TOXIC CONTAMINANTS IN THE SAN FRANCISCO BAY-DELTA AND THEIR POSSIBLE BIOLOGICAL EFFECTS DAVID J.H. PHILLIPS AQUATIC HABITAT INSTITUTE 180 Richmond Field Station 1301 South 46th Street Richmond, CA 94804 (415) 231-9539 August 26, 1987 CONTENTS Acknowledgments ................ (i) I . INTRODUCTION ................. 1 I1 . TRACE ELEMENTS IN THE BAY-DELTA . 5 A . Silver .................. 7 B . Copper .................. 40 C . Selenium ................. 68 D . Mercury .................111 E . Cadmium .................133 F . Lead ...................148 G . Zinc ................... 163 H . Chromium .................171 I. Nickel ..................183 J . Tin ...................194 K . Other Trace Elements ...........200 111 . ORGANOCHLORINES IN THE BAY-DELTA .......202 A . Polychlorinated Biphenyls ........205 B . DDT and Metabolites ...........232 C . Other Organochlorines ..........257 IV . HYDROCARBONS IN THE BAY-DELTA ........ 274 A . Introduction ..............274 B . Hydrocarbons in the San Francisco Estuary . 281 C . Summary .................304 V . BIOLOGICAL EFFECTS OF BAY-DELTA CONTAMINANTS . 306 A . The Benthos of the Bay-Delta ...... 307 B . Fisheries of the Bay-Delta ........ 319 C . Bird Populations ............ 351 D . Mammalian Populations. Including Man . 354 E . Bioassay Data ............. 359 VI . CONCLUSIONS ................. 377 Literature Cited .............. 382 ACKNOWLEDGMENTS Thanks are due to a large number of people for their contributions to this document. Staff at the Aquatic Habitat Institute have provided their support, encouragement and talent. These include Andy Gunther, Jay Davis, Susan Prather, Don Baumgartner and Doug Segar. Word processing services were provided by Ginny Goodwind, Emilia Martins, Renee Ragucci, Audi Stunkard, Lori Duncan, and Susan Prather. Tat Cheung and Johnson Tang of the County of Alameda Public Works Agency contributed their time and talent to the preparation of figures. Melissa Blanton copy-edited the text, surviving the requirements of the author in respect of Anglicisation of local terminologies. Portions of the text were reviewed and improved by the considerable experience and expertise of Bob Spies (Lawrence Livermore National Laboratory), Sam Luoma (U.S. Geological Survey, Palo Alto) and David Young (EPA Laboratory, Newport, OR), as well as by AH1 staff. I am particularly grateful to these technical reviewers who gave their time and talent without complaint. Additional reviewers of the draft report are also acknowledged. Many scientists and non-scientists contributed unpublished data, reprints of material, opinions and ideas. Among these were Ed Long, Don Stevens, Brian Finlayson, Brian Melzian, Chris Foe, Harry Ohlendorf, Jim Arthur, Kris Lindstrom, Jerry Bruns and his staff, Susan Anderson, Mike Carlin, Don Smith, Russ Flegal, Mark Stephenson, Mike Martin, Bob Risebrough, Randy Brown, Del Rasmussen, Greg Cutter, John Calder, Victor DeFlaming, Jeannette Whipple, Bruce MacFarlane, Perry Herrgesell, Mike Josselyn, Jack Linn, Fred Nichols, Don Palawski, Nancy Richard, Greg Karras, Tom Wakeman, Jerry Oglesby and Larry Moritz. Particular thanks are due to Susan Anderson of the San Francisco Regional Water Quality Control Board, who contributed a great deal of effort and time to discussions of the data, and much patience in her role as contract officer. Leo Winternitz is due appreciation for his belief that the report would be completed, in the face of considerable odds. Members of the AH1 Board of Directors should also be mentioned and thanked for their needed votes of confidence at critical periods. Finally, I wish to again note the extraordinary patience, understanding and support of my wife, Lee Phillips, who not only contributes directly to all my products, but also endures their product ion. (ii) -I. INTRODUCTION The San Francisco Bay-Delta Aquatic Habitat Institute (AHI) has been requested under the terms of contract WRCB No. 5-290-120-0 to undertake a variety of tasks for the California State Water Resources Control Board. One of these tasks, termed a IICoordination Element," includes a requirement for the following: I'Prepare a comprehensive report summarizing results of studies that address the effects of pollutants on San Francisco Bay/Delta biota. The report shall include a critical review of the most important research. Whenever possible, summary data shall be presented in an accessible table format and discussed in the text. Conclusions shall address the existing links between pollutant loading and detrimental biological effects with discussion of potential alternative hypotheses." The present report has been prepared in response to this portion of the contract between AH1 and the State Water Resources Control Board. The San Francisco Bay-Delta is