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

2. 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

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

4. 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

5. 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 chemicals – drinking water

6. 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 osprey nesting and breeding success – PFOA , PBDE, found in concentration above 1 ug/g wet weight. OC and PCB were also analyzed.

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

8. 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)
Concentration of individual OWC between 1 to 500 ng/L (Alvarez et al 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).

9. 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

10. 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 Effects of Pharmaceuticals on Aquatic Invertebrates (Ch16) in Ed. Kummerer, Pharmaceuticals in the Environment

11. 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

12. 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 ug/L), and Del R. at Trenton, NJ (0.005 ug/L)
Diazinon – MCL 0.6 ug/L- DRBC regulatory criteria

13. 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