds for this study Additional matching funds for USACE, SCVWD, provided by the CEP, and SCVURPPP. Engineers. Data for all of these graphs are for water Data for all of these graphs years (Oct 1 to Sep 30). Biofouling of water quality sensors. Photograph by Emily Novick. Minimum dissolved oxygen percent Chlorophyll a, averaged over top Sediment samples are tested using Chlorophyll a, averaged over top 3 Chlorophyll a, averaged over top 3 Bay-wide average methylmercuryBay-wide average Average of Bay Area summer beach Average Bay-wide average dioxin TEQ Bay-wide average dioxin TEQ Chlorophyll a in South Bay, averaged Chlorophyll a in South Bay, Chlorophyll a, averaged over top 3 Bay-wide average PCB concentrations. Bay-wide average PCB concentrations. saturation from each South Bay station, averaged over all stations. Minimum dissolved oxygen values typically occur at or near the bottom. Horizontal line indicates 50% saturation. concentrations. The San Francisco concentrations. The San Francisco Quality Control Board has Bay Water for dioxin developed a screening value TEQs of 0.14 partsWhite per trillion (ppt). skin from croaker were analyzed with 1994-2006, and without skin in 2009. meters and all stations, in San Pablo Bay (stations D41, s11, s12, s13, s14, and s15). The no consumption advisory tissue level two servingfor PCBs is 120 ppb, and the advisory tissue level is 21 ppb. White skin in croaker were analyzed without years. 2009, and with skin in previous 4) 5) 2) 3) 1) 4) 5) PAGE 39 Data from USGS: sfbay.wr.usgs.gov/ access/wqdata. Data from prior to 1969 from USGS. Data collected monthly at fixed stations along the spine of the Bay. Data for stations D10, D8, D7, D6, and D41 from IEP: http://www.water.ca.gov/ bdma/meta/Discrete/data.cfm. 3) 2) Graph Details Graph PAGE 38 1) WATER QUALITYTRENDS A GLANCE AT over top 3 meters, all stations, and June- line Trend October season for each year. is a smoothed fit. 3 meters and all stations, in South Bay (stations s21, s22, s23, s24, s25, s26, s27, s28, s29, s30, s31, s32, and s33). amphipods and mussel larvae. meters and all stations, in Suisun Bay meters and all stations, in Suisun Bay (stations D10, D8, D7, D6, s4, s5, s6, and s7). concentrations. Averages for striped bass Averages concentrations. for individual fish based on concentrations normalized consumption to 60 cm. The no advisory for mercury tissue level is 440 ppb, and the two serving advisory tissue level is 70 ppb. season (April-October) grades from Heal annual beach report card. the Bay’s 46 CEC MONITORING 4747 TIER 4 TIER 3 TIER 1 TIER 2 Fipronil 83 IN THE BAY IN THE BAY s Perfluorooctane Sulfonate 55 Pyrethroids 79 P N Introduction The RMP Emerging Contaminants Workgroup Contaminants RMPThe Emerging Polybrominated Diphenyl Ethers Ethers Diphenyl Polybrominated Chlorinated Paraffins Paraffins Chlorinated Currently Used Pesticides Pesticides Used Currently On the Lookout for CECs New On Lookout the Furans and Dioxins olybrominated Alkylphenols Alkylphenol and Ethoxylates Alternative Flame Retardants Products Care Personal and Pharmaceuticals Nanomaterials or anoparticles Triclosan Triclosan M CONCERN IN SAN FRANCISCO BAY FRANCISCO IN SAN CONCERN 71 75 87 91 92 93 94 51 54 59 63 67 A GUIDE TO CEC TO A GUIDE OF EMERGING CONTAMINANTS ONITORING 54 48 JAY DAVIS, MEG SEDLAK, and REBECCA SUTTON HIGHLIGHTS MONITORING San Francisco Estuary Institute Contaminants of emerging concern (CECs) are synthetic or naturally occurring chemicals that are not regulated or commonly monitored but have the potential to adversely impact CONTAMINANTS water quality Determining which of the thousands of chemicals in commerce are CECs and whether or not they may be a problem is a OF EMERGING CONCERN formidable challenge due to a lack of knowledge of what chemicals are in use, analytical methods, and information on toxicity to aquatic species IN SAN FRANCISCO BAY San Francisco Bay is one of the most thoroughly-monitored aquatic ecosystems in the world with respect to CECs

The RMP is employing a three-pronged approach to identify and monitor CECs in the Bay, including targeted monitoring using a risk-based, tiered prioritization scheme; keeping an eye on chemicals under evaluation by other programs and investigators; and applying open-ended, “non-targeted” monitoring tools that can screen for broad classes of compounds

Surveillance of CECs using this three-pronged approach is going to remain a high priority for the RMP in years to come

48 CEC MONITORING MONITORING CEC s

| 49 ) and PBDEs ) and ). PHARMACEUTICALS: ~3,000 PESTICIDES: ~1,000 COSMETIC AND ADDITIVES: ~3,000 PAGE 55 PAGE FOOD ADDITIVES: ~9,000 PAGE 63 PAGE ). These studies also appear to be providing providing to be alsoappear studies ). These ~ 84,000 CHEMICALS INDUSTRIAL PAGE 63 PAGE evidence that actions to reduce the uses of CECs and their their and of CECs the uses reduce to actions evidence that concentrations in lowering be effective can the Bay input to ( for PBDEs as seen in the Bay, A Bright Spot in CEC Monitoring CEC in Spot A Bright Program Monitoring to the Regional Thankslargely is thoroughly one of the most Bay Francisco San (RMP), with in the world respect ecosystems aquatic monitored the has allowed base stable funding The RMP’s CECs. to of water the needs meet to continually adapt to Program of the challenge addressing including quality managers, as mercury such RMP problems of legacy studies CECs. trap be a long-term can the Bay shown how have PCBs and with decades taking recovery contaminants, for persistent is extensive. when centuries the contamination or even this into contaminants the entry of problematic Preventing protect to way the ideal is therefore ecosystem vulnerable in mind, the RMP lessons these With quality. water Bay to identify years and effortrecent a concerted in made has the RMP by have others studies and CEC CECs. monitor by be a hotspot for contamination to the Bay revealed ( as PFOS such certain substances, (

FIGURE 1 challenge. Approximately 100,000 Approximately 100,000 pose the greatest risks to pose the greatest risks which of these chemicals which of these chemicals chemicals were registered chemicals were registered for commercial use in the US for commercial use in the water quality is a formidable from 1975-2005. Identifying from 1975-2005. Identifying ntities of many chemicals used in commer- chemicals used ntities of many Footnote: From Muir and Howard (2006). nalytical methods to measure many CECs in the CECs many nalytical measure methods to ittle to no information existsto no information toxicityittle on many for environment (sediment, water, and aquatic organ- aquatic and water, (sediment, environment not exist, do analytical of new development isms) and methods for chemicals is expensive. realis- effects from chemicals, especially for sublethal toxicity exposures, species, aquatic in tic longer-term as endocrine such endpoints toxicological or sensitive disruption. for of toxic of action modes Knowledge is details and minimal, of toxicity studies CECs most typically are manufacturers chemical by conducted review. for public not available The ide product- and their applications, cial formulations, business confidential as characterized are specific uses other due to available not readily or are information reasons. A L

• • • These obstacles make it very challenging for environmental very it make environmental for challenging obstacles These for CECs target pre-emptively to regulators and researchers majority the vast of chemicals For control. and monitoring toxicity and data persistence, the occurrence, today, in use ecosystems aquatic of uses the beneficial protect to needed in shortare supply. ). Global ). Global FIGURE 1 Photograph by Ellen Willis-Norton. The CEC Challenge TheCEC or ap- registered been 100,000 chemicals have than More than more including in the US, use for commercial proved 3,000 84,000 industrial chemicals,food additives, 9,000 ingredients, 1,000 pesticide active ingredients, cosmetics 2006; Howard and drugs (Muir 3,000 pharmaceutical and 2013) ( USEPA et al.Benotti 2009, chemical production is projected to continue growing by by growing continue to is projected production chemical (Wilson every double and and 24 years year, per 3% about 2009). Schwarzman in majority for the vast of chemicals currently However, limit the ability gaps information of scientists major use, risks, of these their potential monitoring assess and to Effortsto monitor occur. not routinely chemicals does severely chemicals are of these impacts the environmental on their presence of information the lack by hampered in the environ- their movement products, in commercial chemicals that As many a result, their toxicity. and ment, impacts for their potential tested adequately not been have the into wildlife and humans released to continuously are ecosystems aquatic into washing ultimately environment, Bay. Francisco as San such agencies government and researchers decade, the last Over toxicity and data fate, occurrence, collect begun to have regulated been not yet have for a variety of chemicals that Analytical impacts. methods have for environmental detection frequent which to led has continually improved, chemicals in the of a variety of previously unmonitored classified been chemicals have of these Some environment. can CECs (CECs). concern of emerging as contaminants occurringsynthetic naturally any or as defined be broadly monitored or commonly is not regulated that chemical the enter to the potential but has in the environment health or human ecological adverse cause and environment identify include high to used CECs Characteristics impacts. for toxicity and species, potential in aquatic use, volume in the environment. occurrence which of the thousands of chemicals in com- Determining be a problem whether and or not they may CECs are merce a chemicals in use, most For is challenge. a formidable assessing from researchers prevent of limitations number risks.their potential  Keys to the Success of RMP Stable funding, guidance from leading scientists, and collabora- CEC Monitoring tion have been key to the success of RMP CEC monitoring Three ingredients have been key to the success of RMP monitoring for CECs. The first, already mentioned above, is a stable base of funding that has been allocated to inves- a wide variety of CECs in mussels on the California coast, of specific CECs are available and affordable. The frame- tigating CECs over the past 10 years. Current plans for the including the Bay. This major collaboration with the Na- work provides guidance on inclusion of each chemical in RMP (SFEI 2012) call for continuing the flow of funding tional Oceanic and Atmospheric Administration, Southern RMP “status and trends” monitoring (routine monitoring for this high priority topic over the next several years. California Coastal Water Research Project, State Water of water, sediment, mussels, sport fish, and bird eggs) and Another essential ingredient of RMP CEC monitoring Resources Control Board, and others culminated in a series on the need for special studies on sources, fate, or effects. has been guidance from leading CEC scientists. In 2006 of papers published in a special issue of Marine Pollution The results of the monitoring and special studies help to the RMP formed the Emerging Contaminants Work- Bulletin in 2013. refine the placement of chemicals within the framework. group (ECWG). RMP workgroups consist of regional With regard to management, the framework also guides de- scientists and regulators and invited scientists recognized cisions on actions needed to reduce impacts on Bay water as authorities in their field. The workgroups guide the RMP CEC Studies to Date quality (PAGE 8). planning and implementation of RMP studies. The RMP The sustained focus of the RMP on CECs over the past CEC science is a rapidly growing and evolving field, with a has had the extremely good fortune of having some of the 10 years, aided by guidance from the science advisors and vast amount of work occurring beyond the boundaries of world’s experts on CECs serve as advisors on the ECWG stakeholders and extensive collaboration, has allowed the the RMP. The second element of the RMP CEC Strategy (PAGE 51). The guidance of these outstanding scien- Program to perform a substantial body of work (TABLE is to learn as much as possible from work being done by tists has helped the RMP focus on the CECs of greatest 2). These studies have yielded a wealth of information on others. This entails thoroughly reviewing the scientific concern for the Bay and on using monitoring techniques CECs in the Bay that has supported policy decisions, and literature, staying apprised of other CEC aquatic monitor- with the greatest likelihood of yielding valuable informa- they have made the Bay a primary proving ground for test- ing efforts, and maintaining a dialogue with leading CEC tion. In addition, many of these scientists have conducted ing advanced approaches for CEC monitoring. scientists as a means of identifying new CECs to target and pro bono work for the RMP, including monitoring the A RMP-funded summary of CEC monitoring in the Bay to new approaches for monitoring. Candidate chemicals for Bay for perfluorinated compounds PAGE( 55), nanopar- date was recently completed (Klosterhaus et al. 2013). This monitoring are evaluated by the ECWG, and the chemicals ticles (PAGE 91), and chlorinated paraffinsPAGE ( 92). review set the stage for development of a CEC monitoring with the greatest potential to impact Bay water quality are The ECWG has become an important forum where the strategy (Sutton et al. 2013) to guide RMP studies over selected for preliminary studies to determine whether they cutting edge of CEC science is applied to answering ques- the next several years. The review also served as a source of are present in the Bay. tions regarding Bay water quality. much of the information presented in this edition of The A major challenge in monitoring CECs is the absence of A third important ingredient in RMP CEC monitoring has Pulse. analytical methods to perform targeted monitoring of been collaboration. Pro bono work, matching funds, and many of the thousands of chemicals that occur in the en- partnerships with many organizations have substantially A Three-Pronged Approach vironment. The third element of the Strategy circumvents augmented RMP studies (TABLE 1). AXYS Analytical this problem by employing open-ended, “non-targeted” (www.axysanalytical.com), for example, is a laboratory that The RMP CEC Strategy calls for a three-pronged approach monitoring tools that can screen for broad classes of performs chemical analysis of organic contaminants for the to identifying and monitoring CECs in the Bay. The first compounds. One non-targeted approach is based on the RMP. AXYS is a world leader in development of analytical element of the Strategy applies to chemicals where occur- use of an analytical instrument called a mass spectrometer, techniques for CECs, and has performed a considerable rence data for the Bay are available. For these chemicals, which can allow identification of unknown compounds by amount of pro bono work for the RMP on a diverse array of relative risk is evaluated using a tiered framework (FIGURE breaking the contaminant molecules into fragments and CECs, including pharmaceuticals, personal care products, 2). With regard to monitoring, the framework guides then examining the atomic masses of the fragments (“mass alkylphenols, perfluorinated compounds, and brominated decisions on “targeted” investigation of CEC sources, spectra”). Sometimes, but not all the time, the analytical dioxins (Klosterhaus et al. 2013). Another significant occurrence, and impacts on Bay water quality. Targeted chemist can deduce the identity of a contaminant based example of collaborative CEC monitoring was a survey of monitoring is possible when methods for chemical analysis on comparison to libraries of mass spectra or through an

50 CEC MONITORING MONITORING CEC s

| 51 DEREK MUIR, Environment Canada KEITH MARUYA, Southern KEITH MARUYA, California Coastal Water Research Project MEG SEDLAK, San Francisco Estuary Institute JUNE SOO PARK, California Department of Substances Control Toxic REBECCA SUTTON, San Francisco Estuary Institute DON YEE, San Francisco Estuary Institute Regional Scientists Regional JONATHAN BENSKIN, BENSKIN, JONATHAN AXYS Analytical San Francisco DAVIS, JAY Estuary Institute DODDER, Southern NATE California Coastal Water Research Project RICHARD GRACE, AXYS Analytical DENISE GREIG, California Academy of Sciences DAVID SEDLAK, DAVID University of California – Berkeley KELLY MORAN, MORAN, KELLY TDC Environmental TOM MUMLEY, San Francisco Bay Board Regional Water KARIN NORTH, City of Palo Alto USEPA LUISA VALIELA, IAN WREN, San Francisco Baykeeper SIMRET YIGZAW, City of San Jose PHIL GSCHWEND, Massachusetts Institute of Technology Stakeholders EVA AGUS, EBMUD EVA MIKE CONNOR, East Bay Dischargers Authority ERIC DUNLAVEY, City of San Jose AMY CHASTAIN, San Francisco Public Utilities Commission NAOMI FEGER, San Francisco Bay Board Regional Water

JENNIFER FIELD, JENNIFER FIELD, Oregon State University Science Advisors LEE FERGUSON, LEE FERGUSON, Duke University An essential key to the success key to the success An essential monitoring has of RMP CEC from leading been guidance CEC scientists and stakeholders. In 2006 the RMP formed the - Work Emerging Contaminants workgroups group (ECWG). RMP and consist of regional scientists scientists regulators and invited in their recognized as authorities guide the field. The workgroups planning and implementation has of RMP studies. The RMP fortunehad the extremely good world’s of having some of the experts on CECs serve as advi- sors on the ECWG. The guidance of these outstanding scientists has helped the RMP focus on the CECs of greatest concern for the Bay and monitoring techniques with the greatest likelihood of yielding valuable information. In addition, many of these scientists have conducted pro bono work The ECWG has be- for the RMP. come an important forum where the cutting edge of CEC science is applied to answering questions regarding Bay water quality. The RMP Emerging Contaminants Workgroup Contaminants RMP Emerging The ) and reduced use of toxic use reduced ) and PAGE 13 PAGE understanding of general fragmentation fragmentation general of understanding collaboration in with The RMP, patterns. and of Standards Institute the National a two- completed recently Technology, biota in Bay CECs for screening study year spectrometry mass a sophisticated using al. et in prep). (Kucklick method non- another The RMP evaluating is also for screen to aims that approach targeted of compounds withclasses a similar mode envi- many example, For of toxic action. as “endocrine act contaminants ronmental with interfere chemicals that disruptors,” by often controls, hormonal physiological hormones like es- endogenous mimicking cortisol, or thyroxine. testosterone, trogen, in 2013 is develop- A RMP initiated study of the presence for evaluating a tool ing from compounds in samples estrogenic contami- other and CECs Many the Bay. this is work mimics. If estrogen are nants it willsuccessful, measure be possible to potency of the com- estrogenic the overall in Bay present of contaminants bination This samples. typereferred technique is of as a “bioanalyticalto it uses because tool” the CECs measure to a biological response in a sample. this three- using Surveillance of CECs remain to is going approach pronged prioritya high to for the RMP in years Thisis one critical monitoring come. the oc- prevent to of a strategy component problems contamination of new currence and of present the health threaten that wildlife of Bay Bay and future generations chemis- “green Ultimately, residents. Area try” ( chemicals in products is the ideal way to to way is the ideal chemicals in products of the emergence from the Bay protect chemicals of concern. new TIER ASSIGNMENTS MANAGEMENT MONITORING

TIER 4 303(d) listing HIGH No CECs TMDL or alternative Studies to support TMDL management plan. CONCERN currently or an alternative in this tier Aggressive control actions management plan for all controllable sources

PFOS Action plan or strategy Consider including in TIER 3 Fipronil Status and Trends Aggressive pollution Monitoring MODERATE Nonylphenol prevention and nonylphenol Special studies of fate, CONCERN Low-cost ethoxylates effects, and sources, control actions PBDEs pathways, and loadings

FIGURE 2 The first element of the RMP’s three-pronged HBCD Low-cost source Discontinue screening, identi cation and control or periodically screen in approach to CEC monitoring applies to chemicals TIER 2 Pyrethroids where occurrence data for the Bay are available. water, sediment, or biota Low-level pollution For these chemicals, management and monitoring LOW Pharmaceuticals prevention Periodic screening are guided by a tiered framework based on the and personal care CONCERN in wastewater efuent degree of risk associated with each chemical. products Track product use or urban runoff With regard to monitoring, the framework guides and market trends decisions on “targeted” investigation of their PBDDs and PBDFs to track trends sources, occurrence, and impacts on Bay water quality. The framework provides guidance on inclusion of each chemical in RMP “status and trends” monitoring (routine monitoring of water, sediment, mussels, sport fish, and bird eggs) Identify and prioritize Alternative and on the need for special studies on sources, TIER 1 contaminants of Screening in water, ame retardants fate, or effects. The results of the monitoring and potential concern, sediment, biota, special studies help to refine the placement of POSSIBLE Pesticides track international efforts wastewater efuent, chemicals within the framework. With regard CONCERN urban runoff to management, the framework also guides Plasticizers Develop targeted and non-targeted decisions on actions needed to reduce impacts Many, many others on Bay water quality (PAGE 8). analytical methods

