Organic Contaminants in the Shenandoah River – A possible link to declining fish health? David Alvarez US Geological Survey, Columbia Environmental Research Center, Columbia, MO U.S. Department of the Interior U.S. Geological Survey

USGS’s Role in the Shenandoah River Valley USGS has been approached in recent years by other Federal, State, and non-profit organizations to conduct studies to help understand the causes for increased incidences of fish kills and intersex in a variety of fish species. The Columbia Environmental Research Center (CERC) has played a major role in determining the types of chemical contaminants that are present in the surrounding watershed which may be linked to declining fish health.

USGS’s Role in the Shenandoah River Valley Since 2005, CERC has conducted several contaminant studies related to fish health issues in Maryland, West Virginia, and Virginia partnering with: Friends of the North Fork of the Shenandoah River Virginia Department of Environmental Quality Virginia Poultry Foundation US Fish and Wildlife Service US Geological Survey

2005/2006 FWS study (6 sites) Spring/Summer 2007 NF Shenandoah River (2 sites) Spring 2007 VADEQ (10 sites) Spring 2007 USGS (6 sites) Spring 2008 VADEQ (8 sites) Monitoring Sites Using Passive Samplers

Passive samplers – What are they and how do they work? Non-mechanical devices made of plastics and fatty substances that are put into the water for periods of weeks to months They accumulate chemicals from the water in a manner similar to how a fish picks up chemicals They are left in the water for weeks to months Sample 10s-100s more water than standard methods Catch episodic events (surface runoff, spills, etc.)

Passive samplers – What are they and how do they work? Two types of samplers were used: Semipermeable Membrane Device (SPMD) Fat soluble chemicals Polar Organic Chemical Integrative Sampler (POCIS) Water soluble chemicals SPMD POCIS

Chemical Classes Typically Targeted in Each Study Water Soluble Fat Soluble Pesticides Petroleum Chemicals Plasticizers Flame Retardants Industrial Chemicals Hormones Pharmaceuticals Personal Care Products Soaps, Fragrances Lotions/Creams Items used everyday

2005/2006 FWS study 2007 NF Shen R VADEQ study 2007 USGS study 2008 VADEQ study Pesticides Petroleum Chemicals Fragrances Flame Retardants Plasticizers * * Did not look for pharmaceuticals Pesticides Petroleum Chemicals Pharmaceuticals Hormones Pesticides Petroleum Chemicals Fragrances Plasticizers Pharmaceuticals Hormones Pesticides Petroleum Chemicals Fragrances * Pharmaceuticals Hormones * Data Analysis Not Complete Pesticides Petroleum Chemicals * Flame Retardants * * Data Analysis Not Complete Chemical Classes Found During Each Study

Fish Health Determinations in VA, WV, and MD Fish health measurements have been made largely on smallmouth bass; however, largemouth bass and suckers have also been looked at. General Health External Lesions Hormone Levels Vitellogenin Gonad Histology Sperm Quality

Data courtesy of Dr. Vicki Blazer, USGS Leetown Science Center, WV Intersex = organism exhibits characteristics of both sexes (female egg cells in male gonads) Out of basin sites low intersex no fish kills South Branch sites moderate intersex moderate fish kill rates Shenandoah River sites high intersex high fish kill rates Intersex in Smallmouth Bass collected in

Conclusions A wide range of chemicals has been identified, many of which can be linked to agriculture and wastewater/sewage effluents. Pesticides/Herbicides were commonly found throughout the studies. Atrazine was the most commonly found chemical and generally was present at the highest concentrations (up to 2.1 ppb). Pharmaceuticals, fragrances, flame retardants, and caffeine (all wastewater markers) were commonly found, but at low concentrations.

Conclusions Declining fish health and fish kills were evident at many of the study areas indicating a possible link to the contaminants which were present. Pharmaceuticals and personal care products are an emerging, but not new, group of chemicals. These emerging contaminants can enter the environment through many pathways including: treated effluents, direct disposal, leaking septic tanks and runoff. Very little data exists on the fate and transport of these chemicals in the environment.

Acknowledgements CERC Environmental Chemistry Branch Walter Cranor, Stephanie Perkins, Vickie Schroeder, Randal Clark Virginia Department of Environmental Quality Don Kain, Robert Brent, Ted Turner, William VanWort Friends of the North Fork of the Shenandoah River John Holmes, Bud Griswold US Fish and Wildlife Service Chris Guy, Fred Pinkney, Susan Lingenfelser US EPA Region III Lou Reynolds, John Forren, Patricia Mazik Virginia Poultry Foundation Hobey Bauhan US Geological Survey Vicki Blazer, Luke Iwanowicz, Ed Furlong, Steve Werner, Steve Zaugg, Mike Meyer, James Gray, Bill Foreman, Dana Kolpin, Doug Chambers

For more information David Alvarez, USGS, , Investigation of organic chemicals potentially responsible for mortality and intersex in fish of the North Fork of the Shenandoah River, Virginia, during spring of 2007: U.S. Geological Survey Open-File Report Reconnaissance of persistent and emerging contaminants in the Shenandoah and James River Basins, Virginia, during Spring of 2007: U.S. Geological Survey Open-File Report Work by Douglas Chambers, USGS, West Virginia Science Center A reconnaissance for emerging contaminants in the South Branch Potomac River, Cacapon River, and Williams River Basins, West Virginia, April-October 2004: U.S. Geological Survey Open-File Report