the largest estuary on the western coast of the United States, with a surface area of 1,240 2 2 km and a drainage basic of 153,000 km , the latter being about 40% of the area of California. Recent general reviews of the estuary were provided by Conomos & d. (1985) and Nichols a. (1986). The latter authors emphasized the very great historical changes which have occurred in the estuary, particularly since the arrival of white settlers in 1769. These changes include topographic alterations caused by the washdown of debris from hydraulic mining in the Central Valley to the estuary and by the reclamation of land. In addition, much of the natural freshwater inflow to the estuary has been diverted for uses elsewhere, principally in the Central Valley and Southern California. The 1 increasing human population in the Bay-Delta has also had considerable impacts on the estuary, which receives not only sewage and industrial wastes, but also agricultural drainage fro. croplands in the upstream catchment and the Delta itself. In view of these dramatic changes to the Bay-Delta environment, it might be anticipated that equally drastic effect would have been documented with respect to the biological resources of the estuary. To some extent, this is indeed the case. Thus, massive losses of wetland areas have occurred since the mid-1800s. Benthic communities in the Bay-Delta have been totally altered from historical populations, mainly because of the introduction of exotic species. The fishery resource in the estuary has also undergone long-term changes, and some fish populations appear to be continuing to decline. It is a popularly-held belief that pollution of the Bay- Delta has contributed (and is contributing) to the changes in biological resources of the estuary. However, incontrovertible evidence of such effects is rare for any ecosystem, and the Sari Francisco Bay-Delta is no exception. If pollutants are exerting detrimental effects on biota of the Bay-Delta, it is most likely that the contaminants of particular toxicity and persistence in the ecosystem are those with the greatest impact. These so- called lltoxicsllinclude trace metals, organochlorines (chlorinated hydrocarbon pesticides and PCBs), and hydrocarbons. The present report concentrates upon data characterizing these groups of contaminants in the estuary. Published data relating to each of these contaminant types are reviewed, conclusions being reached on the existence or otherwise of elevated 2 concentrations of particular toxicants in components of the Bay- Delta ecosystem. Areas of particular contaminant enrichment are discussed, and where relevant, the estuary is compared to other locations, in order to place local data into a wider context. In the penultimate section of the report, published data concerning biological effects as such are reviewed, a variety of ecosystem resources being considered. Conclusions and recommendations for future study are presented in the final section. The demonstration that contaminants in a given aquatic ecosystem are present at significantly elevated levels and are exerting detrimental effects on biological resources is a challenging task. Toxicants are present in such systems in a bewildering variety of physical and chemical forms, and their toxicological significance is highly dependent upon the precise forms present. For example, contaminants may exist in the water column in solution, in chelates or colloidal forms, or in suspension. Each of these categories includes many types of chemical species, displaying unique bio-availabilities and toxicities to biota. Similarly, toxicants in sediments may be more or less available to biota depending on their exact chemical form and method of binding to sediment particles. Both estuaries themselves and the contaminants residing in these areas are under a continual state of dynamic flux; this interferes with the elucidation of cause-and-effect relationships between toxicants and their biological effects. In most cases, presently-available research and analytical methods provide only a crude picture of the potential for toxic effects of contaminants in aquatic ecosystems. So little is 3 known of the incidence or significance of different chemical forms of even the better-characterized pollutants that their adverse effects generally have to be dramatic for these to be recognized. Similarly, the control of environmental concentrations of contaminants through the regulation of their mass emissions, to permit the attainment and maintenance of watex quality standards or objectives, takes little account of the subtleties of toxicant speciation or bio-availability. The understanding of such matters can be improved only through further research and diligent attempts to enhance present methodologies.