52 CEC MONITORING MONITORING CEC s

| 53 Oros et al. 2003 PUBLICATIONS/STATUS Lunder and Sharp 2003 Harrold et al. 2009 Sedlak et al. 2012, work ongoing; Sedlak et al. 2012, work Houtz and Sedlak 2012 Klosterhaus et al. 2009 (SETAC Poster), Klosterhaus et al. 2009 (SETAC 2012a; work ongoing Completed small pilot study Completed small pilot study Klosterhaus et al. 2011, 2012b Completed small pilot study; potential UM article forthcoming Rattner et al. 2011; Rattner et al. 2013 Kucklick et al. 2013 Klosterhaus et al. 2013 Maruya et al. 2013a,b; Dodder et al. 2013; Alvarez et al. 2013 Klosterhaus et al. 2013 Sutton et al. 2013a Work ongoing Work Sutton et al. 2013b Klosterhaus et al. 2012 Sedlak, Muir, Sverko,Yee -- unpublished data Sverko,Yee Sedlak, Muir, echnol- COLLABORATORS COLLABORATORS Environmental Working Group Environmental Working University of California at Berkeley; The Marine Mammal Center; CDFW Duke University; Southern Illinois University; The Marine Mammal Center Canada Department of Fisheries and Oceans; The Marine Mammal Center USEPA California Polytechnic, San Luis Obispo Diehl et al. 2012 AXYS Analytical; University of MN; The Marine Mammal Center USGS ogy; Southern California Coastal Water Re- ogy; Southern California Coastal Water search Project; The Marine Mammal Center, San Diego State University AXYS Analytical National Oceanic and Atmospheric Administration; Southern California Coastal Research Project; State Water Water Resources Control Board University of Florida; SCCWRP USGS; Duke University Environment Canada

PBDEs in Bay Fish CECs in Bay Water TOPIC Pharmaceuticals and Personal Care Water Products in Effluent and Bay Perfluorinated Compounds Alternative Flame Retardants Chlorinated Paraffins in Biota Chlorinated Paraffins in Triclosan in Sediment Triclosan Profiles on CECs in Wastewater: Triclosan Wastewater: Profiles on CECs in Alkylphenol Ethoxylates, and Triclocarban, Carbamazepine Nonylphenol in Small Fish AXYS Brominated Dioxins in Sediments and Biota PBDE Effects on Terns Broadscan Screening of Biota for CECs National Institute of Standards and T AXYS Mussel Study NOAA Mussel Pilot Study CEC Synthesis CEC Strategy Bioanalytical Tools PBDE Synthesis Nanoparticles Siloxanes in Bivalves TABLE 2 to Date. RMP CEC Studies

Applied Marine Sciences AXYS Analytical California Department of Fish and Wildlife Cal Poly San Luis Obispo Canada Department of Fisheries and Oceans City of Palo Alto Duke University Environment Canada The Marine Mammal Center National Institute of Standards and Technology National Oceanic and Atmospheric Administration San Diego State University Southern California Coastal Research Project Water Southern Illinois University Board State Water University of California – Berkeley University of Florida University of Minnesota US Environmental Protection Agency US Geological Survey Pro bono work, matching funds, Pro bono work, and partnerships with many organizations RMP studies. have substantially augmented TABLE 1 This section of The Pulse provides a A GUIDE TO CECs guide to the chemicals that are brightest on the CEC surveillance radar screen. IN THE BAY For each chemical or class of chemicals, a synopsis is provided that describes the A bewildering array of chemicals is swirling around in properties, uses, sources, environmental the Bay. As part of the RMP, water quality scientists and fate, occurrence, trends, risks, managers are rising to the challenge of identifying the information gaps, and milestones in subset of these chemicals that poses the greatest and management. These concise summaries clearest threats to Bay health. are based on thorough reviews and

FOR MORE INFORMATION more extensive documents that are listed RMP Web Page on CECs: www.sfei.org/content/RMPCEC on the RMP web page on CECs (link CEC Synthesis Report: Klosterhaus et al. 2013. Contaminants of Emerging Concern in San Francisco Bay: provided on this page). A Summary of Occurrence Data and Identification of Data Gaps. RMP Contribution #698. San Francisco Estuary Institute, Richmond, CA. CEC science is a rapidly evolving field. CEC Strategy Document: Sutton et al. 2013. Contaminants of Emerging Concern in San Francisco Bay: A Strategy for Future Investigations. RMP Contribution #700. San Francisco Estuary Institute, Richmond, CA. New information is continually being generated, including quite a bit by the RMP, that is causing shifts in the levels of concern associated with individual CECs. This guide represents a series of snapshots based on what we know now (August 2013). The RMP will continue to track advances in CEC science, evaluate their relevance for the Bay, and provide this information to managers, scientists, and the public in a manner that supports protection of Bay water quality.

54 CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 55 PF Kannan the 2001). At and in 2000 (Giesy the world be a pervasive also it was found to time, con- same al. et (Hansen in the US blood in human taminant PFCs of manufacturer US 2001). As the major a result, structurally other and voluntarily withdrew PFOS America in North similar its use and compounds, and PFOS reductions, use Despite restricted. was Europe as a result in the environment be detected to continues degrade that precursors of PFOS use of the continued historic reservoirs chemicals prod- in of these PFOS, to impurities PFOS in other the environment, ucts and PFC and of PFOS production the continued and PFCs, as China. parts such in other of the world, precursors F applications. consumer and in industrial, commercial, for carpets, repellent as a stain used been has PFOS (“grease-proof” products paper); textiles, paper and - refin at used (AFFF) film-forming foams in aqueous eries, airports, military and or industrial facilities to and metal-finishing; and electronics in fires; suppress as a pesticide. extensively used been have PFCs 50years, or thelast in wildlife first was OS detected widely throughout • What Is It Used For? For? Used It Is What • PF PF is a very that oil) and persistent water in both is soluble contaminant. environmental PF are compounds that of fluorine-containing class diverse surfac- excellent the environment, in stable extremely of applications. in a wide used and range tants, inbiota. accumulates OS that (chemical surfactant isOS afluorine-containing –a isOS (PFC) atype chemical ofperfluorinated • What Is It? • • - - MEG SEDLAK, MEG SEDLAK, San Francisco Estuary Institute ([email protected])

1/4 Perfluorooctane (PFOS) Sulfonate mers; and as an insecticide. PFOS repels both water and and both water repels PFOS insecticide. as an and mers; used been it has Consequently, oil is stable. and highly in the global widely been has detected and extensively and birds Bay Francisco in San including environment, eggs Bird in fishand extent bivalves. a lesser to and seals in 2006 portion in the southern of the Bay collected a threshold above of PFOS levels 2009 contained and on offspringsurvival for impacts Fortunately, in birds. (2012) Bay in South results egg PFOS recent the most this well below prior and than levels 70% lower were do in seals concentrations PFOS However, threshold. by which these pathways The similar declines. not show not fully are understood. the Bay compounds enter Quick Summary Quick widely been as a has used 1940s, PFOS the late Since for textiles, carpets; and furniture, as a repellant stain pro finishing metal and foams in fire-fighting surfactant cesses; as an ingredient in the production of fluoropoly in the production ingredient as an cesses; TIER 3 CONCERN MODERATE 2/4 TIER 3 Perfluorooctane Sulfonate (PFOS)

How Is It Getting Into the Bay? • Shorter-chained fluorinated compounds are being • Cormorant eggs have been collected from three Bay sites substituted for PFOS. Perfluorobutanesulfonate (PFBS), on three occasions: 2006, 2009 and 2012. Average PFOS The ourcess and pathways of PFOS to the Bay are not • one of the substitutes, has been detected in Bay effluents concentrations in eggs from the South Bay in 2006 fully understood. and tributaries at relatively low concentrations (10 (1,300 ppb) and 2009 (1,200 ppb) exceeded a threshold • Research in the Great Lakes and elsewhere suggests that ng/L). Shorter-chained compounds such as PFBS are of 1,000 ppb, above which adverse outcomes have been wastewater effluent and urban tributaries are important believed to be less toxic and less bioaccumulative. observed for survival. In 2012, PFOS in South Bay bird pathways. Also potentially significant are point sources • Precursors that degrade to PFOS may be another source eggs was substantially lower (385 ppb). such as contaminated sites where PFOS has been di- (Higgins et al. 2005). • Concentrations of PFOS in seal blood have remained rectly released to the environment (e.g., as a result of the relatively constant over time. Similar to birds, the use of AFFF to fight fires, spills from production sites, highest concentrations were observed in the South Bay and the land application of biosolids). What Happens to It in the Bay? (1,000 ng/mL, parts per billion (ppb) followed by Cen- • Municipal wastewater treatment plant (WWTP) efflu- tral Bay (80 ppb)). Background concentrations observed ent is a major pathway. Uses in consumer, commercial, General Properties in seals from Tomales Bay in the Point Reyes National and industrial products result in transport to WWTPs. • Longer-chained PFCs (with eight carbons or more) Seashore were much lower (12 ppb). WWTPs are not effective at removing PFCs and in some can degrade to PFOS, which is not known to undergo • PFOS was infrequently detected in sport fish tissues. Of instances promote the formation of PFOS from precur- further degradation in the environment. the 21 fish analyzed in 2009, PFOS was detected in four sors (Schultz et al. 2006, Becker et al. 2008). • Unlike legacy contaminants such as PCBs and DDT that samples (leopard shark, anchovies, and white sturgeon) • In a recent RMP study, the average concentration in accumulate in fatty tissues, PFOS binds to proteins and with a maximum concentration of 18 ppb. There are effluent from six Bay Area WWTPs was 24 nanograms is most frequently detected in blood and liver. no California thresholds for evaluating risks to humans per liter (ng/L) (Sedlak and Allen in prep). This value is from PFOS concentrations in Bay sport fish. The State on the low end of the range of concentrations commonly Patterns of Occurrence in the Bay of Minnesota has established a sport fish threshold of 40 seen in effluent nationally (Plumlee et al. 2008). Con- and in Other Aquatic Ecosystems ppb for one serving of fish per week. centrations from WWTPs receiving industrial wastewa- • PFCs do not appreciably bioaccumulate in mussels. ter are typically higher. • Bay sediment concentrations ranged from 0.4 to 3.2 parts per billion (ppb) (Sedlak and Allen in prep). The As part of a larger California survey and a RMP special • Urban stormwater, which flows directly into the Bay un- highest concentrations were observed in the South Bay. study, PFOS was monitored in mussels at 13 Bay sites in treated, is another potential source of PFOS to the Bay. 2010. PFOS was detected in two samples from the South ° These values are consistent with prior studies of Bay at concentrations of 35 ng/g dw and 76 ng/g ww. ° In a survey of three Bay Area tributaries, PFOS San Francisco Bay and are within the range of concentrations ranged from below detection to 14 concentrations observed nationally in estuaries ng/L (Sedlak and Allen in prep). These values are and lakes. For example, concentrations from Lake Trends in the Bay and Nationally in the range observed in other Bay Area studies Ontario were higher on average (26 ppb) (Myers • No trend data for Bay sediment and water are available. and nationally (Plumlee et al. 2008, Houtz and et al. 2012). Sedlak 2012). • PFOS was lower in the most recent sampling of Bay bird • Average PFOS concentrations in Bay surface water in eggs, but no sign of a trend has been observed in Bay Unknown precursors in tributaries may be con- 2009 were 7 ng/L. These were generally lower than other ° seals (FIGURES 1 AND 2). verted to PFOS (Houtz and Sedlak 2012). urban water bodies such as Tokyo Bay (0.3-58 ng/L) and • Rain can be a pathway for PFOS. Concentrations of Lake Ontario (3.6-38 ng/L), but exceed concentrations PFOS in Bay Area rainwater have not been measured. measured in more pristine environments. Is There a Risk of Harm in the Bay? • Other possible point sources are facilities that may use • PFOS accumulates in Bay birds and seals to levels that • In mammals, PFOS exposure has been associated with AFFF such as refineries and airports, or facilities where may be of concern (FIGURES 1 AND 2). Bay seal and compromised immune systems, reproductive and devel- these materials are discarded such as landfills. PFC bird egg concentrations have been some of the highest opmental defects, neurotoxicity, and cancer (DeWitt et concentrations at such point sources have not been observed worldwide. al. 2012). monitored in the Bay Area. 56 CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 57 TIER 3

FIGURE 1 seals and PFOS accumulates in Bay be of concernbirds to levels that may observedand are among the highest of PFOS worldwide. Concentrations relatively in seal blood have remained highest constant over time. The concentrations were observedin the partsSouth Bay (1,000 ng/mL, per by Central Bay billion (ppb)) followed concentrations (80 ppb). Background Bay in observed in seals from Tomales the Point Reyes National Seashore were much lower (12 ppb). Tomales Tomales 2007-2009 2010-2011

Richmond Bridge Don Edwards Corkscrew Corkscrew Rocks Castro 2012 2006 2009

Wheeler Island Island Wheeler Mowry Predicted no effect concentration 0 0 800 600 400 200

800 600 400 200

1200 1000 2000 1800 1600 1400 1200 1000

PFOS in Seal Blood (ppb) Blood Seal in PFOS PFOS in Eggs (ppb wet wet (ppb Eggs in PFOS

FIGURE 2 Wheeler Island Mowry Slough Don Edwards substantially lower (385 ppb). for embryo survival. In 2012, PFOS concentrations in South Bay eggs were adverse outcomes have been observed Footnote: Each bar represents the average of three ppb) and 2009 (1,240 ppb) exceeded a threshold of 1,000 ppb, above which eggs from the South Bay in 2006 (1,250 Slough Richmond Bridge, Castro Rocks composite samples, with seven eggs in each composite. Average PFOS concentrations in cormorant Average Corkscrew Perfluorooctane (PFOS) Sulfonate 3/4 4/4 TIER 3 Perfluorooctane Sulfonate (PFOS)

• A predicted no effect concentration for PFOS has been Key Information Gaps • Manufacturers are shifting to fluorinated compounds developed for bird eggs of 1,000 ppb (Newsted et al. that are expected to be less toxic and less likely to ac- Few studies have evaluated the effects of PFOS exposure 2005). Concentrations in Bay cormorant eggs have • cumulate in biota. It will be important to monitor to in seals. exceeded this threshold, but the most recent data from ensure that these are not accumulating in the Bay or in 2012 were substantially below this threshold. • The ourcess of PFCs to Bay biota are not well under- Bay biota. stood. • In a study of California sea otters (Kannan et al. 2006), Little is known regarding the presence and pathways by PFOS concentrations similar to those observed in Bay • harbor seals were associated with a higher incidence of which precursors form PFOS in the Bay. disease and mortality.

Management Timeline 2009 European Union places PFOS on its Stockholm Convention list of Persistent and Organic Pollutants, which are 2000-2002 2002 severely restricted or prohibited from use. Phase-out of the US Environmental Protection Agency (USEPA) production of PFOS issues Significant New Use Rules restricting use Environment Canada 2012 places PFOS on the and structurally of PFOS and 88 structurally similar perfluoroalkyl USEPA restricts use of Virtual Elimination List to similar compounds sulfonate compounds. In 2007, USEPA expands PFOS in some metal- eliminate the production in North America. the list by 183 more perfluoroalkyl substances. finishing operations. and use of the compound.

2001 2003 2004 2005 2006 2007 2008 2010 2011 2013 2014 2015

2006 2010-2015 European Union restricts the use USEPA obtains agreement by eight major of PFOS; Environment Canada manufacturers to replace PFOA (another abundant places PFOS on the List of Toxic PFC) and related chemicals by 95% by 2010 Substances, a list of chemicals with a complete phase-out of these compounds in that are considered toxic and may 2015 (USEPA’s 2010/2015 PFOA Stewardship be regulated to prevent adverse Program). Environment Canada has developed a releases to the environment. similar agreement.

58 CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 59

L com- other and form nonylphenol to treatment pounds like short-chain APEs oxidized and APEs. and on nonylphenol focused have studies Most monoe- like nonylphenol ethoxylates nonylphenol or diethoxylates. thoxylates R but APEs high, and are sorption sludge through to com- nevertheless are products their breakdown of result as a effluent in wastewater monly detected of use. volume the high during wastewater APEs biodegrade ong-chain treatment wastewater efficiencies in emoval ° ° A A They a M and cleaning products for industrial and institutional institutional for industrial and products cleaning and the products for common in less now are They settings. home. performance. enhance to “inert ingredients” tile processing, metalworking, as oilfieldand chemicals in spills,for dispersal of petroleum as ingredients and spermici- and products, care personal adhesives, paints, lubricants. dal although environments, aquatic to pathway the major pathways. potential on other is needed information more U application including discharge, direct deposition, and important other are vegetation, aquatic to of pesticides pathways. detergents in assurfactants used commonly PEs are as pesticide formulations to added been PEs have tex- and leather production, inpaper also used re is effluent likely plant treatment wastewater unicipal atmospheric seepage, system septic stormwater, rban • • How Are They Getting Bay? the Into • • What Are They Used For? For? Used They Are What • detergent-like compounds that have been widely been used have compounds that detergent-like the 1940s. since 2010); (USEPA ethoxylates nonylphenol are the US the next APE common most are octylphenol ethoxylates al.et 2010). (Chiu alkylphenols octylphe- and likedown nonylphenols into nols as prioritiesethoxylates for nonylphenol identified has voluntary phase-out. pounds consisting of chains of carbon atoms, typically atoms, of carbon chains of pounds consisting atoms, or nine carbon eight of consisting and branched to a six-carbon phenol ring. attached A E Onc The U A APE surfactants, make to used lkylphenols are ofthe in inuse APEs percent eighty-five ighty to break APEs often theenvironment, into e released Agency (USEPA) Protection S Environmental afamily com- lkylphenols ofsynthetic are organic • • • • What Are They? • CHRISTINE WERME, CHRISTINE WERME, Independent Consultant ([email protected])

Quick Summary Quick octyl- and Alkylphenols, nonylphenol including of alkylphenol products breakdown key are phenol, in common once surfactants, (APE) ethoxylate products cleaning other and detergents household of industrial applications. in a number alsoand used in water, detected been Alkylphenols APEs and have egg cormorant small fish,and mussel, sediment, high relatively at sometimes the Bay, from samples Alkylphenols APEs some are and concentrations. known endocrine disruptors. While concentrations those below been mostly have in the Bay measured toxicity chronic organ- in marine cause known to the existing is evidence of new that levels isms, there withalkylphenols APEs, and in combination pyre- fish popula- Bay be affecting may pesticides, throid endocrine RMP disruption. tions through A recent al. et 2012) presents report on APEs (Klosterhaus fate production, and on use information additional the environment, and plants treatment in wastewater gaps. information and impacts, potential Alkylphenols and Alkylphenol Ethoxylates Alkylphenol and Alkylphenols 1/4 TIER 3 CONCERN MODERATE 2/4 TIER 3 Alkylphenols and Alkylphenol Ethoxylates Nonylphenol Monoethoxylate

