EMERGING CONTAMINANTS OF CONCERN IN THE DELAWARE ESTUARY AND WATERSHED A. Ronald MacGillivray Delaware River Basin Commission www.drbc.net DELAWARE ESTUARY SCIENCE CONFERENCE 2007

EMERGING CONTAMINANTS OF CONCERN Substances that have been detected in humans or other living organisms, have been found to be toxic in some way, or are persistent in the environment Not routinely monitored Fate and transport not well understood Consensus has not been reached concerning toxicity Emerging Contaminants – Concern is for both environmental and human health effects/ toxicity PBDE/PFOA – accumulation in fish and humans PPCP - environmental effects

USGS Target List Criteria Quantities in use Anticipated environmental behavior Pathways for release Health significance Ability to measure compound Potential indicator/tracker Stakeholder priorities

USGS National Survey Steroids, nonprescription drugs, and an insect repellent were the three chemical groups most commonly detected in susceptible streams. Detergent metabolites, steroids, and plasticizers generally were found at the highest concentrations. Kolpin et al., ES&T, 2002 Assinpink Creek included in this study Asssunpink Creek at Trenton erythromycin (estimated at) 0.04 µg/L ECOC include phthalate, perchlorate, brominated flame retardants, nanoparticles, pharmaceuticals and personal care products

Activities with Basin Component USGS Surface water Assunpink Creek Delaware River Groundwater Sources of Drinking Water WWTP USEPA Fish tissue study 2006 Target National Sewage Sludge Survey Literature database Contaminated Candidate List (CCL) Interagency Task Group Surface water – Assunpink Creek – passive in-situ sampler – ag/ mun/ ind wastewater Groundwater – fewer cpds and lower conc than surface water Sources of drinking water – 125 cpd at 25 sites WWTP – upstream, effluent, downstream USGS - Streambed sediment, municipal biosolids, landfill leachate – DRB? Other biosolid studies have found the antibacterials triclosan and triclocarban – Rolf Halden – Johns Hopkins U. USEPA – first fish tissue pilot study sample – Aug 2006 – vicinity of West Chester, PA Sewage Sludge Survey – triclosan , triclocarban CCL- Contaminant Candidate List – OGW and DW UCMR 2 – unregulated contaminant monitoring rule 2- 25 chemicals – drinking water

Activities with Basin Component Basin States Delaware New Jersey New York Pennsylvania Others Dr. Rominder Suri, Villanova U. Dr. Jeffrey Ashley, Philadelphia U. Phate model Toschik et al., U Md, USGS, USFWS PWD City of Wilmington Surface water – Assinpink Creek – passive in-situ sampler – ag/ mun/ ind wastewater Groundwater – fewer cpds and lower conc than surface water WWTP – upstream, effluent, downstream USGS - Streambed sediment, municipal biosolids, landfill leachate – DRB? DE and NJ – PBDE NY – NYC reservoirs Dr. Rominder Suri – estrogen homones and antibiotics in WWTP and streams WWTP 4 of 12 estrogens detected 60 to 00% removal antibiotics in WWTP effluent 21 out of 21 streams had detectable estrogens 8 different estrogens were detected 2 streams had 6 different estrogens Limited number od antibiotics were detected Toschik, Pamela , Barnett Rattner , David Carter and others. ET&C vol 24 no 3. pp 617-628 - osprey nesting and breeding success – PFOA , PBDE, found in concentration above 1 ug/g wet weight. OC and PCB were also analyzed.