PALH What Happens to Them in the Bay? Detection was sporadic in RMP mussel samples, ° GCGC but concentrations were sometimes high, with BBBE North General Properties maximum measurements of nonylphenol, Coast nonylphenol monoethoxylates, and nonylphenol TBSR • Alkylphenols and APEs entering the water column have DRDP a strong tendency to bind to sediment particles. diethoxylates of 1,290, 300, and 1,420 ppb, respec- tively. • APEs can be broken down by microbes or sunlight into SFEM High concentrations of nonylphenol (maximum SF alkylphenols and other compounds in the Bay, depend- ° SFYB Bay ing on environmental conditions. The environmental 123 ppb) and nonylphenol ethoxylates (maximum SFSM fate of these breakdown products is not well understood. 228 ppb) have also been found in Bay cormorant eggs. MBES • Nonylphenol itself does not break down easily and is Central considered a persistent pollutant in aquatic environ- ° Octylphenol was not detected in water, sediment, MBVG Coast ments. or mussel samples. SLSL • The NOAA Mussel Watch California CEC Pilot Study • Alkylphenols and APEs are somewhat volatile, so a por- CPSB (Mussel Watch) 2010 found lower concentrations in tion of these chemicals may be removed from the Bay by SCRJ transfer into the air. some cases than had been measured in RMP samples, but still higher concentrations than many other contami- MULG • Alkylphenols and APEs are known to accumulate in nants found in Bay mussels. MUOS wildlife, especially invertebrates and fish. Most stud- SMOH Concentrations of some compounds in Mus- ies have focused on nonylphenol and octylphenol, as ° TBSM they are readily accumulated and stored in fat tissues sel Watch samples, for example 4-nonylphenol monoethoxylate, were high, at levels comparable RBMJ and there is concern for toxicity, particularly endocrine LBBW disruption. to sites in Southern California (FIGURE 1). The SPFP maximum level of 4-nonylphenol monoethoxylate So Cal measured in the Bay was 300 ppb. NHPB Bight Patterns of Occurrence in the Bay and in Other NBWJ Aquatic Ecosystems ° Bay mussel concentrations for other compounds, for example nonylphenol, were low in comparison CCSB • There are RMP occurrence data for nonylphenol, to samples from Southern California (FIGURE 2). DNPT octylphenol, and nonylphenol ethoxylates in the Bay OSBJ (Klosterhaus et al. 2013a). • Overall, levels found in Bay samples were typically lower than those found in effluent-dominated systems, and AHLG Only nonylphenol has been detected in Bay ° similar to or lower than other marine and estuarine areas CDRF water samples, with concentrations less than 100 of the US. SCRF nanograms per liter (ng/L), compared to a USEPA SLLJLJSL saltwater chronic water criterion of 1,700 ng/L. • Diehl et al. (2012) found that concentrations of non- SDCB ylphenol in mussels and small fish (gobies) from San Nonylphenol, nonylphenol monoethoxylates, ° Francisco Bay were lower than in Morro Bay and To- IBJN and nonylphenol diethoxylates were consistently males Bay, two undeveloped coastal areas. The maximum detected at moderately high concentrations in 0 100 200 300 concentration of nonylphenol in Bay small fish was 420 RMP sediment samples, with a median of 35 ppb Concentration (ppb dry weight) ppb. Seepage from septic systems appeared to be one for nonylphenol. major pathway for nonylphenol to enter Morro Bay, with FIGURE 1 Of the three alkylphenol compounds that are detected frequently toilet paper a likely source (Diehl et al. 2012). in the environment, 4-nonylphenol monoethoxylate is relatively abundant in San Francisco Bay as well as at stations in Southern California. It was detected in all 32 of the NOAA Mussel Watch stations sampled. Red lines indicate limit of detection. Footnote: SFEM-San Francisco Bay, Emeryville; SFYB-San Francisco Bay, Yerba 60 Buena; SFSM-San Francisco Bay, San Mateo Bridge CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 61 TIER 3

FIGURE 2 4-Nonylphenol was found at the highest concentration, 3,000 ppb, in a NOAA Mussel River in Tijuana sample from the Watch Southern California. The concentration in the Bay sample from near the Dumbarton Bridge (SFDB) was not high relative to other stations. Red lines indicate limit of detection. SF Bay Bight Coast North So Cal Concentration (ppb dry weight) Nonylphenol in Mussels 0 1000 2000 3000 BBE TJRE IBNJ SCID SBSB SCFP SFDB CDRF MDSJ ANAI LARM SDCB LBBW ABWJ tory fishto mixtures exposed pesticides, pyrethroid of alone did not cause alkylphenols, Pesticides APEs. and endo- that suggested results Their activity. estrogenic crine disruption, mixtures, these by be could caused partially for the observed of pelagic declines responsible Bay-Delta. Francisco San in the fish populations pacts on barnacle settlement due to exposure to nonyl- to exposure due settlement on barnacle pacts (Billinghurst in water of 60 ng/L concentrations phenol al.et 1998). be at and contaminants of these concentrations higher risk. greater S disruptors. concentra- well below generally are in the Bay oxylates as the such organisms, aquatic be toxic to tions shown to criterion of 1,700 ng/L. water chronic saltwater USEPA A S A C N activity inlabora- al. et estrogenic (2012)found chlenk forim- thepotential is suggesting n exception astudy have outfalls may orstormwater wastewater near ites known endocrinelkylphenols APEs some are and eth- nonylphenol and ofnonylphenol oncentrations available. are data o trend • • • Is There a Risk of Harm in the Bay? the in Harm of a Risk There Is • • Trends in the Bay and Nationally and Bay the in Trends • Alkylphenols and Alkylphenol Ethoxylates Alkylphenol and Alkylphenols and alkylphenols, insecticides, of pyrethroid mixtures caused by disruption Endocrine 3/4 (POD) decline organism to the pelagic be contributing could ethoxylates akylphenol 4/4 TIER 3 Alkylphenols and Alkylphenol Ethoxylates

Key Information Gaps for a full range of long-chain APEs and a greater APEs and alkylphenols with pesticides like pyre- variety of important degradation products. throids. • Although APEs and alkylphenols are widely used and ubiquitous in the environment, even in remote areas, ° Information on potential long-term effects on Bay ° Better sampling and analytical methods for alkyl- there is a need for basic information. wildlife. phenols and APEs. Information on combined effects of multiple endo- ° More complete characterization of concentrations ° of alkylphenols and APEs throughout the Bay and crine disruptors in mixture exposures. particularly near outfalls, including monitoring ° Information on combined biological effects of 2012 USEPA releases report identifying safer alternatives to nonylphenol ethoxylates.

The California Air Resources Board ban on APEs in a Management Timeline variety of cleaning products (non-aerosol general purpose cleaners and degreasers, 2006 glass cleaners, heavy-duty US Environmental Protection hand cleaners, and both 1986 2000 Agency (USEPA) launches the aerosol and non-aerosol oven Switzerland Canada adds nonylphenol Safer Detergents Stewardship or grill cleaners) goes into bans use of and nonylphenol ethoxylates Initiative (SDSI) to recognize effect at the end of the 2012. nonylphenol to Toxic Substances List and detergent and cleaning product Products that contain APEs ethoxylates requires that users develop manufacturers that voluntarily and were manufactured in laundry and implement Pollution reformulate products to remove before the ban may be sold detergents. Prevention Plans. nonylphenol ethoxylates. through 2015 or 2016.

1990 1995 2001 2002 2003 2004 2007 2008 2009 2011

1990-2000’S 2005 2010 2013 Several European Union European Union restricts USEPA releases Chemical The Textile Rental Services countries ban or restrict the use nonylphenol ethoxylates Action Plan for nonylphenol Association, which of APEs (including nonylphenol and nonylphenol for most ethoxylates and nonylphenol represents 98% of the ethoxylates) and nonylphenol. products and uses. (USEPA 2010). industrial laundry facilities, has pledged to end use of nonylphenol ethoxylates in industrial liquid detergents by 2013. Use in powdered detergents will end in 2014.

62 CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 63 . PAGE 67) PAGE Di path- the major considered facilities are treatment water to PBDEs) abundant of the most for BDE-47 (one way the Bay. enter Flo the Bay. to minor PBDE pathways are B is this phase-out voluntary, Because in the US. factured products. in imported still be present may DecaBDE I will goods of consumer likelyrevised, manufacturers for retardants flame chemical new substitute simply are retardants flame alternative of these Some PBDEs. or wildlife health human harmfulpotentially to have and ( in the Bay detected been already The C revised flammability standards safetyhas proposed fire will the that requiring without protection provide fire con- many in retardants flame chemical of added use goods. sumer PBDEs a via escape they can so them, contain that products a are They particles. the air or on loose to volatilization of indoor dust. contaminant major the major pathway for BDE-209 (another abundant abundant for BDE-209 (another pathway the major to the primaryPBDE, and of DecaBDE) component the Bay. enter On the othe is considered stormwater urban r hand, waste- municipal from wastewater oftreated scharges deposition atmospheric direct and ws theDelta from will of2013,DecaBDE end y the bemanu- nolonger not existingare flammabilitystandards f California’s with product consumer charged alifornia bureau thepolymers notchemically or boundto re • Bay? the into Getting They Are How • • • • • • - - D with used virtually typeretardant any of polymer, of con- plastics, textiles,including back-coatings and electronics. sumer S toxic, and highly bioaccumulative, persistent, are that found in the Bay. commonly C the unusually strict flammability meet to products to furniture of California. Most the state by set standards flammability California standards. meets in the US sold O BDE-183, BDE- (e.g., six, bromines eight and seven, in retardant BDE-203), as a flame 197, and used was equipment. electronic electrical for and housings plastic A cl U textiles.and P PentaBDE, in each: of bromines number the average DecaBDE. and OctaBDE, P BDE-47and BDE-99), (e.g., bromines five four and in polyure- retardant as a flame used commonly was mat and in furniture seats, cushions, car foam thane and packaging in foam-based also was used It tresses. carpet padding. P were They in the US. products new to or added tured still they are in 2006. However, in California banned the ban before made goods consumer found in many effect. into went primarily composed ofPBDEscontaining entaBDE, manufac nolonger are OctaBDE and entaBDE primarily composed ecaBDE, ofBDE-209, is aflame pollutants oflegacy aclass tructurally PCBs, similar to added often are like PBDEs retardants flame hemical primarily composed ctaBDE, ofPBDEscontaining chemicals. ofsyntheticass bromine-containing plastics, foam, inpolyurethane retardants asflame sed mixtures for named commercial inthree roduced • • For? Used They Are What • • • • What Are They? • • • REBECCA SUTTON, REBECCA SUTTON, San Francisco Estuary Institute ([email protected])

Quick Summary Summary Quick common in foam once retardants flame PBDEs are Bans products. other many and electronics, furniture, new chemicals from these eliminating are phase-outs and today in use in products present but they remain goods, extensively been PBDEs have in the wastestream. and and sediment, water, Bay Francisco in San monitored wildlife. over be declining wildlife, to In appear levels Preliminary bans. the chemical to likely a response time, may seals harbor in Bay concentrations indicates research eggs harmful found in bird but those levels, at be present of PBDE contami- Levels be problematic. to do not appear in sportnation fish do not pose risks eat to people who effects about the is little information there However, them. of the fish themselves. on the health of contamination have unusually strict flammabilitystandards California’s in retardants flame chemical of use in widespread resulted An effortreviseproducts. standards to is underway these added safety for the need provide fire reducing whileto flameretardants. Polybrominated Diphenyl Ethers (PBDEs) Ethers Diphenyl Polybrominated 1/4 TIER 3 CONCERN MODERATE 2/4 TIER 3 Polybrominated Diphenyl Ethers (PBDEs)

What Happens to Them in the Bay? PBDEs in Bay Bivalves 60 General Properties Rivers Individual PBDEs have different chemical properties de- • 50 San Pablo Bay pending on the number of bromine atoms they contain. This range of chemical properties affects how individual Central Bay FIGURE 1 40 PBDE levels in Bay bivalves PBDEs behave in the environment. South Bay have declined over the last • PBDEs tend to associate with sediment particles, and Lower South Bay decade, likely a result of both those with more bromine atoms show a stronger particle 30 the nationwide phase-out affinity. Bay sediment tends to contain a large propor- and state ban of PentaBDE tion of all PBDEs, especially BDE-209, which has ten and OctaBDE. BDE-47 is 20 the dominant form of PBDEs bromine atoms. BDE-47, with four bromine atoms, is in wildlife and is graphed the dominant PBDE found in Bay water, though it is still 10 here as an indication of mainly found in sediment. overall PBDE levels. BDE-47 is a major component of the • PBDEs are generally lipophilic (“fat-loving”), and many BDE-47 Concentration (ng/g dry weight) 0 PentaBDE mixture. accumulate in organisms. However, the most lipophilic, 2002 2004 2006 2008 2010 2012 BDE-209, is not often detected in Bay wildlife. It may be too strongly bound to sediments to be transferred to or- Footnote: River bivalves are resident clams, while Bay bivalves are primarily mussels deployed ganisms. It may also be too large to pass readily through for 90 days and then collected for monitoring. The higher levels present in river bivalves are an organism’s cell membranes. likely due to their longer exposure time. • PBDEs are generally persistent chemicals in the environ- ment. However, PBDEs with larger numbers of bromine • However, sediment from two contamination “hotspot” a fish that tends to feed over a relatively small territory, atoms can be debrominated via microbial and metabolic sites located in the margins of the Bay (San Leandro Bay indicate regional variation in contamination, along processes or exposure to sunlight, forming PBDEs with and Mission Creek), contained more than four times the with an overall decline in PBDEs from 2003 to 2009 fewer bromines. maximum amount reported for more typical Bay locations (FIGURE 2). • Debromination of BDE-209 can result in formation of (220 and 240 ppb, respectively). • A tern egg collected from the Bay in 2002 contained the less-brominated PBDEs with higher toxicity and greater • In Bay water samples, BDE-47 is the dominant PBDE highest level of PBDEs ever measured in an organism at tendency to bioaccumulate. detected. The Baywide average level of BDE-47 was 43 that time, 63,300 ppb lipid weight (nanograms of PBDE picograms per liter (pg/L) in 2011 (PAGE 36). per gram of lipid [or fat] in the sample) (She et al. 2008). Patterns of Occurrence in the Bay and in Other • PBDEs are detected in all Bay wildlife monitored by the • The RMP analyzed tern eggs in 2009 and found a Aquatic Ecosystems RMP. The dominant PBDE in wildlife samples is BDE-47. maximum value of 2,400 ppb lipid weight (lw); the eggs • PBDEs are common in Bay sediment (PAGE 37). The BDE-209 is rarely detected. averaged 1,400 ppb lw. dominant PBDE found in sediment is BDE-209 (PAGE • Cormorant eggs collected by the RMP from three differ- 37), the major component of the DecaBDE commer- • Bay mussels are widely contaminated with PBDEs. The ent locations also generally show declining levels of PBDE cial mixture. National Oceanic and Atmospheric Association consid- ers Bay mussels highly contaminated relative to other contamination from 2002 to 2009 (FIGURE 3). • In 2011 and 2012, most sediment samples contained parts of the US (Kimbrough et al. 2009). However, RMP • A decade ago, a California Environmental Protection PBDE levels totaling 52 parts per billion (ppb) or less. measurements from 2002 to 2012 show levels have begun Agency study showed PBDE levels in Bay harbor seal Levels are similar to those found in other areas, such as to decline (FIGURE 1). blubber samples were as high as 8,300 ppb lw and were the coastal regions of Southern California and Canada doubling every 1.8 years (She et al. 2002). Recent results (Grant et al. 2011, Dodder et al. 2012). • Bay sport fish also contain PBDEs, with concentrations that vary widely by species. Levels in shiner surfperch, suggest that contamination in adult harbor seals may have stabilized or begun to decline. 64 CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 65 TIER 3 Delta (Wheeler Island) Bridge) Central Bay (Richmond South Bay

2003 2004 2005 2006 2007 2008 2009 2002 0 FIGURE 3 PBDE levels in cormorant from 2002 eggs show general declines phase-out and to 2009, likely a result of both the nationwide state ban of PentaBDE and OctaBDE. Cormorants are piscivores and prefer to forage in open Bay waters. Footnote: Each value is an average of two or three composite samples. Each composite sample is made up of the contents of seven to ten eggs.

5000

20000 15000 10000 PBDE Concentration (ng/g lipid) lipid) (ng/g Concentration PBDE 2009 2006

2003

5 0

30 25 20 15 10 PBDE Concentration (ppb wet weight) wet (ppb Concentration PBDE Footnote: Bars indicate average concentrations. Points represent composite samples. The RMP examined eight sport fish species2009; in shiner surfperch had the highest levels of contamination, exposure. worst-case the represent therefore and FIGURE 2 PBDE concentrations in shiner surfperch, a popular Bay sport fish, were significantly lower in 2009 as compared to previous years. This decline is likely due to the nationwide phase-out and state ban of PentaBDE and OctaBDE. All sportfish examined in the Bay contained PBDE levels below 100 ppb, meaning an adult person can safely eat up to three servings per week according to the California Office of Environmental Health Hazard Assessment (Klasing and Brodberg 2011). ). PAGE 37 PAGE ). 3 and and FIGURES 1, 2, 1, FIGURES decline as well.decline One study (Arkoosh et al. 2010) documented increased increased al. et documented 2010) (Arkoosh One study in young microorganisms susceptibility pathogenic to been has that a PBDE concentration at salmon Chinook samples fish Bay fishsamples. Bay in some exceeded in prior of PBDEs than years. levels lower 2009 had from PBDE le and development of Bay birds, according to a recent a recent to according birds, of Bay development and embryos tern (Rat- to of the toxicitystudy of PentaBDE al. et 2011). tner al. further et 2005), though (Neale seals harbor Bay to health potential these investigate to is needed research impacts. The make them unfit for human consumption based on com- on based consumption human unfit for them make Office the California by developed thresholds parison to (Klasing Assessment Hazard Health of Environmental 2011). Brodberg and PBDEs al C over the past 10 years ( 10 years the past over of continuing in existing be sources can products present time. over of the environment contamination B including osprey eggs in the Pacific Northwest (Henny (Henny Northwest in the Pacific eggs osprey including northeast the from Pacific salmon al.et 2009), sockeye in the Great trout al. et 2011), and (Ikonomou Ocean al. et 2012). (Crimmins Lakes BDE C the last ten years, RMP monitoring of bivalves, fish,and RMP of bivalves, monitoring years, ten the last pollution of falling levels indicates consistently eggs bird ( Othe PBDE le risk declining, should are ofharm vels any so ofPBDEson ontheeffects fish. studies few are re reproduction the affect unlikely to appear so beharmful may contamination ofPBDE levels urrent would sport that PBDElevels fishay contain donot declined have to also appear insediment -47 levels evidentasPBDEs declines, despite remains oncern PBDEdeclines, potential identified have r studies wildlife. inBay Over declining generally are vels • • • • Is There a Risk of Harm in the Bay? the in Harm of a Risk There Is • • • • Polybrominated Diphenyl Ethers (PBDEs) Ethers Diphenyl Polybrominated Nationally and Bay the in Trends • 3/4 4/4 TIER 3 Polybrominated Diphenyl Ethers (PBDEs)

Key Information Gaps • Characterization of PBDE levels in Bay water, sediment, • Toxicity assessment of lower-brominated congeners and biota in the margins of the Bay, where localized created through environmental debromination processes The impact of current levels of contamination on Bay • “hotspots” of contamination are likely. and not found in commercial mixtures. harbor seals and fish. • Degradation and debromination rates for BDE-209, the primary component of DecaBDE.

Management Timeline 2013 In response to pressure from USEPA, the major manufacturers 2004 2006 of DecaBDE agree to stop producing this mixture by the end In response to pressure The state of California bans production, use, and of 2013. from the US Environmental sale of products containing PentaBDE and OctaBDE. The California state agency responsible for flammability Protection Agency (USEPA), USEPA issues a Significant New Use Rule for standards (www.bearhfti.ca.gov) proposes new standards that the major manufacturer of PentaBDE and OctaBDE, allowing the agency will eliminate the need for added chemical flame retardants PentaBDE and OctaBDE to review and regulate any new uses for these in many consumer goods (www.bhfti.ca.gov/about/laws/ agrees to stop producing compounds. propregs.shtml). the compounds in 2004.

2005 2007 2008 2009 2010 2011 2012

 Photograph by Denise Greig.

66 CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 67 T in floor plasticizer and as a retardant as a flame acrylicpolishes, and plastics, paints. T lic fluid. T tris”): briefly in used or “chlorinated (TDCPP widely Now in the 1970s. pajamas children’s in a range found and foam in polyurethane used strollers baby including items, of household pillows, mattress products, foam baby other and furniture. foam and pads, T in flexible and in rigid foams used polyurethane for furniture upholstery. and foams polyurethane T foams. polyurethane T automotive in the a plasticizer and retardant applica- other and in paper, in roofing industry, 550, a flame of Firemaster Alsotions. a component mixture widely in polyurethane used retardant foam. used (TBEP): phosphate ris (2-butoxyethyl) hydrau- inaircraft used ributyl (TBP): phosphate phosphate ris (1,3-dichloro-2-propyl) (TCPP): phosphate ris (1-chloro-2-propyl) in used (TCEP): phosphate ris (2-chloroethyl) asaflame used (TPhP): phosphate riphenyl ° ° ° ° ° ° M is little there although the Bay, to pathway the major ably pathways. potential on other information U is a Stormwater pathway. potential is another untreated, for PBDEs, the compounds the alterna- known pathway the Bay. enter replacing, to are tives Othe the Delta. inputs from and prob- is effluent plant treatment wastewater unicipal Bay the into which flows directly stormwater, rban deposition includeatmospheric sources r potential How Are They Getting into the Bay? the into Getting They Are How • • • H or boards panels in polystyrene insulation used also used insulation); thermal in buildings (e.g., and in the automotive and for furniture, in foams industries. electronics P in tex- and electronics; other and cables, boards, polyurethane. tiles, and adhesives, 1,2,- tempera- high require in plastics that used BPE): and as polystyrene, such during manufacture, tures in resins. B for in coatings used Plus): or Dechlorane (DP materials roofing in plastic and wires cables and used also been buildings. DP has for commercial as a pesticide. primarily (HBCD): exabromocyclododecane incircuit used (PBEB): entabromoethylbenzene (BT- ethane Bis tribromophenoxy) (2,4,6, cyclooctane is (hexachlorocyclopentadieno) ° ° ° ° such as plasticizers. Increased use of these compounds as of these use Increased as plasticizers. such of followingbans classes two occurred retardants flame of PBDEs. varied. are Bay mine, chlorine, or phosphate. or phosphate. chlorine, mine, the bind to to reactions chemical undergo Some tures. while retardants), flame (“reactive” they treat products retardants). flame do not (“additive” others U U S The purposes,some other and for retardants asflame sed inthe detected retardants flame ofthealternative ses chemicals typicallyynthetic organic bro- containing awide variety struc- compounds have se chemical of What Are They Used For? Used They Are What • • What Are They? • • CHRISTINE WERME, CHRISTINE WERME, Independent Consultant ([email protected])

LOW HBCD TIER 2 CONCERN

Most Quick Summary Quick ether diphenyl of polybrominated classes After two manufacturers banned, were retardants flame (PBDE) chemicals in retardant flame other substitute to began been chemicals have of these Some products. consumer of phase-out The while new. for decades, in use are others of PBDEs class final by the and willthe third complete be of the diverse of 2013. Littlemany end about is known chlorine-, phosphate-containing and of bromine-, array studies Recent PBDEs. replaced have compounds that retardants flame alternative of these some detected have con- in lower found they are Typically, samples. in Bay observed concentrations The PBDEs. than centrations exist that for a thresholds the effects below far been have chemicals of these compounds, but for most of these few to changes risks unknown. Proposed the potential are the lessen may strict flammabilitystandards California’s products consumer in retardants flame of chemical use risks the potential lessen in the Bay. therefore and Alternative Retardants Flame 1/4 TIER 1 CONCERN POSSIBLE Compounds 2/4

TIER 1 Alternative Flame Retardants

• Concentrations of alternative flame retardants in the Bay What Happens to Them in the Bay? Concentrations of HBCD and DP, two of the alter- TIER 2 ° are similar to or lower than concentrations in other loca- native flame retardants most frequently detected tions (Klosterhaus et al. 2012). General Properties in sediment samples, tended to be highest in the • Depending upon their individual physical and chemical Central and Lower South Bay (FIGURE 1). • Four other bromine-containing and six phosphate-con- taining chemicals have been targeted for analysis but have traits, the alternative flame retardants may adsorb to sedi- Phosphate flame retardants TDCPP, TCPP, and ° not been detected in Bay samples (TABLE 2). ment particles; degrade by chemical processes, sunlight, TPhP are relatively abundant in Bay sediment, with or metabolic activity; volatilize into the atmosphere; or concentrations comparable to those of PBDEs and accumulate in Bay biota. polychlorinated biphenyls (PCBs) in the same Trends in the Bay and Nationally samples. • Very little trend information is available for many alterna- tive flame retardants. Patterns of Occurrence in the Bay • Alternative flame retardants detected in Bay wildlife in- and in Other Aquatic Ecosystems clude HBCD, PBEB, DP, TCPP, TCEP, TBEP, and TPhP • Measurements of HBCD in California sea lions indicate • Five water soluble alternative flame retardants were (TABLE 1). levels of contamination increased from 1993 to 2003 (Stapleton et al. 2006). Increasing HBCD contamination present in Bay waters analyzed using passive samplers: In general, concentrations of alternative flame retar- TABLE 1 ° has also been observed in marine mammals and fish else- TDCPP, TCPP, TPhP, TCEP, and TBP ( ). dants in Bay wildlife are low compared to concen- where in the US (Chen et al. 2011; Hoguet et al. 2013). • Compounds detected in sediment samples include trations of PBDEs (Klosterhaus et al. 2012, 2013). Analysis of sediment cores from the Great Lakes indi- HBCD, PBEB, BTBPE, DP, TDCPP, TCPP, and TPhP In Bay wildlife samples, HBCD was detected at lev- • TABLE 1 ° cates DBDPE and BTBPE contamination is increasing ( ). els that were one-tenth to one-thousandth of PBDE exponentially. DBDPE levels doubled every 3-5 years concentrations in the same samples. from 1950 to present in Lake Michigan and every 7 years ° PBEB was detected in all adult and most harbor in Lake Ontario. BTBPE levels doubled every 7 years seal pups sampled. from 1950 to present in Lake Michigan and every 5 years Despite its occurrence in sediment samples, BT- from 1950 to 2000 in Lake Ontario, though recent Lake ° Ontario measurements suggest contamination may be San Pablo BPE was not detected in Bay wildlife. leveling or declining (Yang et al. 2012). Bay ° DP was detected in most wildlife samples but in Suisun concentrations lower than HBCD in the same • DBDPE, BTBPE, and HBB were commonly detected in Bay samples. eggs collected from colonies of Great Lakes herring gulls. The measurements suggest a possible increase in these ° TCPP, TCEP, and TBEP were detected in all bird compounds during the most recent years of sampling egg samples. Central 1 (2004-2006). Trends were not obvious for the other Berkeley Bay 0.5 ° TPhP was detected in mussel samples. flame retardants examined (Gauthier et al. 2009). 0 • DP levels in Great Lakes herring gull eggs show greater Oakland contamination starting in the mid-1990s (Gauthier and San DP Francisco Letcher 2009). In contrast, measurements of DP and HBCD related compounds in Niagara River suspended sediment as well as Lake Ontario sediment cores and lake trout suggest peak contamination in the 1980s followed by South declines (Shen et al. 2011). Bay FIGURE 1 Concentrations of DP and HBCD (ng/g dry weight), two alternative flame retardants most frequently detected in sediment samples, tended to be highest in the Central and Lower South Lower South Bay (Klosterhaus et al. 2012). Bay 68 CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 69 TIER 1 TIER 2 Newly identified, phosphate flame retar- dant used in polyurethane foam (Fang et al. 2013) Many phosphate flame retardants are not found in biota and appear to be metabo- lized rapidly; detection of metabolites would indicate exposure A widely used additive flame retardant with predicted high persistence and potential for bioaccumulation Likely not used in high volume, but has been detected in environmental samples, with predicted high persistence, toxicity, and bioaccumulation; causes reproduc- tive toxicity in American kestrels and thyroid disruption in juvenile brown trout REASON FOR MONITORING REASON FOR MONITORING T fertility identi- been has and animals in laboratory Chemicals Sub-Agency a as European by the fied to added was TCEP Concern. High Very of stance the 65 list of chemicals known to the Proposition in 1992. cancer cause to of California state TP European The sperm production. lowered to AgencyChemicals very TPhP considers toxic to lasting long of producing capable and life, aquatic effects. TBEP m toxicity is unknown. reduce tumors and cause shown to been has CEP linked been has and hP is aknown neurotoxin liver affect function; itslong-term ay ° ° ° T forwildlifeoxicity data limited. extremely threshold are

• Phosphate flame retardant metabolites Ethylene bis-tetrabromoph- thalidimide – EBTEBPI 1,2-dibromo-4-(1,2- dibromoethyl)cyclohexane – TBECH or DBE-DBCH COMPOUND V6 TABLE 2 Possible additional target alternative flame retardants for monitoring in San Francisco Bay.

x x x • SEALS SEALS

x x x x x x x x x x x • • •

x SPORT FISHSPORT BIRD EGGS T The B disruptors. DP i C 65 list of Proposition the to added was It cinogen. cause to of California the state chemicals known to potential the also in 2011. TDCPP has cancer endocrine and disruptor as a neurotoxin act to al. et 2011). 2010, Dishaw Stapleton and (Meeker is structurallyCPP known carcinogens. similar to notoxicity forPBEB. are data re isTBPE structurally known endocrine similar to insecticide. asan used and insects s toxic to car- and tris is orTDCPP amutagen hlorinated ° ° ° ° °

x x x x

xxx x x x x x x • ••••••••••••

x x •••••••• • WATER* SEDIMENT MUSSELS

H neurodevelop- also cause may It crine disruptor. detected Levels fertility. decrease and harm mental toxicity than for thresholds lower are in the Bay is use 2012), and Staskal and (Birnbaum algae agree- global following decline a recent likely to retardant. out this flame phase to ment endo- and beaneurotoxin to is considered BCD ° for the wide variety compounds. of chemical R BTBPE TPrP * Qualitative detections via passive water samplers indicating presence or absence in Bay waters. ** Possibly not detected due to methodological issues. TDCPP or Chlorinated Tris TCPP TCEP TBEP Dechlorane Plus (DP) PBEB DBDPE HBB BEH-TBP** EH-TBB** ALTERNATIVE FLAME RETARDANTS ALTERNATIVE HBCD TBP TEHP TPhP ofinformation alack unknown dueto isks largely are indicates detection; x indicates lack of detection. Tris(2,3-dibromopropyl) phosphate, Tris(2,3-dibromopropyl) phosphate, 2-Ethylhexyl- Tricresyl diphenyl phosphate, Tris(2-bromo- 4-methylphenyl) phosphate TABLE 1 Alternative flame retardants that have been detected in San Francisco Bay (from Klosterhaus et al. 2013a,b). • Alternative Retardants Flame Bay? the in Harm of a Risk There Is • 3/4 4/4

TIER 1 Alternative Flame Retardants

TIER 2 Key Information Gaps • Little is known about the toxicity of individual com- pounds, and even less is known about cumulative effects Additional compounds could be targeted for monitor- • of complex mixtures. ing (TABLE 2). • Trend monitoring will be needed to track changes in Some flame retardants are proprietary mixtures with • environmental concentrations in response to evolving unknown formulations, so other compounds may be regulation and use. present but not included on lists of potential analytes.

2013 Management Timeline CBEARHFTI proposes revisions to Technical Bulletin 117 that would 1975 change standards in order to improve fire safety while The California bureau charged with improving reducing the need for fire safety of products, now called the Bureau chemical flame retardants. of Electronic and Appliance Repair, Home Furnishings and Thermal Insulation (CBEARHFTI), 2004 Following pressure begins development of performance-based In response to pressure from USEPA, the major flammability standards through a series of from USEPA, the major manufacturers of decaBDE Technical Bulletins. Technical Bulletin 117 manufacturer of PentaBDE agree to stop production by (“Requirements, Test Procedures and Apparatus and OctaBDE, two of the end of the year. for Testing the Flame Retardance of Resilient three commercial mixtures Global agreement to Filling Materials Used in Upholstered Furniture”) 2010 of PBDE flame retardants, begin phase-out of is first issued, requiring that furniture foam be agrees to stop producing USEPA releases HBCD is announced. able to withstand the heat of an open flame, a the compounds by the action plan very strict standard that has led to widespread end of the year. for HBCD. use of chemical flame retardants.

19851980 19951990 2001 2002 2003 2007 2008 2009

2000 2005 2006 2011 2012 CBEARHFTI issues the most USEPA issues report California ban California adds TDCPP Governor Brown directs recent version of Technical on chemical flame retardant on manufacture, to the Proposition CBEARHFTI to revise Bulletin 117. alternatives to PentaBDE in distribution, and 65 list of suspected Technical Bulletin 117. foams for upholstered furniture. processing of carcinogens, chemicals USEPA proposes rules to PentaBDE and known to the state of regulate use of HBCD in OctaBDE goes California to cause consumer textiles. into effect. cancer, which requires businesses to provide warnings to consumers.

70 CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 71 ). TABLE 1 The m S M H (ng/L) liter per nanograms 1,060 was water in Bay antibiotic. an for sulfamethoxazole, progressive and heart failure, pressure, blood removal of the wide variety com- removal chemical of these methodologies treatment pounds, but standard Removal some PPCPs. removing at effective are varyefficiencies compound. by samples water and effluent, in influent, maceuticals withcomparable findings Bay, South in the Lower regions. in other similar studies to aximum ofapharmaceutical concentration high treat to valsartan (used ulfamethoxazole, for notengineered are systems sewage unicipal phar- 18of39target al. et detected (2009) arrold ° ° ° ° U in which like the Bay, quantifying in ecosystems PPCPs concentra- and are quickly diluted, effluents wastewater wildlife be and to tions in sediment expected are samples al. et 2013a.) (Klosterhaus low The al. et 2013a,b). (Klosterhaus in the Bay metabolites C metabo- nicotine stimulants, antibiotics, blockers, beta antidepressants, lipid reducers, relievers, headache lites, repel- insect and anxiety hypertension relievers, reducers, lent ( U pathway. potential is another untreated, Flo in agriculture. used veterinary pharmaceuticals D adsorption to be subject may PPCPs cal characteristics, the to volatilization particles, degradation, sediment to organisms. into or uptake atmosphere, methods for noreliable were there ntil recently, and 100PPCPs about for data occurrence now are re up asoupof make samples inwater hemicals detected Bay the into which directly flows stormwater, rban particularly for beasource, may theDelta w through upon theirindividual chemi- and epending physical • Other in Bay the and in Occurrence of Patterns Aquatic Ecosystems • • • • • Bay? the in Them to Happens What Properties General ) and triclocarban are antibacterial antibacterial are triclocarban ) and PAGE 75 PAGE PPC bathing, laundering, of excretion, flushing and medicines. unused through wastestream thesewage enter Ps ° agents commonly added to soaps and other consumer consumer other and soaps to added commonly agents products. M infor- more although the Bay, to pathway the major ably pathways. potential on other is needed mation A fe plasticizers bisphenol A and including with PPCPs, known as phthalates. P in many and steroids, anti-epileptics, estrogenic sants, applications. or veterinary health human other ( Triclosan S perfumes, in cosmetics, used detergents, are ingredients products. household other and supplies, cleaning B of food cans. the linings P also in nail found polish, are home care Some longevity. and in floors, for wood fragrance like treatments products supplies. cleaning and products mixtures care in personal N repellent. widely insect used S shampoos, deodorants, and like antiperspirants products in dry- also used are They cosmetics. conditioners, and cleaning. A w agents; diagnostic veterinary drugs their metabolites; and ingredients vitamins nutritional supplements; other and repellants; lotions; insect and sunscreens, in cosmetics, products. in many used ingredients fragrance and prob- is effluent plant treatment wastewater unicipal along measured often compounds are w additional asantibiotics, used drugs antidepres- are harmaceutical artificial and ynthetic musks natural other fragrance and in and epoxy resins and inplastics Aisisphenol used flexibility increase to plastics to and added are hthalates is themost known asDEET, ,N-diethyl-m-toluamide, care inpersonal ingredients common iloxanes are and ide variety over-the-counter, ofprescription, How Are They Getting into the Bay? the into Getting They Are How • • For? Used They Are What • • • • • • • What Are They? •

CHRISTINE WERME, CHRISTINE WERME, Consultant Independent ([email protected]) TIER 1 CONCERN POSSIBLE Phthalates Bisphenol A