DRBC Monitoring Fish tissue analysis PBDE, PFOA/PFOS and dioxins/furans along with priority pollutants, PCB, cl-pesticides and metals 2004, 2005, 2006 samples

USGS – Assunpink Creek Alvarez et al. Chemosphere 61 (2005) 610-622 Compared standard depth and width WC sampling to passive in situ sampler 96 target analytes Detected pharmaceuticals, herbicides, flame retardants, plasticizers, alkyl phenols, insecticides, personal care and consumer products Chemosphere 61(2005) 610-622 Concentration of individual OWC between 1 to 500 ng/L (Alvarez et al. 2005 Chemosphere) 32 OWC in polar organic chemical integrative sampler (POCIS), 9 to 25 OWC in individual WC samples Passive samplers – pro – intergated over longer time period con – not quantitative , dissolved compounds only pharmaceuticals (acetaminophen, carbamazepine, dehydronifedipine, diltiazem, diphenhydramine, sulfamethoxazole, thiabendazole), herbicides (atracine, bromacil, metolachlor, and prometon, 3,4-dichlorphenyl isocyanate), flame retardants (tri-(2-chloroethyl)phosphate, tri(dichloroiosopropyl)phosphate and tri(2-butoxyethyl phosphate), plasticizers (bisphenol A, Passive in situ sampler –qualitative - diethylhexyl phthalate, and triphenol phosphate), alkyl phenols (cumylphenol, 4-tert-octylphenol, NPEO2, and OPEO1), insecticides (diazinon and pentachlorophenol), ingredients from personal care and consumer products (anthraquinone, benzophenone, caffeine, cotinine, DEET, HHCB, indole, methyl salicylate, tonalide (AHTN), triclosan, and triethyl citrate).

Endocrine Disruptors An endocrine disruptor is an exogenous substance or mixture that alters function(s) of the endocrine system and consequently causes adverse health effects in an intact organism, its progeny, or (sub)populations. (WHO, 2002) Endocrine system - Hormones act as "messengers," and are carried by the bloodstream to different cells in the body From endocrine glands are pituitary, thyroid, and adrenal glands. Role in body body metabolism, growth and development, and reproduction Endocrine disruptors – mimic, bind or inhibit hormone activity

Toxicity Testing If a substance is a suspected endocrine disruptor, toxicity endpoints and test organisms must be able to display such effects. acute and chronic toxicity test aquatic - fish, daphnid, algae sediment- oligochaete, midge and mudsnail clofibric acid – acute toxicity to daphnid carbamazepine – chronic toxicity to midge Carbamazapine – antiepileptic agent Clofibric acid – metabolite of lipid lowering compound clofibrate Chironomidae - Chironomus riparius – arrested development in the fourth larval stage, disabling the formation of the pupae Larvae observed lying on the surface of the sediment convulsing Nentwig et at. 2004. Effects of Pharmaceuticals on Aquatic Invertebrates (Ch16) in Ed. Kummerer, Pharmaceuticals in the Environment

EPA Endocrine Disruptor Screening Program Tier 1 Screening Assays (In final validation peer review stage) Fish screen Pubertal female assay (rat) Pubertal male assay (rat) Uterotrophic assay (rat) Tier 2 Testing Assays (none in final development) Amphibian development, reproduction Avian 2-generation Pubertal assay - Abnormalities in sex organs and puberty markers, as well as thyroid tissue. Uterotrophic assay – in vivo – uterine weight in ovariectomized or immature female rats

Transition From Unregulated to Regulated Compound and Criteria Development EPA Ambient Aquatic Life Water Quality Criteria 2006 freshwater µg/L saltwater µg/L acute chronic diazinon 0.17 0.82 nonyl phenol 28 6.6 7.0 1.7 Nonyl phenol 0.41 µg/l (site 2) – 2 miles downstream of a WWTP Alvarez et al. 2005 Design for the Environment Safer Detergents Stewardship Initiative (SDSI) Diazinon detected at two sites tested by USGS – Del R at Port Jervis, NY (estimated at 0.001 ug/L), and Del R. at Trenton, NJ (0.005 ug/L) Diazinon – MCL 0.6 ug/L- DRBC regulatory criteria

DRBC Moving Forward Identify Understand Prioritize monitoring Understand fate and effects Prioritize develop Delaware River Basin target list Compilation of within basin data on ECOC Identification of data gaps Adapting monitoring to current priorities Partnering on ECOC initiatives