LOW Quick Summary Summary Quick Pharmaceuticals and personal care products (PPCPs) in- (PPCPs) products care personal and Pharmaceuticals clude a wide variety over-the-counter and of prescription and in personal fragrances drugs, sunscreens, cosmetics, in homes, used products other and products, home care the enter PPCPs agriculture. facilities,medical even and bathing, laundering, excretion, and through wastestream have scientists Although medicines. of unused flushing in the environment, of their presence aware been long to analytical developed methods been have only recently ecosystems found in aquatic concentrations the low detect in Of the thousands of chemicals used as the Bay. such 100 for analy- about the RMP targeted products, has these include samples water in compoundssis. The detected metabo- nicotine stimulants, antibiotics, blockers, beta antidepressants, lipid reducers, relievers, headache lites, and plasticizers, anxiety hypertension relievers, reducers, also been chemicals have of these Many repellents. insect wildlife and sediment Concen- in Bay samples. detected found those than lower are in the Bay of PPCPs trations there where streams rivers and in wastewater-dominated for other is as reported dilution, less the same about and unknown due Risks largely or marine areas. estuarine are the wideto variety compounds, the generally of chemical found, the lack which and at they are concentrations low compoundses- on of these on the effects of information generally are concentrations However, tuarine organisms. do exist. that the thresholds below Pharmaceuticals Products Care Personal and 1/4 Tested TIER 2 CONCERN Most Compounds 2/4 TIER 2 Pharmaceuticals and Personal Care Products

kidney disease related to diabetes), erythromycin hydrate (an antibiotic TABLE 1 TIER 1 degradation product), and gemfibrozil (used to lower blood lipid levels) PPCPs detected in Bay samples (from Klosterhaus et al. 2013b). Data collected as part of RMP studies, other were detected consistently in a special RMP PPCP study of five sites in research, and mussel samples collected in 2010 and analyzed as part of NOAA’s Mussel Watch Program. the Bay. PHARMACEUTICALS Other compounds detected in water samples included carbamazepine ° COMPOUND USE WATER SEDIMENT MUSSELS EGG and caffeine. These compounds have low removal efficiencies by waste- Albuterol Bronchodilator – asthma, breathing issues x water treatment plants and are persistent in the environment. Amitriptyline Antidepressant – pain, minor depression x x 10-hydroxy-amitriptyline Metabolite of amitriptyline x The aximumm concentration of a non-pharmaceutical PPCP was 459 Amphetamine Psychostimulant – fatigue, appetite x x x ° Atenolol Beta blocker – blood pressure, angina x x ng/L of bis(2-ethylhexyl) phthalate, a plasticizer. Benzoylecgonine Analgesic and metabolite of cocaine x PPCP concentrations in Bay water samples were generally highest in Caffeine Stimulant x x ° Carbamazepine Mood stabilizer and anti-epileptic x x the southern Bay segments, where dilution is lowest, and residence Ciprofoxacin Antibiotic – diarrhea, nausea, vomiting x times are highest. Clarithromycin Antibiotic – ulcers, tonsillitis, other infections x Cocaine Local, topical anesthetic x x x • Fewer PPCPs have been detected in sediment samples than in water or wildlife Cotinine Metabolite of nicotine x Dehydronifedipine Metabolite of difedipine (blood pressure) x x (TABLE 1). Desmethyldiltiazem Metabolite of diltiazem x Diazepam Valium – anxiety, muscle spasms, seizures x ° Pharmaceuticals detected in Bay sediment include stimulants, antibi- Digoxigenin Steroid found in Digitalis – immuno-tag x otics, and a diuretic, with a maximum concentration of 678 parts per Diltiazem Calcium channel blocker – blood pressure x x billion (ppb) for ciprofloxacin (an antibiotic). Diphenhydramine Benadryl® – allergies, cold, nausea, hives x x Enalapril ACE inhibitor – blood pressure, heart x The aximumm concentration of other PPCPs in sediment was 605 ppb Enrofloxacin Antibiotic – veterinary issues x ° Erythromycin-H2O Antibiotic degradation product x x x bis(2-ethylhexyl) phthalate. Fluoxetine Prozac – depression, panic disorders x Gemfibrozil Fibrate – high cholesterol, trigleridea x ° Triclocarban, an antibacterial agent used in disinfectants and soaps, was Hydrocodone Analgesic – pain relief, cough x unusual among PPCPs in that it was detected in sediment samples but Ibuprofen Analgesic – pain relief, inflammation x Lomefloxacin Antibiotic – urinary tract, other infection x not in water. The maximum measured concentration was 33 ppb. Meprobamate Tranquilizer – tension, anxiety, nervousness x Methylprednisolone Corticosteroid – inflammation, allergy x • Compounds detected in biota include Benadryl®, the popular insect repellent Metoprolol Beta blocker – blood pressure, angina x DEET, antidepressants such as Zoloft®, other pharmaceuticals, and fragrance Naproxen Anti-inflammatory – fever, pain x ingredients (TABLE 1). Ofloxacin Quinolone – ear infection x Propoxyphene Analgesic – no longer available in US x The aximumm concentration of pharmaceuticals in Bay mussels was Propranolol Beta blocker – blood pressure, angina x ° Ranitidine Antihistamine – heartburn, ulcers x about 90 ppb for both lomefloxacin, an antibiotic, and sulfamethazine, Sertraline Zoloft® – OCD, PTSD, other depression disorders x an antibiotic mostly used for veterinary applications. Sulfamethazine Antibacterial – veterinary x Sulfamethizole Antibacterial – urinary tract infection x x ° Compounds measured in mussels at a majority of sites included amitrip- Sulfamethoxazole Antibacterial – usually used in combinations x x tyline, DEET, sertraline (Zoloft®), and dehydronifedipine. Thiabendazole Parasiticide – roundworm, pinworm x x Triamterene Diuretic – hypertension, edema x x x The aximumm concentration of other PPCPs in mussels was 2,620 ppb Trimethoprim Antibacterial – urinary, ear infection x x ° Valsartan Angiotension receptor blocker – heart, stroke x of di-n-butyl phthalate, a plasticizer. Verapamil Calcium channel blocker – blood pressure, angina x Virginiamycin Antibiotic – veterinary x ° In Bay cormorant eggs, maximum concentrations of bis(2-ethylhexyl) OTHER PPCPS phthalate, a plasticizer, reached 1,880 ppb. COMPOUND USE WATER SEDIMENT MUSSEL EGG N,N-diethyl-m-toluamide DEET – insect repellant x x x • The NOAA Mussel Watch California CEC Pilot Study (Mussel Watch) mea- Celestolide Musk (fragrance ingredient) x sured a variety of PPCPs in mussels from the Bay. Galaxolide Musk (fragrance ingredient) x x Tonalide Musk (fragrance ingredient) x x ° The ntidepressanta sertraline was detected frequently in California, with Versalide Musk (fragrance ingredient) x FIGURE 1 Bis(2-ethylhexyl) phthalate Plasticizer x x x x a maximum concentration in the Bay ( ). Butylbenzyl phthalate Plasticizer x x x The ntihistaminea diphenhydramine (Benadryl®) was also found at Di-n-butyl phthalate Plasticizer, adhesives, printing inks x x x x ° Triclocarban Antibacterial soap x x relatively high levels in the Bay (FIGURE 2). Antibacterial soap, toothpaste, Triclosan x 72 other consumer goods CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 73 TIER 2 TIER 1 SF Bay Bight Coast Coast North So Cal Central 100 5 0 Concentration (ng/g dry weight) LJLJ LATI TJRE SLSL PPJB IBNJ PLSR SNIF SPSP SCRJ TBSR PVRP KRFR SDHI SCID SFYB PGLP PALH SSSS BBBE SBSB SCFP PCFB SFDB SCRF OSBJ RBMJ EUSB CPSB PDPD SCBR DRDP CDRF PRNS PCPC MDSJ PDSC SFEM ANAI DNPT CBAP SFSM HMBJ TBSM LARM SMPS SDCB SYRN MBES CCSB MBSR LBBW AHLG NHPB MBVB ABWJ SRDM MBML MBSC SGSG MULG NBWJ MBVG MUOS AHCM SMOH GCGC Compound : Diphenhydramine Compound : ) right SF Bay Bight Coast So Cal Central FIGURE 2 ( FIGURE 3 4 5 ) 1 2 below California. Red lines indicate limit of detection. Concentration (ng/g dry weight) 0 Compound: Sertraline Mussel Watch detected it at only 11 of 68 stations. detected it at only 11 of 68 stations. Mussel Watch antihistamine used mostly to fight allergy symptoms. stations and at a Newport Harbor station in Southern Diphenhydramine, widely known as Benadryl®, is an (11 ppb). High levels were also detected at other Bay TJRE SLSL IBNJ SPFP PVRP SDHI SFYB SBSB CPSB PDPD CDRF MDSJ DNPT SDCB CCSB The highest concentration was in mussels from Emeryville NHPB FIGURE 1 ( FIGURE sertraline,The antidepressant the trade sold under 22 Mussel Watch was detected in 14 of name Zoloft, (5.5 The highest concentrations stations in 2010. parts from the San ppb) were in mussels per billion or High levels Buena station (SFYB). Francisco Bay Yerba Southernwere also found at some California sites. Red lines indicate limit of detection. MBVB ABWJ MULG NBWJ AHCM SMOH ). PAGE 75 PAGE ). FIGURE 3 - with a “pre associated those than or greater similar to were samples toxicity on chronic based calculated concentration” no effect dicted contaminated more al. et 2008). These (Grung algae blue-green to Further arm of the Bay. the southern from obtained were samples if this see antibiotic be harming to could be warranted may study algae. Bay Thr T of antibiotic-resistant development promote may and laboratory exist concerns Similar for triclosan ( bacteria. S effects. health adverse ist on potential A wildlife of and be indicative sediments, may samples in water, ence concentrations. at low even effects, potential The a ( Bay in the level high a relatively water surface inBay ofsulfamethoxazole of15measurements ee endocrine bean disruptor shown to inthe been has riclocarban ex- studies Few bioaccumulative. and ynthetic persistent musks are theirpres- and biologically active, inherently are ll pharmaceuticals California, throughout with ntibiotic lomefloxacin detected was ° ° ° ° ° the generally low concentrations at which they are found, and the lack of the lack found, which and at they are concentrations low the generally compoundsestuarine organisms. on of these on the effects information do exist. that the thresholds below generally are concentrations However, more prudent use, and source separation. Examples of these measures Examples measures of these separation. source and prudent use, more livestock, controlled and in humans use in product include reductions and treatment, on-site education, consumer products, of unused returns stream. waste of urine the general from separation conceivably, R ceuticals across all income groups (Hoebert et al. et 2011). (Hoebert all groups income ceuticals across R dredth of those reported for sites in freshwater systems, which are often often which are systems, in freshwater sites for reported of those dredth for other as reported outfalls, the same about and wastewater to close also but occur outfalls may wastewater where or marine areas, estuarine al. et 2013a). (Klosterhaus dilutionwhere is greater outfall. wastewater ocean California a Southern N Glo C C thewide unknown dueto varietyisks compounds, ofchemical largely are control, onsource depend would occur, ininputs,shouldthey eductions ornationally. fortheBay available are data trend o general ofpharma- use reports increasing Organization Health theWorld bally, typically one-hun- are to intheBay one-tenth ofPPCPs oncentrations typically were at ofthose one-tenth water inBay ofPPCPs oncentrations Pharmaceuticals Products Care Personal and 3/4 Is There a Risk of Harm in the Bay? the in Harm of a Risk There Is • • Trends in the Bay and Nationally Nationally and Bay the in Trends • • • • 4/4 TIER 2 Pharmaceuticals and Personal Care Products

TIER 1 Bisphenol A is a known endocrine disruptor. • The cienceS Advisory Panel for CECs in California’s What is the fate of PPCPs in the Bay? ° Aquatic Ecosystems identified the hormone-mimic bisphe- ° ° Many phthalates are known to be endocrine disrup- nol A and the synthetic musk galaxolide for monitoring in ° What PPCPs are bioaccumulating in organisms? tors and may cause other health effects. Phthalates coastal embayments. What are the acute and chronic effects? included on California’s Proposition 65 list of ° chemicals known to be harmful include butylben- ° Which compounds are endocrine disruptors, and zyl phthalate (developmental effects), bis(2-eth- Key Information Gaps how may they affect marine life? ylhexyl) phthalate (cancer, developmental effects, • Information about occurrence, sources, fates, and potential How do observed concentrations compare to effect male reproductive toxicity), diisodecyl phthalate ° effects of PPCPs is evolving. While most PPCPs examined levels? (developmental effects), di-n-butyl phthalate (de- in Bay samples were found at levels that do not appear to velopmental effects, male and female reproductive How are inputs and Bay concentrations changing be harmful, for a few there is greater uncertainty (bisphe- ° toxicity) and di-n-hexyl phthalate (male and female through time? nol A, bis(2-ethylhexyl) phthalate, butylbenzyl phthalate). reproductive toxicity). • Continued efforts to understand potential effects of mix- • Many basic questions remain. • A recent study (Brodin et al. 2013) reported behavior tures, as well as of individual chemicals, is necessary. and feeding-rate alteration in fish from natural popu- ° What PPCPs are reaching the Bay and in what con- lations exposed to a psychoactive drug (the anxiety centrations? reducer oxazepam). ° What are the sources and pathways?

Management Timeline 2011 US Food and Drug Administration (USFDA) 2007 and USEPA initiate regulatory review of 1999 Canada publishes a summary of research and triclosan in antibacterial soaps and other policy directions, assessing the status of PPCPs products. Some manufacturers announce US Environmental Protection in the environment (Klegwegt et al. 2007). phasing out of triclosan use. Agency (USEPA) publishes 2013 a critical review of issues US White House Office of National Drug The state of California passes legislation to USFDA bans use of associated with PPCPs in Control Policy issues consumer guidance on ban bisphenol A in baby bottles and sippy bisphenol A in baby the environment. proper disposal of prescription drugs. cups. The ban would go into effect in 2013. formula packaging.

2000 2001 2002 2003 2004 2006 2009 2010

2005 2008 2012 California Department of Toxic Substances USEPA issues interim report USFDA bans use of bisphenol A Control requests that industries producing on disposal of unused in baby bottles and sippy cups. medicinals and botanicals, pharmaceutical pharmaceuticals. Canada concludes that triclosan is toxic to preparations, diagnostic substances, and Congress bans several the environment and proposes regulation. biological products submit information phthalates in children’s toys to categorize facilities and major Alameda County Board of Supervisors and child care articles. wastestreams and reduce waste. passes ordinance requiring drug manufacturers to pay for programs to dispose of unwanted and expired medications. Pharmaceutical trade groups 74 sue to stop enforcement of the ordinance. CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 75 - - - ment plant in 2006 (ranging from <500 to 900 900 <500 to from in 2006 (ranging plant ment (Jacksoncompa ng/L) were 2008) Sutton and observed in other concentrations effluent to rable studies. in 2008 (15-20 plants treatment Area two Bay of average the nationwide similar to were ppm) Sewage National 2009 Targeted 16 ppm (USEPA Survey). Sludge products that are disposed of in residential drains, drains, disposed of in residential are that products wastewater municipal in transport to resulting plants. treatment on the >99.5%, depending 60% to from range used. type of treatment in treat triclosan is detected commonly plants, effluent. plant ment C A O R G treat Area Bay from a ineffluent oncentrations from sludge insewage concentrations verage inconsumer are 95%oftriclosan uses ver plants typically treatment efficiencies in emoval intreatment removal theincomplete iven ° ° ° ° ° Ac M only evidence of effectiveness is in toothpaste in prevent- toothpaste in is only evidence of effectiveness gingivitising (http://www.fda.gov/forconsumers/con- sumerupdates/ucm205999.htm). more although the Bay, to pathway the major probably pathways. potential on other is needed information U the use due to pathway potential is another untreated, for activities products as such of triclosan-containing washing. car and exterior cleaning Drug the and Administration, Food theUS to cording is effluent plant treatment wastewater unicipal Bay the into which flows directly stormwater, rban

How Is It Getting Into the Bay? the Into Getting It Is How • • • microbial that is found in bar soaps and is and also a concern soaps is found in bar that microbial environments. in aquatic antibacteri- including industrial products, and consumer body washes, weight), (0.1-0.3% by soaps al liquid hand deodor- detergents, toothpaste, mouthwash, cosmetics, cutting furniture, including products other and ants, sportsand carpets. floors, boards, equipment, used plastics into triclosan, is also incorporated contains consumer other and utensils, kitchen toys, in children’s triclosan another Biofresh®, and industrial products, and clothing. in some isproduct, embedded 2005). Paull and (Halden US antimicrobial agent. antimicrobial fungi. and bacteria S A M Es S Ki The A the necessity or efficacy of triclosan and other or efficacythe necessity and other of triclosan (WMI products care in personal agents antibacterial fighting germ the best that indicate 2006). Physicians - wash of hand act be the actual to continues measure alcohol- for extra or assurance, with soap, ing regular sanitizers. hand based Association notendorsed has merican Medical anti- popular tructurally another triclocarban, similar to 1960sinthousandsof theearly since used ntimicrobial sometimes that product release aslow icroban®, 300,000kg/yr than inthe ofmore use annual timated is abroad-spectrum that chemical ynthetic chlorinated including lls orinhibits thegrowth ofmicroorganisms,

• For? Used It Is What • • • • What Is It? • • Cl

Triclosan is a personal care product ingredient of particular interest that was Triclosan the subject of a RMP fact sheet (www.sfei.org/news_items/factsheet-triclosan). This profile presents an update of the information in the fact sheet. Cl

JAY DAVIS, DAVIS, JAY San Francisco Estuary Institute ([email protected]) O

OH LOW Quick Summary Quick widely used chemical in is antimicrobial an Triclosan Triclosan soaps. as liquid hand such products, care personal observed concentrations The sediment. in Bay accumulates risks but potential thresholds, effect well below been have not fully the efficacy about Doubts of are understood. for its potential concern and triclosan of its uses in some quality whether question its uses call into on water impacts should be curtailed. Triclosan 1/4

TIER 2 Cl CONCERN 2/4 TIER 2 Triclosan

What Happens to It in the Bay? • In a 2010 RMP Bay survey, triclosan was not detected Is There a Risk of Harm in the Bay? in surface water (< 60 ng/L) or sediment (< 62 ppb); Laboratory studies have suggested that triclosan can act however, typical concentrations in estuaries are below • General Properties as an endocrine disruptor in fish and mammals, but con- these detection limits (<1 to 26 ng/L in water and The fate of triclosan in the Bay has not been studied, centrations in the environment are generally much lower • from below detection to 86 ppb in sediment). A more but predictions can be made based on information from than the exposure concentrations used in these studies. sensitive method would be needed to detect triclosan other studies. in Bay water. • Algae appear to be the most sensitive to triclosan expo- Upon entry into the Bay, triclosan is expected to be sure (acute toxicity threshold 200 ng/L) (Chalew and • • Triclosan was not detected in mussels collected from quickly removed from the water column through Halden 2009). the Bay in 2010 (< 33 ng/g wet weight) (unpublished binding to sediment particles, photodegradation, and data). • Most of the toxicity threshold data currently available biodegradation. Some of the degradation products are are from acute effects studies, which are not indicative of • Sediment concentrations are comparable among the problematic, however (more on this below). the potential effects due to long-term, chronic exposure US estuaries that have been studied, including San Triclosan is expected to accumulate primarily in to concentrations that are typically found in aquatic • Francisco Bay. sediment (due to its high affinity for organic matter environments. • Studies in other parts of the US indicate concentra- and sediment particles) where it can be taken up by In chronic toxicity studies, effects on the endocrine tions are generally highest in water and sediment • sediment-dwelling organisms and passed up the food system in amphibians and the structure and function of near municipal wastewater treatment plant outfalls or chain. algal communities have been observed at concentrations waters with known inputs of raw wastewater (Glass- Triclosan can persist in sediments with a half-life as long occurring in the environment (Veldhoen et al. 2006; • meyer et al. 2005). as 540 days and resists biodegradation under low oxygen Wilson et al. 2003). • Triclosan was one of the most frequently detected conditions when it is associated with sediments (Halden Additional concerns include the potential for indirect wastewater contaminants in a 1999-2000 survey of US • and Paull 2005). effects on algal and aquatic plant grazers due to the stream waters – detected at 58% of sites nationwide Other degradation products include chloroform, toxicity of triclosan to algae and the combined effects of • (Kolpin et al. 2002). chlorophenoxyphenols, chlorophenols (e.g., 2,4-dichlo- persistent antimicrobial compounds, such as triclosan rophenol and 2,4,6-trichlorophenol), and 2,8-dichloro- • Though few studies have investigated triclosan bioac- and triclocarban, on microbial communities. cumulation, triclosan has been detected in the US and dibenzo-p-dioxin; some of these chemicals are probable Some of triclosan’s transformation products are probable Europe in algae, fish tissues (bile, plasma), marine • human carcinogens. Triclosan is suggested as the largest human carcinogens. source of lower chlorinated dioxins to aquatic environ- mammals (plasma), and humans (milk, blood, urine). ments (Buth et al. 2010). • One transformation product, methyl triclosan, is more Trends in the Bay and Nationally (PAGE 3) persistent than triclosan and has been found to accumu- • No trend data are available for the Bay. late in fish (Leiker et al. 2009). • Data from other parts of the US suggest that sediment concentrations were highest in the 1960s and 1970s, de- Patterns of Occurrence in the Bay and in Other clined significantly with the adoption of activated sludge Aquatic Ecosystems wastewater treatment, but may have recently begun • In a 2008 Bay sediment survey, concentrations ranged rising (Cantwell et al. 2010). from < 5 to 40 ppb (FIGURE 1) (unpublished data).

76 CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 77 TIER 2

WWTP Discharges <5 5.0 - 7.5 7.6 - 10.0 10.1 - 39.9 40.0 - 41.0 ND Triclosan* (ng/g dw) Triclosan* * Limit of quantification 5 ng/g FIGURE 1 in Bay sediment, 2008. Triclosan ND ND ND Triclosan 3/4 4/4 TIER 2 Triclosan

Key Information Gaps • The potential for transfer of triclosan and methyl triclo- • The occurrence of potentially toxic degradation and san through the food web to act as a source of exposure transformation products in the Bay. Relative contributions of stormwater runoff and munici- • to wildlife. pal wastewater as pathways of triclosan to Bay surface • The identity, extent of use, and potential environmen- waters. • Concentrations in sediment and biota influenced by tal health impacts of chemicals used as replacements Bay Area treatment plant outfalls, where exposures are for triclosan. Potential chronic effects on algae and microbes due • anticipated to be highest. to long-term exposure to concentrations of triclosan and other antimicrobials that are typically found in • Potential development of widespread antimicrobial aquatic environments. resistance due to the presence of triclosan in aquatic environments.

Management Timeline 2008 US Environmental Protection Agency (USEPA) re-registration 2010 2012 decision approves triclosan Kaiser Permanente Canada classifies for most uses, but specifically pulls products triclosan as toxic. moves up the next re-registration containing triclosan 1972 decision to 2013, given the from all of its Beginning of use in hospitals. rapidly developing science. hospitals across the country.

1980 2000 2001 2002 2003 2004 2005 2006 2007 2009 2013

1990's 2006 2011 Becomes common in The Bay Area Pollution Prevention Group The US Food and Drug Administration regulates the consumer uses of consumer products. encourages their member agencies to triclosan in antimicrobial hand soaps, body washes, toothpastes, and some adopt an environmentally preferable cosmetics. USEPA also regulates the use of triclosan as an antimicrobial purchasing policy to stop purchasing in a variety of products including industrial equipment uses. Both federal triclosan-containing hand soaps. agencies are engaged in reviewing the uses of triclosan. Two major manufacturers announce that they are phasing out triclosan from many products. Colgate-Palmolive announced they are phasing triclosan out of Softsoap® liquid soaps. It will remain in toothpaste (Colgate Total®). Johnson and Johnson is phasing triclosan out of all their products. In the Bay Area, the focus is on encouraging less consumer usage of triclosan-containing antimicrobial hand soaps and other consumer products, and other source control measures.

78 CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 79 P primary be the in of pyrethroids to source appear un- are runoff.applications urban Landscaping all of the Nearly important be an source. likely to other pyrethroids of second-generation use urban use bifenthrin (80%) of the urban most than and to applicators professional by of bifenthrin are - buildings (TDC Environ around pests control 2010). mental U toxicity exceed often together that of pyrethroids (2-21 organisms aquatic for sensitive thresholds The ten-fold. than more by sometimes ng/L), bifenthrin of the pyrethroids, persistent most is usually >100 ng/L) sometimes (concentrations the toxic potency in a to contributor the leading 2010, 2012; Lydy and Weston (e.g., sample water 2013). Ensminger A toxic amphipod to the to be sufficient centrations occur but toxic levels >2 ng/L) (i.e., azteca Hyalella Weston (e.g., runoff in urban than frequently less 2010). Lydy and A impervious spraying like buildinginvolve surfaces, of which some directly drain walls walkways, and drains. wash off Pyrethroids storm and gutters to impervious these from more substantially surfaces areas landscaped from than efficiently (Jorgenson al.et 2012). applications control structural pest rofessional runoff rban samples typically mixturescontain con- at pyrethroidsgricultural runoffcontain can buildings around insects control to pplications ° ° ° ° P problems. bug bed and lice, head I clothing. mosquito-repellent treated T 2013). in 2011 (CDPR U path- the are untreated, Bay the into which directly flows of pyrethroids which concentrations by the highest ways the Bay. enter flea, pet control indoors to used yrethroids are ofpermethrin- sales approved 2000s,USEPA n theearly 455,000kg about were sales pyrethroids California otal agricultural extent runoff – to alesser runoffrban and – • • • Bay? the Into Getting They Are How • D non-professional to available products landscaping and small comprise a relatively products these consumers, in quantity used of pyrethroids of the total fraction areas. urban P rates. application low relatively at L (ng/L) liter per < 10 nanograms concentrations at 2009). Jackson and 2008; Weston Moran and (Werner P likepyrethroids bifenthrin, cypermethrin, cyfluthrin, in the detected commonly most permethrinand are environment. B areas. urban and I pyre- second-generation popularity when photostable 1980s. 1970s and in the late developed were throids I chlor- (e.g., insecticides of organophosphate uses urban the primary became pyrethroids pyrifos diazinon), and marketplace. in the urban available of insecticides class P of organisms, unlike classes other mammals, because of metabo- capable enzyme extensive systems more have 2011). detoxifyinglizing and (EPA the pyrethroids I pyre- second-generation primary of photostable users insects control to outdoors applied whichthroids, are to underground and buildings (particularlyaround ants) termites. subterranean control A fa structure of pyre- on the chemical compounds based derived insecticides occurring botanical thrins, naturally chrysanthemumfrom flowers. garden, lawn, of pyrethroid number thelarge espite insects control that insecticides broad-spectrum otent, crustaceans) (e.g., organisms aquatic sensitive to ethal generation” “second insunlight) (stable hotostable widely insecticides inagricultural road-spectrum used in grew inthe1950s,pyrethroids nitially developed 2000s,with allowable n theearly ofmost thephase-out organophosphates than forhumans safer yrethroids are the are applicators professional licensed areas, n urban similar synthetic adozen chemical than mily more of • • • • For? Used They Are What • • • • • What Are They? •

* HIGH KELLY MORAN, KELLY TDC Environmental ([email protected]) Creeks TIER 4 CONCERN Bay Area Urban Bay Area Urban

Most LOW * Pyrethroids are of low concern high concern but in in the Bay, Bay Area urban creeks Quick Summary Summary Quick Pyrethroids a family widely insecticides of both are used pests insect control to areas indoors in urban and outdoors have Pyrethroids termites. and bugs, bed fleas, like ants, in organisms of toxicity incidents sensitive to to linked been wa- and in both effluent, runoff,urban wastewater undiluted Francisco but not in San creeks, urban in sediment and ter pesticide state in 2012 by Restrictions implemented Bay. (but not completely) should nearly perhaps regulators Pes- toxicity runoff. in urban pyrethroid-caused eliminate the evaluate to continue quality regulators ticide water and actions. management additional for need Pyrethroids 1/4 TIER 2 CONCERN Compounds 2/4 TIER 2 Pyrethroids

TIER 4 • Municipal wastewater treatment plant effluent is likely a What Happens to Them in the Bay? Bifenthrin and permethrin pathway to the Bay. o No Bay Area municipal wastewater treatment plant General Properties were among the pyrethroids monitoring data have been published. • The fate of pyrethroids in the Bay has not been studied, most commonly detected in o Limited published monitoring data from waste- but predictions can be made based on other studies of water treatment plants elsewhere in California their environmental fate. Bay sediment (Weston and Lydy 2010; Robertson-Bryan 2012; • After entry into the Bay, pyrethroids are expected to be other unpublished data support the following removed from the water column through binding to points. sediment particles. The presence of pyrethroid-caused • Concentrations of pyrethroids in wastewater flowing toxicity in water samples from urban creeks indicates into municipal wastewater treatment plants prior to that this binding process does not occur instantaneously. treatment are similar to concentrations in urban runoff. • Pyrethroids likely accumulate primarily in sediment. TABLE 1 • Municipal wastewater treatment plants generally remove Sediment-dwelling organisms are probably exposed to A recent review of California urban watershed most, but not all, pyrethroids in wastewater. the Bay’s highest pyrethroid concentrations. pyrethroid monitoring data published between 2003 and 2012 found that 14 pyrethroids • Pyrethroids have been detected in undiluted treatment • Pyrethroids persist in aquatic sediments; most have half- lives (time it takes for a 50% reduction) between 100 have been detected in water and sediment plant effluent at concentrations less than 20 ng/L, much (Ruby 2013). lower than concentrations in urban runoff, but some- and 500 days. The half-life of bifenthrin in sediments is greater than 700 days (Gan et al. 2005, Budd et al. times above toxicity thresholds for sensitive aquatic allethrin organisms. Effluents may not necessarily cause toxicity 2011). due to dilution and changes in pyrethroid bioavailability bifenthrin in receiving waters. Patterns of Occurrence in the Bay and in Other cyfluthrin o Users wash some indoor pyrethroid products, such Aquatic Ecosystems as pet flea shampoos and head lice treatments, • In Bay sediment, total pyrethroid concentrations have cyhalothrin generally been below 10 parts per billion (ppb), with down indoor drains immediately after use. Impreg- cypermethrin nated fabrics, like insect-repellent clothing and bed only one sample from Suisun Bay showing a higher bug repellent mattress pads, gradually lose their concentration (16 ppb). Bifenthrin and permethrin were deltamethrin/tralomethrin pyrethroid content when machine or hand washed among the pyrethroids most commonly detected, found after use. Post-application cleanup, cleaning treated in around 30 to 40% of samples. esfenvalerate/fenvalerate surfaces, seepage into underground sewer lines • In the Southern California Bight in 2008, sediment py- fenpropathrin during subterranean termite treatments, spills, and rethroid concentrations were highest near urban runoff improper disposal may also transfer pyrethroids sources, where average total pyrethroid concentrations fluvalinate into indoor drains and sewer lines, resulting in were 22 ppb. Consistent with other studies, bifenthrin permethrin transport to municipal wastewater treatment plants was most commonly detected (32% of all samples) and (Moran and TenBrook 2011). the dominant contributor to pyrethroid toxic potency. phenothrin Near urban runoff sources, total pyrethroid concentra- prallethrin tions exceeded effects levels for the amphipodEohaus- torius estuarius, but the presence of pyrethroids did not resmethrin directly correlate with toxicity measurements, suggest- ing that the presence of the many other anthropogenic tetramethrin chemicals in these sediments affected toxicity measure- ments (Lao et al. 2012). 80 CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 81 TIER 2 TIER 4 altwater test organism most sensitive to pyrethroids pyrethroids to sensitive most organism test altwater Both w C appears to be the be to appears bahia The Americamysis crustacean s S typically creeks urban Area toxicity exceed thresh- Bay and (BASMAA azteca 2013; Weston olds for Hyalella 2013). 2010, 2012; Ensminger Lydy 2011-2012 watersheds, urban California other to water creek 9 of 11 urban found that testing Area Bay (BASMAA azteca 2013). Hyalella toxic to were samples (acute toxicity thresholds <10 ng/L). Although toxicity <10 ng/L). thresholds (acute waters, in Bay measured not been have pyrethroids toxicity in tributaries exceed sometimes concentrations to impacts and organisms, for freshwater thresholds areas in the immediate occur might organisms estuarine their entry the Bay. near to toxicity organisms. acute in test cause that those than sediment of 98 Bay in 57 detected Pyrethroids were 2011. Of the eight 2008 and between collected samples only two one sample, least in at detected pyrethroids concentrations at occurred phenothrin) and (allethrin sedi- no relevant are Although there 2 ppb. than greater they generally pyrethroids, toxicity for these ment data toxicities permethrin, which similar to aquatic has have mortality 50% causing to (concentration LC50 a 10-day for the amphipod test) in a 10 day organisms of test al. et 2008). (Anderson of 140 ppb estuarius Eohaustorius (bifen- toxicpyrethroids detected highly The most thrin, cyfluthrin, cyhalothrin,were and cypermethrin) and limits (0.03-0.6 ppb) detection below frequently individually 1.1 ppb of 1.6 ppb. exceeded or a total never available only the than lower are concentrations These toxicity in this for a chemical group, sediment thresholds for the amphipod bifenthrin, LC50 for which 10-day the al. et 2008). is (Anderson 8 ppb estuarius Eohaustorius in concentrations pyrethroid sediment and ater similar and with concentrations pyrethroid onsistent likely lower are Bay inthe concentrations ediment • • • Is There a Risk of Harm in the Bay? the in Harm of a Risk There Is • 2008, but concentrations have not shown significant not shown significant have 2008, but concentrations trends. or increasing decreasing starting in the early concentrations environmental and of organo- regulation with2000s, coincident the greater insecticides. phosphate insec- to other shift may but users areas, in urban use also are that and indoxacarb, ticides, as fipronil such organisms. aquatic toxic to highly and agricultural streambeds in 25 states, pyrethroids pyrethroids in 25 states, streambeds agricultural and the Bifenthrinwas in 78% of samples. detected were by followed (58% of samples), detected frequently most cyfluthrin (17%), and permethrin (31%), resmethrin predicted (14%). Although toxicity not measured, was attributed and areas for urban toxicpotency greater was bifenthrin, cyfluthrinto and cypermethrin, whileagri- in toxic potency primarily was the predicted areas cultural Kuivilaand (Hladik to bifenthrin 2012). attributed P C R I since sediments inBay monitored been yrethroids have usage inpyrethroid increases indicate alifornia data pyrethroids reduce likely to are egulatory restrictions 36urban from survey samples n aUSGS sediment of Trends in the Bay and Nationally Nationally Bay the and in Trends • • • • ). For water samples where where samples water ). For TABLE 1 pyrethroids were detected, the average concentrations concentrations the average detected, were pyrethroids of bifenthrin, cyfluthrin, cypermethrin,and permethrin toxicity acute to cause that concentrations exceeded 2013). (Ruby organisms aquatic sensitive pyrethroids, lower pyrethroid concentrations, and less less and concentrations, pyrethroid lower pyrethroids, and Weston (e.g., toxicity watersheds urban than severe 2010). WhileLydy agricultural Area no survey of Bay sediment Valley Central conducted, been has watersheds surveys exhibited toxicity found 16-20% of samples pyrethroids to attributed was that azteca to Hyalella al. et 2008, 2013). (Weston Francisco Bay Area urban creeks are similar to data from from data similar to are creeks urban Area Bay Francisco RMP sampling In watersheds. urban California other most the pyrethroids in Hayward, drainage urban of an 285 permethrin (maximum were detected frequently 46 ng/L). bifenthrin and (maximum ng/L) A pyrethroid (64% of water samples, 69% of sediment 69% of sediment samples, (64% of water pyrethroid toxic potency in to contributor the greatest and samples) 2013). (Ruby samples sediment and both water P throid monitoring data published between 2003 and 2003 and published between data monitoring throid in detected been have 14 pyrethroids 2012 found that ( sediment and water I in water and sediment samples from from samples sediment and in water azteca pod Hyalella areas urban major in all creeks of California’s urban al. et 2008). 2013; Holmes (Ruby A r P fewer contain generally gricultural watersheds San toxicity from and data concentration yrethroid detected bifenthrin is frequently most the areas, n urban pyre- watershed urban reviewofCalifornia ecent toxicity theamphi- to to linked been yrethroids have Regulatory restrictions are likely to reduce pyrethroid users may shift to other use in urban areas, but and indoxacarb, that are insecticides, such as fipronil also highly toxic to aquatic organisms • • • • Pyrethroids • 3/4 4/4 TIER 2 Pyrethroids

wastewater treatment plants (including several Bay Area TIER 4 Key Information Gaps • Potential environmental impacts of chemicals used as replacements for the pyrethroids, such as fipronil and in- plants), anticipated in late 2013, will better characterize Potential for aquatic toxicity in water and sediment at • doxacarb. Limited available data indicate that concentra- wastewater discharges and will provide more thorough Bay margins due to pyrethroid-containing urban runoff tions of fipronil and its multiple toxic, stable degradation insights on treatment plant removal efficiencies. and wastewater effluents, accounting for dilution and products are approaching effects thresholds in aquatic bioavailability in these waters. • Identification of the major sources of pyrethroids in ecosystems (Ruby 2013) (PAGE 83). wastewater. Potential chronic effects on mysids and amphipods due • • The esultsr of a statewide survey of concentrations in to long-term exposure to concentrations found in Bay influent, effluent, and biosolids from about 30 California waters (if detected) and sediment.

Management Timeline

2004-2005 First peer-reviewed reports of pyrethroid 2009 insecticides in California surface waters, USEPA requests including Bay Area urban creeks, at that manufacturers concentrations causing acute toxicity and of non-agricultural growth impairment to the amphipod Hyalella pyrethroid azteca (Weston et al. 2004, 2005). products voluntarily update labels 2013 with application 2011 instructions that Results of wastewater 2005 better protect water At DPR’s request, all treatment plant pyrethroids bifenthrin manufacturers survey to be published. San Francisco Bay Water Board quality. agree to modify Data will be evaluated by adopts Urban Creeks Diazinon 2009-2012 enforceable product USEPA, DPR, and Water and Pesticide-Related Toxicity Total labels to add special Boards to determine if Maximum Daily Load (TMDL), USEPA initiates additional restrictions additional investigation which includes a management Registration Reviews for professional and management action strategy to address pyrethroids for pyrethroids. applicators. are warranted. and other future pesticide-related toxicity in urban creeks. 2008 2010

2006 2007 2012 2013-2015 California Department of USEPA approves DPR regulations modifying allowable DPR and Water Boards will Pesticide Regulation (DPR) San Francisco Bay usage of pyrethroids by professional conduct coordinated monitoring initiates reevaluation of area Urban Creeks structural pest control applicators become to examine the effectiveness of pyrethroid insecticides. Diazinon and effective. Together with bifenthrin label DPR’s pyrethroids regulations Pesticide-Related changes, regulations should reduce to determine if additional Toxicity TMDL. pyrethroid toxic potency in urban runoff management action is warranted. by 80-90% (Jorgenson 2011).

82 CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 83 I N N T tion (DPR) began to allow professional applicators applicators allow professional to began tion (DPR) nuisance control to buildings around fipronil spray to uses Other use). outdoor only significant (the insects insect containerized treatments, “spot-on” flea pet are for injection solutions control termite and baits, control structures. soil beneath into au- are applicators professional where Valley, Coachella control to solely of fipronil use limited make thorized to ants. fire 2013). 2003 (CDPR tripled since have Regula- ofPesticide Department theCalifornia n 2003, California’s inSouthern except onlandscaping ot used inCalifornia. use o agricultural 18,000kg 2011and in about were sales California otal • • • What Is It Used For? For? Used It Is What • ). Chronic toxicity to the crustacean America- toxicity the crustacean ). Chronic to TABLE 1 has been reported at concentrations less than than less concentrations at reported been has bahia mysis species aquatic some 2007). For 0.003 µg/L (USEPA degradation – fipronil’s bahia as Americamysis – such itself. fipronil toxic than more are products three of which (fipronil sulfide, fipronil sulfone, and de- sulfone, fipronil sulfide, of which (fipronil three standard with measured readily be can fipronil) sulfinyl techniques. analysis chemical aquatic and crustaceans (e.g., organisms aquatic sensitive (µg/L) liter per <1 microgram concentrations at insects) ( use in the late 1990s. in the late use withshare colonies. F F S A slo products, degradation four stable least at has ipronil to lethal are products degradation itsstable and ipronil for approved first ynthetic insecticide broad-spectrum carryand can to insects back that toxicant w acting • • What Is It? • • KELLY MORAN, KELLY TDC Environmental ([email protected])

Quick Summary Summary Quick with insecticide is use a broad-spectrum growing Fipronil Fipro- on pets. fleas and structures around pests control to been have products degradation nil stable its multiple and runoff,Bay and urban creeks, Area urban in Bay detected in urban detected has been fipronil Nationally, sediment. sediment and water effluent, runoff,wastewater municipal in estuary Observed and creeks, sediment. con- in urban exceeding cases in some and approaching are centrations for potential an increasing suggesting thresholds, effect ecosystems. to pose risksaquatic fipronil to Fipronil 1/4 TIER 3 CONCERN MODERATE 2/4 TIER 3 Fipronil

How Is It Getting Into the Bay? • Although there are no local monitoring data, municipal Applications to control in- wastewater treatment plant effluent is probably also a Urban stormwater, which flows directly into the Bay • pathway to the Bay. untreated, is a pathway to the Bay due to use of fipronil sects around buildings in- outdoors around buildings. ° Fipronil and its degradation products were de- volve spraying impervious tected in both filtered effluent and effluent solids In samples from Bay Area storm drains and creeks ° from eight of nine Columbia River Basin (Wash- in two watersheds collected between 2008 and surfaces, like building walls ington and Oregon) municipal wastewater treat- 2011, Ensminger et al. (2013) measured fipronil ment plants (Morace 2012). All fipronil detections and walkways, from which concentrations up to 0.46 µg/L. Nine percent of Bay exceeded USEPA’s chronic aquatic invertebrate Area fipronil detections exceeded the US Envi- protection benchmark of 0.011 µg/L (USEPA fipronil and its degradation ronmental Protection Agency (USEPA) chronic 2013). aquatic invertebrate protection benchmark of 0.011 products can be washed into µg/L (USEPA 2013). Urban runoff concentrations ° The only indoor use of fipronil is a “spot-on” gutters and storm drains measured in the Sacramento, Orange County, and treatment for fleas and ticks on pets, which could San Diego regions were higher – up to 10 µg/L. subsequently be washed into the sewer system when the pet is bathed. Other possible pathways to In an intensive two-year sampling program in Sac- ° the sewer system include post-application cleanup ramento and Orange Counties, median concentra- activities, seepage into underground sewer lines tions of fipronil plus its three degradation products from subterranean termite treatments, spills, and in runoff were 0.014 to 0.441 µg/L (Gan et al. improper disposal. 2012). ° Applications to control insects around buildings involve spraying impervious surfaces, like build- TABLE 1 ing walls and walkways, from which fipronil and its Toxicity thresholds for fipronil and its degradation products. All concentrations in µg/L. degradation products can be washed into gutters LOWEST USEPA PESTICIDE and storm drains. In laboratory simulations, fipronil AMERICAMYSIS BAHIA and its degradation products appeared in runoff AQUATIC LIFE BENCHMARKS from concrete surfaces at concentrations >140 µg/L CHEMICAL NAME LOWEST OBSERVED LC50 one day after application, >30 µg/L two weeks after EFFECT CONCENTRATION application, and >1 µg/L 56 days after application 0.011 (Thuyet et al. 2012; Jiang et al 2010). Fipronil 0.14 0.005 (invertebrates, chronic)

Fipronil Sulfone 0.037 0.56 0.0026 (MB46136) (invertebrates, chronic)

Fipronil Sulfide 0.11 0.077 0.0087 (MB45950) (invertebrates, chronic)

Desulfinyl Fipronil 0.59 1.5 -- (MB46513) (fish, chronic)

84 CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 85 TIERTIER 3 3 S A The pe A r I B regulatory to in response increase is likely to cides, usage on pyrethroids. restrictions could potentially products and its degradation of fipronil organisms, test sensitive for levels effect be approaching points. discharge near margins, the Bay particularly at in sediment. accumulation to lead monitoring data published between 2003 and 2012 2012 2003 and published between data monitoring samples water in 39% of was detected fipronil found that observed of levels Average samples. sediment 19% of and chronic USEPA’s exceeded (0.09 µg/L) water in fipronil of 0.011 benchmark protection invertebrate aquatic degrada- of fipronil concentrations µg/L, while average as of magnitude order same on the were tion products protec- aquatic chronic USEPA respective their lowest 2013). (Ruby tion benchmarks (0.037-0.590 µg/L) recent in more found generally compoundswere fipronil 2002-2003 samples, to compared (2009-2012) samples, not detected. often in which they were in trend” upward significant a identified “widespread and of fipronil frequency concentrations and detection al. et (Ryberg 2000-2008 from products two degradation 2010). insecti- pyrethroid to the fipronil an alternative ince is concentrations that indicate data monitoring vailable could products degradation offipronil rsistence fipronil watershed urban ofCalifornia review ecent of monitoring,n RMP concentrations sediment higher USGS sites, urban 10nationwide from ondata ased Trends in the Bay and Nationally Bay the and in Trends • • • Bay? the in Harm of a Risk There Is • • •

. (Bay et al. et 2010). (Bay 100% of sediment samples collected in 2007-2009 from in 2007-2009 from collected samples 100% of sediment CA). The high- estuary Angeles, (Los Creek the Ballona In most was 6 ppb. concentration fipronil measured est sulfonewas fipronil product the degradation samples, some In 9.8 ppb. up to concentrations, higher at present toxic potencyplus degradation of fipronil the total cases, for Chironomus tentans the EC50 exceeded products, concentrations at in 100% of samples, nil detected was 0.020 µg/L. Thirty-six 0.006 to from these of percent life aquatic chronic USEPA’s exceeded samples discrete 2013). of 0.011 µg/L (USEPA benchmark protection ucts in Bay sediment in 2002-2003 and 2009-2012. The 2009-2012. and in 2002-2003 sediment ucts in Bay for individual 0.56 ppb up to concentrations, highest Bay. South in Lower measured compounds,were fipronil (sediment-dwelling) benthic for saltwater data Toxicity found reduced study One laboratory limited. are species with crustacean ad- benthic in a saltwater reproduction al. et 2004). The (Chandler sediment dition to of 30 ppb the exceed observed in the Bay concentrations highest immobilization for immobilization causing (level EC50 species, benthic of a freshwater organisms) in 50% of test Chironomus tentans F I The R in detected were products itsdegradation and ipronil fipro- creeks, urban Area Bay offour n 2012monitoring prod- and itsdegradation fipronil MP measured • • Patterns of Occurrence in the Bay and in Other Other in Bay the and in Occurrence of Patterns Aquatic Ecosystems • degradation products, which may have half-lives (time (time half-lives have which products, may degradation in as 700 days as long for a 50% reduction) required 2007). (USEPA environments aquatic significantly reduces the uptake of fipronil and its of fipronil the uptake reduces significantly toxicity organisms, thresholds by products degradation carbon organic of sediment on the basis expressed are of organic gram per of fipronil micrograms (e.g., content carbon). L predictions can be made based on information from from on information based be made can predictions prod- degradation its stable and Fipronil studies. other in the sediment and both water in occur likely to ucts are expo- by breakdown and sediment into Partitioning Bay. activity microbial and sunlight likely determine to sure Bay. in the fate ultimate fipronil’s I The fa offipronil fate the exist characterize data to imited carbon oforganic thepresence because n sediment, studied, but has notbeen Bay inthe offipronil te Concentrations of fipronil and its degradation and its degradation Concentrations of fipronil be approaching effect products could potentially particularlylevels for sensitive test organisms, at the Bay margins, near discharge points • • General Properties General • Fipronil Bay? the in It to Happens What 3/4 4/4 TIER 3 Fipronil

Key Information Gaps • Toxicity identification evaluation methods that allow evaluation of the potential for linkage between fipronil Aquatic toxicity and environmental fate data, particularly • exposures and incidents of toxicity to testing organisms. for fipronil degradation products. • Application rates and techniques that maintain pest Monitoring data for fipronil and its stable degradation • control efficacy while reducing the quantity of fipronil in products in Bay water and sediment (particularly near urban stormwater runoff. discharge points, including Bay margins), urban creek sediment, and municipal wastewater effluent.

Management Timeline

2007 The Urban Pesticides Pollution Prevention Project (www.UP3Project.org) finds that the use of fipronil has the potential to cause adverse effects in aquatic ecosystems and recommends management actions including avoiding 2011 outdoor fipronil applications and expanding USEPA initiates fipronil monitoring programs. Registration Review.

2008 2009 2010

2007-2011 Fipronil included in Water Board and DPR surface water monitoring programs.

86 CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 87 ). PAGE 16 PAGE U I P A C plant treatment wastewater municipal and plications, Bay ( to the pathways are all effluent such as ant and termite control around buildings, weed buildings, weed around control termite and as ant such wood roads, along and in landscaping control slug and fungicides preservatives, biocides and in building roofing biocides, swimming drinking paints, and pool and water for antifouling treatments and products, control flea pet hulls. boat not traditionally are that products into incorporated as building mate- such pesticides, contain to understood products. rials cleaning and half of all occurs pesticide use than California more state, areas. in urban 2013). 2011 (CDPR ap- runoff, in-Bay stormwater agricultural and rban uses, ofdiverse hundreds have pesticides areas, n urban commonly are (particularlyesticides antimicrobials) agricultural leading is California thenation’s lthough 280millionalifornia exceeded kg pesticide in sales • • • Bay? the Into Getting They Are How • • Act priority pollutants (e.g., copper, silver, acrolein, and and acrolein, silver, copper, Act priority (e.g., pollutants pentachlorophenol). from away a shift driven market in the pesticide have up the food chain passed are that likepesticides DDT a multiplicity families, of chemical some into of new and organisms. aquatic toxic to highly which are doors. growth, fungi, weed and competing insects, from crops nematodes. inorganic chemicals that are toxic to unwanted organ- unwanted toxic to are chemicals that inorganic isms. S R T I A S Water Clean are pesticides used currently dozen everal health human onprotecting focused egulatory changes out- bothindoors and organisms, unwanted o control to protect used often most are pesticides n agriculture, or organic synthetic 1,000 than natural or ofmore ny pesticides. are asnanosilver, such ome nanoparticles, • • For? Used They Are What • • What Are They? • •

Fipronil TIER 3 CONCERN MODERATE *

LOW KELLY MORAN, KELLY TDC Environmental ([email protected]) TIER 2 CONCERN Pyrethroids

* Pyrethroids are of low concern high concern but in in the Bay, Bay Area urban creeks Quick Summary Summary Quick all includes herbicides,“pesticides” insecticides, term The Although antimicrobials. fungicides, and rodenticides, Agency (USEPA) Protection Environmental both the US Regulation of Pesticide Department the California and gaps use, their first prior pesticides to approve must (DPR) in pesticide resulted have in pesticide procedures review found been have pesticides used pollution. Currently water of envi- the lack Due to environments. aquatic throughout methods currently analysis for most chemical ronmental toxicity availability of aquatic limited and pesticides used risks not fully the potential data, are understood. Currently Used Pesticides Used Currently 1/4 TIER 1 CONCERN POSSIBLE Used Pesticide Other Currently 2/4

TIER 1 Currently Used Pesticides

What Happens to Them in the Bay? TABLE 1 TIER 2 Urban Pesticides Pollution Prevention Project Priority Pesticides List. • Pesticides and their degradation products (which are sometimes more toxic and persistent than their parent PESTICIDE PRIORITY DISCHARGE PATHWAY POTENTIAL POTW TIER 3 chemicals) may occur in water, sediments, and biota in OPERATIONAL the Bay ecosystem. INTERFERENCE • Because environmental fate and aquatic toxicity data URBAN RUNOFF POTW DIRECT TO BAY for estuarine environments are not routinely obtained PYRETHROID INSECTICIDES before pesticides are approved for use, the fate of most Allethrin X X currently used pesticides in the Bay is largely unknown. Bifenthrin X X Cyfluthrin X X • For most currently used pesticides, no published, Cyhalothrin X X validated environmental chemical analysis methods Cypermethrin X X Cyphenothrin X exist, which has greatly limited the availability of data Deltamethrin/Tralomethrin X X to characterize patterns of occurrence in the Bay and in Esfenvalerate X X other aquatic ecosystems. Etofenprox X Permethrin X X • While no trend data are available for the Bay, the general Phenothrin X X trend in pesticide design is away from chemicals that Prallethrin X X accumulate in the food web. Some currently used Resmethrin X X pesticides and their toxic degradation products (e.g., Tetramethrin X X OTHER INSECTICIDES bifenthrin, indoxacarb), degrade slowly and may ac- Carbaryl X cumulate in sediment. Pesticides occurring in municipal Fipronil X X wastewater discharges can be “virtually persistent” (have Indoxacarb X a persistent presence in the Bay) even if they degrade Malathion X X quickly because they are continuously discharged. SWIMMING POOL, SPA, AND FOUNTAIN TREATMENTS Copper and Copper Compounds X X PHMB X X Silver X X ANTIMICROBIALS Copper X Silver (including nanosilver) X X Triclosan X SEWER ROOT CONTROL Copper Sulfate X Dichlobenil X X Diquat Dibromide X X Metam Sodium X X WOOD PRESERVATIVES Copper and copper compounds X X Creosote X Pentachlorophenol X X MARINE ANTIFOULING BIOCIDES Copper oxides X Irgarol 1051 X Zinc Pyrithione X

Source: TDC Environmental 2010, as informally updated in 2011. 88 CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 89 TIER 1 TIER 2 TIER 3

Abamectin Abamectin Bifenthrin Chlorothalonil Chlorpyrifos Cyfluthrin Cypermethrin Deltamethrin Diazinon Diuron Esfenvalerate Fipronil Lambda-Cyhalothrin Malathion Mancozeb Maneb (S)-Metolachlor Oxyfluorfen Paraquat Dichloride Pendimethalin Permethrin Polyhexamethylene biguanide (PHMB) Propanil Propargite Pyraclostrobin Simazine Tralomethrin Trifluralin Ziram Source: Lu and Davis 2009. TABLE 2 of High Overall Board List Water Central Valley Level Pesticides Relative Risk ). TABLE 2 ) (TDC Environmental 2010). ) (TDC Environmental TABLE 1 use reporting data and an earlier version of the UP3 Project of the UP3 Project version earlier an and data reporting use pesticide priorityurban a list of agricultural develop list to relative overall the highest pose that pesticides urban and Joaquin San River, life in the Sacramento risk aquatic to ( watersheds Delta and River, developed for the Bay, its urban and agricultural watersheds, watersheds, agricultural and its urban for the Bay, developed discharges. or its wastewater a simplified prioritizationto identifyoped scheme pesticides threaten likely to most are that areas urban in California used quality ( water I as the highest risk class of chemical compounds (e.g., von von risk compounds (e.g., of chemical as the highest class Ohe 2011), whichder is specifi- unsurprising they are since kill to cally designed organisms. N The U chlorpyrifos), in effluents (e.g., copper-based root control control root copper-based (e.g., chlorpyrifos), in effluents associ- been have pesticides where in creeks, and products), and swimming pool drinking withwater (e.g., fish ated kills pyre- (e.g., challenges current posing are and biocides), ecosys- aquatic harm can pesticides that indicate throids), tems. A for most currently used pesticides and the limited availability the limited and pesticides used currently for most risks toxicity unknown. potential the of aquatic data, are P Due t Although the prioritization was not comprehensive, the Although the prioritization not comprehensive, was which prioritizes is unique in its approach, system ranking in the and presence toxicity, pattern, on use based pesticides market. urban California DPRpesticide used Board Water Valley n 2009,theCentral list ofpesticide been priorities ever has o comprehensive devel- Project Prevention Pollution Pesticides rban ranked often are pesticides contaminants, emerging mong and diazinon (e.g., pollution intheBay pesticide water ast methods analysis chemical ofenvironmental o thelack • • • • • Currently Used Pesticides Used Currently Bay? the in Harm of a Risk There Is • 3/4 4/4

TIER 1 Currently Used Pesticides

TIER 2 Key Information Gaps • Monitoring data in San Francisco Bay waters and sediments (particularly near discharge and use points, A robust system for prioritizing pesticides for develop- • including Bay margins and marinas), urban water and ment of environmental chemical analysis methods. creek sediments, and municipal wastewater effluents. TIER 3 • Environmental fate and aquatic toxicity data for pesti- cides and their stable degradation products , particularly in estuarine environments.

Management Timeline

2006 2009 2013 The Urban Pesticides Central Valley Water Board DPR develops methods for Pollution Prevention Project examines the relative risk prioritizing agricultural (www.UP3Project.org) to aquatic life posed by and urban pesticides for develops the first list of pesticides used in the monitoring (Budd et al. pesticides used in urban watersheds draining to San 2013; Luo et al. 2013). areas that are most likely to Francisco Bay (Lu and Davis threaten water quality. 2009).

2007 2008 2010 2011 2012

90 CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 91 U C tion, and other federal agencies are are agencies federal tion, other and by gap this data address to beginning on the environmental funding research of nanomaterials. implications exposure dose high turingsettings where likely isis a priority. more Founda- Science theNational SEPA, inmanufac- nanomaterials ontrolling • • A lacking. generally are The hi toxicity. for their potential concern S in which species, result oxygen can of reactive creation toxicity organisms. in aquatic The s cell membranes. cells or cross compromise I operations, manufacturing transportof normal and or by products, of nanomaterial-containing use consumer release. accidental Be treatment. wastewater conventional by nanoparticles the chemi- also alter may processes treatment Wastewater nanoparticles. cal properties of engineered S al. et 2010 (Schierz in 2007 and collected sediment Bay 2012). N samples. S toxicity and of nanomaterials. transport, fate, intheenvironment nalytical methods fornanomaterials for is ofnanoparticles cause nature ghly reactive the increase shown to been have ome nanomaterials to allow them can nanomaterials mall ofsome size aresult as occur may wastewater municipal to nputs ofsilver removal shown good nch-scale have studies in notdetected were nanotubes carbon ingle-walled inBay analyzed been have nanomaterials o other existgaps of ignificant scientific inthe understanding • Bay? the in Harm of a Risk There Is • • • • • Bay? the in Them to Happens What • • • Protection Agency (USEPA) Office Office Agency (USEPA) Protection found that General of the Inspector authority the statutory has to "USEPA but currently nanomaterials regulate human and lacks the environmental data toxicological exposure and health effectively.” do so to A 2011 r eport Environmental theUS by • S provide unique methods can of drugnanotubes, delivery specificcells. target to designed S as well as in production energy and applications, tronics or polymers plastic strength withof composite enhanced properties. electrical or thermal The hi is useful one ex- ity commercially; of nanomaterials chemical speed that catalysts is as metal their use ample rates. reaction A common. now are nanoparticles G the to be introduced may substances these materials, municipal including via pathways multiple environment runoff. urban and wastewater I in the country. centers development N textile treat- items; plastic and glass, for ceramic, coatings a host and like sunscreens; products care personal ments; products. of other carbon single-walled including ome nanomaterials, inelec- also beused may nanotubes carbon ingle-walled reactiv- high and ratio volume to area gh surface silver containing products consumer ntibacterial types and ofapplications thewide ofnano- iven range nanotech three oneofthetop was Valley n 2007,Silicon cells; fuel batteries; inelectronics; used are anomaterials • • • • Bay? the Into Getting They Are How • • What Are They Used For? For? Used They Are What • C stances Control has issued two issued informa- has Control stances and manufacturers to tion requests analytical methods, importers regarding transport, informa- and other and fate (2010) and tion nanotubes on carbon forms of silver, nano dots, and quantum dioxide, oxide, titanium cesium iron, zincand oxide (2011). Sub- ofToxic Department alifornia’s • - MEREDITH WILLIAMS, MEREDITH WILLIAMS, San Francisco Estuary Institute [[email protected])

tion and include both inorganic and organic materials. materials. organic and tion include both inorganic and in industry for use others or in products, nanomaterials naturally. occur N W L encompasses otechnology Initiative a range overseeing agencies 27 federal activi regulatory and of research ties. The Initiative’s Environmental, Environmental, Initiative’s The ties. Strategy, Research Safety and Health, guidance in 2011, provides updated in developing agencies federal to priorities. research - Nan 2000,theNational in aunched composi- than rather by size defined are anomaterials synthesizehile engineered avariety now we ofunique, Management Timeline • What Are They? • • Quick Summary Summary Quick or 100 nanometers materials, ultrasmall are Nanomaterials is one One nanometer one dimension. least on at in size less nanomateri- of their size, Because millionth of a millimeter. electronic chemical, and of unique physical, a range als have in a wide be used can spectrumproperties that of applica- unique toxic also have may nanomaterials Some tions. fully not been investigated. have properties that Nanoparticles Nanomaterials or 1/1 TIER 1 CONCERN POSSIBLE 1/1 Chlorinated Paraffins

What Are They Used For? Concentrations observed in Bay TIER 1 • CPs have been used as lubricants in metal forming and cutting industries since the 1930s. They are also used as biota are substantially lower POSSIBLE MEG SEDLAK, a plasticizer and as a flame retardant in plastics. Minor than elsewhere and well below San Francisco Estuary Institute uses include paints, rubber formulation, adhesives and CONCERN [[email protected]) sealants. available effect thresholds • In 2009, the estimated annual use of CPs was more than 150 million pounds per year in the US. MCCPs have the largest use in North America. Production of CPs in China was almost 600 million pounds in 2002 (Bayen et Is There a Risk of Harm in the Bay? al. 2006) and production in India appears to be growing • Limited toxicological information exists; however, the as well. concentrations observed in the Bay are substantially lower than elsewhere and low relative to other legacy Quick Summary pollutants (Santos et al. 2006, Houde et al. 2008, and Chlorinated paraffins (CPs) are chlorine-containing com- How Are They Getting Into the Bay? Bayen et al. 2006). pounds related to paraffin wax that are primarily used as • It is not known how CPs enter the Bay; however, it is • CPs are known to cause narcosis and liver lesions (Cool- lubricants and coolants in the metal forming and cutting likely that wastewater treatment plant effluent is one ey et al. 2001). Concentrations in Bay biota, however, industries. CPs accumulate in biota; however, concentra- pathway. are well below available effect thresholds. tions observed to date in Bay seals, fish, and birds are very • The argestl source of CPs to wastewater treatment low. CPs are exceedingly difficult to analyze; toxicity and plants is spent metal-cutting fluids and wash-off from occurrence data are sparse. As a result, they are classified metal-forming equipment and surfaces, followed by the Management as Tier 1. leaching of CPs from polyvinyl chloride processes and • CPs were a high production volume chemical (produced products, rubber, adhesives, and paints (Environment or imported in excess of 1 million pounds per year) in What Are They? Canada 2008). the late 1990s. Only one US firm produces CPs (Dover Chemical ). As part of a settlement agreement with • CPs are chlorine-containing compounds related to • Landfill leachate is also a suspected source of CPs (Envi- ronment Canada 2008). USEPA, Dover ceased production of SCCPs. SCCPs are paraffin wax. They are grouped into three classes: also being phased out in Europe. MCCPs and LLCPs, short-chained (carbon chain length between 10 and 13, however, remain widely used. SCCP); medium-chained (between 14 and 17, MCCP) What Happens to Them in the Bay? and long-chained (greater than 17, LCCP). • SCCPs are a priority hazardous substances in the Euro- • CPs are viscous oils or solids. They have a strong ten- pean Union and their use is restricted to less than 0.1% • CPs are classified as highly persistent in the environ- dency to adsorb to soil and sediment particles and to in metal working solutions and leather tanning opera- ment, bioaccumulative (accumulating in biota), and bioaccumulate (Bayen et al. 2006). They are very stable tions. SCCPs are classified as compounds of very high toxic to aquatic organisms (Environment Canada 2008, compounds. concern under REACH (PAGE 19). USEPA 2009). SCCPs are believed to be more toxic to aquatic organisms than MCCPs and LCCPs. • In a limited study of Bay biota, CPs were measured at very low concentrations in harbor seal blubber and bird eggs. CPs were not detected in sport fish.

92 CEC MONITORING A GUIDE TO CEC s IN THE BAY

| 93 P B P They a I S P dioxins furans (Melber and polychlorinated similar to Kielhornand 1998). dioxins polychlorinated toxic than less of 10 or more tor their risks furans, so and proportionally are smaller, dioxin-like 5% of total for only around likely accounting activity sediments. in Bay with replaced PBDEs are of PBDEs, unless the phase-out retardants. flame brominated other furans, with an estimated half-life in soil of three to six half-life to in soil furans, with of three estimated an Kielhorn and 1998). (Melber months not dioxin furan compounds and were polybrominated much very concentrations, or found at low detected with for areas in the literature reported those than lower sources. expected large This Bay. Central southern and Bay in South highest Bay, (Steen of PBDEs product be a degradation to is believed al.et 2009, Arnoldsson al. et 2012). with paral- depth, decreased in Japan Bay Osaka from suggesting and cores in PBDEs in those decreases leling al. et time (Takigami over concentrations increasing similar should show in the Bay 2005); concentrations trends. ofaction modes dioxins furans have and olybrominated afac- nearly dioxins furans are and polybrominated ay with dioxins furans shoulddecrease and olybrominated dioxins and thechlorinated than persistent less re toxic themost biotasamples, and sediment n Bay ome 1,3,7-tribromodibenzodioxin foundinthe was core dioxins furans inasediment and olybrominated • • • Bay? the in Harm of a Risk There Is • • Management • • ). PAGE 63 PAGE to particles and settle into sediments, where they may be may they sediments, where into particles settle and to up passed and organisms sediment-dwelling up by taken the food chain. reactions of brominated chemicals and their degradation their degradation chemicalsand of brominated reactions products. research. in laboratory furans are for PBDEs those mirror unknown, but may are the Bay chemicals. synthetic other and brominated in manufacturing, recycling, materials with brominated Area. in the Bay not prevalent generally or incineration, concentra- high had et al. 2003) (Litten Center Trade materials of brominated tions, combustion likely from dioxins of polybrominated 1986). Production (Buser but, structure fires, also in smaller occur furans may and will the amounts disasters, in major usuallyexcept be dispersed.small and P similar in structure and toxicity to chlorinated dioxins toxicitysimilar in structure and chlorinated to furans. and as chemicals such organic of brominated by-products PBDEs ( They a S The only de P M S S P bind to expected dioxins furans are and olybrominated environmental and combustion also by formed re algae. by produced naturally ome forms are dioxins and forpolybrominated uses liberate dioxin furan entry and to forpolybrominated athways onareas focused have intheliterature loads easured World ofthe theburning after York inNew amples chemicals ynthetic occurring brominated ornaturally as formed dioxins furans are and olybrominated What Happens to Them in the Bay? Bay? the in Them to Happens What • • • For? Used They Are What • Bay? the Into Getting They Are How • • • What Are They? • • DONALD YEE, DONALD YEE, San Francisco Estuary Institute ([email protected])

LOW In Bay samples, the most In Bay samples, the most toxic polybrominated dioxin and furan compounds were not detected or found at verylow concentrations Polybrominated dioxins and furans are brominated ver- brominated dioxins furans are and Polybrominated dioxins known chlorinated commonly of the more sions dioxins furans are and Polybrominated furans. and biota, and but sediments in Bay accumulate to expected than lower much concentrations found only at been have of PBDE the phase-out With cousins. their chlorinated dioxinsand furans polybrominated retardants, flame synthetic biologi- from will but some products decrease, forms willcally produced be present. to likely continue Polybrominated Dioxins and Furans and Dioxins Polybrominated 1/1 Quick Summary Quick TIER 2 CONCERN 1/1 On the Lookout for New CECs

Scientists and managers have are under consideration for RMP annually (Howard and Muir 2010) as additives in pesticides. Fluori- the toxicity and potential for these been grappling with the challenge monitoring are presented below. and this compound has not been nated cyclic compounds such as compounds to bioaccumulate are of identifying CECs among the monitored in the environment. perfluoroperhydrophenanthrene not well understood. The RMP has thousands of chemicals in com- Brominated Compounds are used in the electronics industry. monitored for D4, D5, and D6 in merce. Some of the most influential Many of the CECs that are of great- Chlorinated Compounds Analytical techniques to measure bivalves; the primary compound assessments have been conducted est concern for San Francisco Bay Many of the top candidates as new these compounds are in develop- detected was D5 in concentrations by Derek Muir of Environment are brominated compounds that are CECs are chlorinated pesticides ment. Fluorinated alkyl phosphates ranging from approximately 20 to Canada (one of the science advisors flame retardants. For example, eth- (Howard and Muir 2010). Bis(4- have been detected in Canadian 90 ng/g dw. on the RMP Emerging Contami- ylene bis-tetrabromophthalidimide chlorophenyl)sulfone is another effluents in concentrations that are PAGE 51 nants Workgroup – ) and (EBTEBPI) is a high production type of chlorinated compound almost an order of magnitude lower Others Philip Howard. Howard and Muir volume chemical and an alterna- identified by Howard and Muir - a than PFOS (D’Eon et al. 2009). Other compounds identified (2010) screened over 22,000 tive for the DecaBDE formulation high production volume chemical The RMP is currently embarking by Howard and Muir as poten- chemicals in databases of chemi- that is being phased out this year. that is used in the manufacture of on a pro bono study with AXYS tial CECs include the fragrance cals in commerce maintained by Because flame retardants are used plastics and pharmaceuticals. This Analytical to identify possible fluo- ingredients such as traseolide and the US Environmental Protection in high volumes, and are potentially compound has been detected in rinated compounds that undergo galaxolide (see also PAGES 71-74). Agency and Environment Canada persistent, readily accumulated by bird eggs in the Great Lakes and tranformations to produce PFOS An expert panel convened by the to identify new CECs. Each of biota, and toxic, the RMP places bird eggs and seals in the Baltic Sea. and PFOA in the environment State Water Board recommended the chemicals was evaluated for a high priority assessing whether that galaxolide be monitored in persistence, bioaccumulation, and these compounds are a threat in the Fluorinated Compounds Silicone Compounds enclosed bays and estuaries (An- toxicity. Over 600 chemicals were Bay. A special study on alternative Siloxanes and other silicone derson et al. 2012). The RMP has identified, comprising five general Perfluorinated compounds, such as flame retardants is planned for PFOS, have been an area of concern containing compounds are widely monitored galaxolide in water and classes: brominated, chlorinated, 2014. Not all brominated com- used in shampoos and deodorants found concentrations substantially fluorinated, silicone-related, and since our first studies in 2007. Sev- pounds are flame retardants. Muir eral of the fluorinated compounds as well as in lubricants, polymers, below the no effect concentration of “others.” The RMP used a similar and Howard identified in their textiles, and medical devices. 7,000 nanograms per liter. As part approach. Working with Dr. Muir identified in the Howard and Muir top ten list of brominated com- list are replacements for fluorinated Siloxanes with cyclic structures of the development of bioanalytical and other advisers we have identi- PAGE 51 pounds, 1,3,6,8-Tetrabromopyrene compounds such as PFOS (PAGE such as D4 and D5 are widely used tools ( ), galaxolide is one fied a suite of CECs. Several exam- (TBrPy), a compound that is used in these applications. Developing of four chemicals that will be used ples of chemicals that 55). Fluorinated alkyl phosphates in the manufacture of LEDs. It is and fluorinated cyclic compounds analytical methods for monitoring to assess endocrine disruption. The estimated that 500,000 are identified in the Howard and these compounds has been a chal- RMP will consider evaluating ad- lbs of TBrPy are pro- Muir top ten list. Fluorinated alkyl lenge as a result of their ubiquitous ditional fragrances in a future study. duced phosphates are frequently used use and high volatility. In addition,  Photograph by Meg Sedlak.

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Fipronil effects on Monitoring in Agricultural and Urban pubs/sccps_ap_2009_1230_final.pdf 2277-2285. Anderson BS et al. 2008. Relative sensi- from California Urban Watersheds. estuarine copepod (Amphiascus Areas. Prepared by the California tivities of toxicity test protocols with the Prepared for the California Stormwater tenuiremis) development, fertility, and Department of Pesticide Regulation Howard PH, Muir DC. 2011. Identifying amphipods Eohaustorius estuarius and Quality Association. Santa Cruz, CA. reproduction: A rapid life‐cycle assay Environmental Monitoring Branch. new persistent and bioaccumulative in 96‐well microplate format. Environ- organics among chemicals in com- Ampelisca abdita. Ecotoxicol. Environ. TDC Environmental 2010. Pesticides TDC Environmental 2010. Pesticides mental toxicology and chemistry, 23, merce II: pharmaceuticals. Environ Sci Safety 69(1): 24-31. in Urban Runoff, Wastewater, and in Urban Runoff, Wastewater, and 117-124. Technol 45(16): 6938-6946. 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Environ Monit Assess 185(5): 3697-3710. 96 ACKNOWLEDGEMENTS 97 Vallejo Sanitation and Flood Control District CountyWest Agency DISCHARGERS INDUSTRIAL C & H Sugar Company Chevron Products Company Conoco Phillips (Tosco-Rodeo) Cogeneration Crockett Inc.Rhodia, Shell – Martinez Refining Company Refinery Eagle Golden Tesoro USS – POSCO Industries Tosco, Rodeo Valero Refining Company COOLING WATER Energy GenOn STORMWATER Alameda Countywide Clean Water Program Caltrans City and County of San Francisco Contra Costa Clean Water Program Fairfield-Suisun UrbanRunoff Management Program Marin County Stormwater Pollution Prevention Program San Mateo Countywide Water Pollution Prevention Program Santa Clara Valley Urban Runoff Pollution Prevention Program Vallejo Sanitation and Flood Control District DREDGERS Point Alameda BAE Systems Wharf Long Richmond Chevron City of Benicia Marina Conoco Phillips (Tosco-Rodeo) Marin Club Yacht Marina Bay Harbor Yacht Marina Vista Harbor Homeowners Association Napa Club Yacht Port of Oakland Port of San Francisco San Francisco Marina San Rafael Harbor Yacht Harbor Yacht Sausalito US Army Corpsof Engineers Vallejo Ferry Terminal Valero Refining Co. EXPOSURE WORKGROUP AND EFFECTS MichaelDr. US Fish and Fry, Wildlife Service HarryDr. Ohlendorf, CH2M Hill DanielDr. Schlenk, University of California – Riverside SteveDr. Weisberg, Southern California Coastal Water Research Project AND WORKGROUP LOADING PATHWAYS SOURCES BarbaraDr. Mahler, US Geological Survey RogerDr. Bannerman, Wisconsin Department of Natural Resources Kelly Moran,Dr. TDC Environmental Mike Stenstrom,Dr. University of California – Los Angeles RMP Participants DISCHARGERS MUNICIPAL Burlingame Waste Water Treatment Plant Central Contra Costa SanitaryDistrict Central Marin Sanitation Agency City of Benicia City of Calistoga City of Palo Alto Petaluma City of City of Pinole/Hercules City of Saint Helena City and County of San Francisco City of San Jose/Santa Clara City of San Mateo City of South San Francisco/San Bruno City of Sunnyvale Delta Diablo Sanitation District East Bay Dischargers Authority East Bay Municipal Utility District Fairfield-Suisun Sewer District Las Gallinas Valley Sanitation District Marin County Sanitary District Tiburon #5, Millbrae Waste Water Treatment Plant Mountain View Sanitary District Napa Sanitation District Novato Sanitation District Rodeo Sanitary District San Francisco International Airport Sausalito/Marin City Sanitation District Sewerage Agency of Southern Marin Agency County Water Sonoma Authority System Bayside South Yountville of Town Union Sanitary District

RMP Science Advisors Science RMP WORKGROUP CONTAMINANT FATE JoelDr. University Baker, of Washington - Tacoma Frank Gobas,Dr. Simon Fraser University WORKGROUP CONTAMINANTS EMERGING LeeDr. Ferguson, Duke University JenniferDr. Field, Oregon State University Technology of Institute Massachusetts Gschwend, Phil Dr. Derek EnvironmentDr. Muir, Canada DavidDr. Sedlak, University of California - Berkeley POTWs/BACWA, NirmelaPOTWs/BACWA, Arsem, East Bay Municipal Utility District Rod Miller, San Francisco Public Utilities Commission South Bay Dischargers, Hall, Inc. Tom EOA Corporation Integral DeShields, Bridgette Refineries, USS-POSCO Allen, Dave Industry, Stormwater Agencies, Chris Sommers, EOA, Inc. Dredgers, John Prall, Port of Oakland San Francisco Bay Regional Water Quality Control Board, Taberski Karen LuisaUSEPA, Valiela City of San Jose, Eric Dunlavey City/County of San Francisco, Michael Kellogg US Army Corps of Engineers, Robert Lawrence RMP Technical Review Committee Chair in bold print RMP Committee Review Technical RMP Steering Committee Small Karin North, POTWs, City of Palo Alto Medium-sized Daniel POTWs, Tafolla, Vallejo Sanitation and Flood Control District Jim Ervin,Large City POTWs/BACWA, of San Jose Refinery Eagle Golden Tesoro Carroll, Peter Refineries, USS-POSCO Allen, Dave Industry, Cooling Steve Bauman, Water, Mirant Delta LLC Stormwater Agencies, Adam Olivieri, EOA, Inc. Dredgers,John Coleman, Bay Planning Coalition San Francisco Bay Regional Water Quality Control Board, Tom Mumley US ArmyCorps of Engineers, Rob Lawrence print bold in Chair Committee Steering RMP RMP Committee Members and Participants and Members Committee RMP Credits & Acknowledgements

Editors Creative Direction, Reviewers Printing information Jay Davis, Meg Sedlak, Design & Illustration Derek Muir, David Sedlak, Jennifer Field, Marilyn Leoncavallo at Bay Area Graphics Rebecca Sutton, Christine Werme Linda Wanczyk Lee Ferguson, Phil Gschwend, Luisa Valiela, www.bayareagraphics.com Peter Carroll, Denise Greig, Don Yee, Lester McKee, Mike Connor, Keith Maruya, THE PAPER. Contributing Authors Patti TenBrook, Dave Tamayo, Tom Mumley, Information Graphics REINCARNATION™ IS THE MOST Jay Davis, Meg Sedlak, Gail Krowech, Ellen Willis-Norton, Linda Wanczyk, Patty Frontiera, ENVIRONMENTALLY David Senn, Naomi Feger, Don Yee, Kelly Moran Nicole David Ellen Willis-Norton FRIENDLY PAPER STOCK AVAILABLE. ✪ 100% Recycled, 60% Post-consumer RMP Data Management Information Compilation Waste Processed Chlorine Free David Gluchowski, John Ross, ✪ FSC Certified Cristina Grosso, John Ross, Amy Dave Schoellhamer, Lester Ancient Forest Friendly Franz, Don Yee, Adam Wong McKee, Nicole David ✪ ✪ Manufactured with electricity that is offset with Green-e® certified renewable Graphics Assistance energy certificates Joanne Cabling

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Printed on 100% Recycled, 60% Post-consumer Waste Processed Chlorine Free Paper alkylphenol perfluorooctane sulfonate erythromycin hydrate tris (1,3-dichloro-2-propyl) phosphate ranitidine sertraline diuron fenpropathrin triclosan bis(4-chlorophenyl)sulfone polybrominated diphenyl ether hexabromocyclododecane ziram 1,2-bis (2,4,6, tribromophenoxy) ethane bifenthrin bis (hexachlorocyclopentadieno) cyclooctane nanomaterials gemfibrozil tris (1,3-dichloro-2-propyl) phosphate maneb triclocarban 4-nonylphenol bisphenol a diphenhydramine fipronil caffeine sulfamethoxazole n,n-diethyl-m-toluamide carbamazepine bis(2-ethylhexyl) phthalate cypermethrin single-walled carbon nanotubes galaxolide siloxanes chlorinated paraffins dehydronifedipine ciprofloxacin D5 esfenvalerate permethrin di-n-butyl phthalate oxazepam chlorothalonil perfluoroperhydrophenanthrene cocaine traseolide nanosilver polybrominated dibenzo-p-dioxins cotinine 1,3,6,8-tetrabromopyrene indoxacarb cyfluthrin diphenhydramine ethylene bis-tetrabromophthalidimide V6 chlorophenoxyphenols valsartan phenothrin mancozeb