Loadings of Pharmaceutical and Personal Care Products (PPCPs) and Endocrine Disrupting Chemicals (EDCs)from Small Rural Streams into an Urban Drinking Water Source

Thomas B. Huff1,*, Jun Liu1

and Gregory D. Foster21Shared Research Instrumentation Facility, George Mason University, Manassas, VA, 20110, 2

Department of Chemistry and Biochemistry, George Mason University, Fairfax, VA, 22030

Abstract ResultsMethods

Conclusions

Introduction

Pharmaceutical and personal care products (PPCPs) and endocrine disrupting chemicals (EDCs) have been investigated for their potential to disrupt aquatic ecosystems. Current research focuses on their potential to impact human health through incomplete removal in some drinking water treatment systems that rely on surface water

sources that are also receiving sewage effluent and runoff from agricultural practices. Effective mitigation will require knowledge of existing concentrations and loadings from tributaries into drinking water supplies.

Water and suspended sediment samples were obtained on a monthly basis during storm and base flow conditions from Cedar Run and its smaller tributaries. Cedar Run is a creek that drains 242 sq km of rural Fauquier County in Virginia’s Piedmont region. The county land use consists of cattle and corn agricultural operations as well as small towns with septic tank systems. Discharge from Cedar Run has been measured at USGS gauging station number 01656000—the primary sampling location—at greater than 62 cubic meters per second. This discharge enters the Occoquon

River which is the source of drinking water for Fairfax County, Virginia, an urban-suburban county with a residential population of over 1 million.

Samples were analyzed for a suite of 50 common PPCPs and EDCs including antibiotics, estrogenic steroids and household chemicals. Extractions of dissolved phase samples were performed using Oasis solid-phase extraction cartridges (Waters Corp., Milford, MA). Extractions of filtered suspended sediments were performed

using a MARS (microwave accelerated reaction system; CEM Corporation, Matthews, NC). Extracts were analyzed by a combination of GC-MS and LC-MS protocols.

Agricultural EDCs such as atrazine

and its metabolites and PPCPs such as trimethoprim, sulfamethoxazole

and caffeine were frequently detected in concentrations ranging

from ng

to ug

per liter. Instantaneous and seasonally estimated loadings of detected analytes are presented here.

Field Sampling

Cole Parmer Environmental SamplerMasterflex

peristaltic pump with Masterflex

phthallate-free tubing and 20 L stainless-

steel Cornelius kegs

Filtration and Sample Aliquoting Solid Phase Extraction

Solid Phase Extraction ProtocolWaters Corp. Oasis HLB SPE Cartridges

Supelco

Visiprep

vacuum manifold

•6 mL

HLB cartridge with 200 mg sorbent•Wash with 3 mL

MTBE, MeOH

and ultra-pure DI•Load 1 L Filtered River Water per cartridge

at 5-10 mL/min•Wash with 3 mL

ultra-pure DI•Elute with 9 mL

of 10:90 MeOH:MTBE

over Na2

SO4

•Composite 4 1-L extracts per autosampler

vial•Centrivap

and N2 blowdown

to 0.5 mL

GC-MS AnalysisAgilent Technologies

5890 Series II GC5971 Mass Selective Detector

Restek

Rtx®-5 Amine Capillary Column 0.25 mm ID x 0.25 mm x 30 m

Restek

Base Deactivated Gooseneck Liner1.0 mL/min EPC constant flow with pulse

Splitless

injection with 0.5 min purge

Collect and Pressure Filter20 L Surface Water Sample

Solid Phase Extraction Reserve Filtered ParticulatesFor subsequent extraction and analysis

Exchange to Non-Polar Solventfor GC-MS Analysis

Exchange to Aqueous SolventFor LC-ESI-MS Analysis

High Purity Nitrogen Pressure FiltrationWhatman

GF/F 0.7 mm Glass Fiber Filters

Pharmaceuticals and Household Chemicals

Sulfonamide Antibiotics

Acidic Herbicides

LC-ESI-MS Analysis

Mobile phase A: 0.1% acetic acid in ultra-pure water -

Mobile Phase B: 0.1% acetic acid in acetonitrile

–

Flow Rate 0.200 mL

per minute

Waters Corp. 2695 Alliance Separations ModuleWaters ZQ 2000 ESI Single-Quad Mass SpectrometerWaters Atlantis dC18 column 5 μm 2.1 mm x 150 mm

ON & OP PesticidesIDL

(ng/L) % rsdDI Spike

(N=5)Dichlorvos 1.8 2.2% 77%EPTC 1.5 1.4% 72%Mevinphos 3.5 4.4% 69%Butylate 3.0 2.7% 69%Vernolate 1.4 1.5% 70%Pebulate 1.7 1.6% 71%Molinate 3.5 3.3% 75%Propachlor 1.9 1.9% 79%Ethoprop 4.2 5.3% 91%Atrazine-desisopropyl 8.0 9.0% 52%Atrazine-desethyl 2.1 2.4% 86%Simazine 3.7 4.0% 80%Atrazine 3.0 2.7% 82%Propazine 4.0 4.0% 84%Diazinon 8.2 12.1% 68%Acetochlor 4.2 5.2% 85%Methyl parathion 7.2 9.3% 75%Alachlor 3.0 3.9% 88%Metolachlor 3.6 4.0% 86%Hexazinone 5.7 5.4% 94%

ON & OP Pesticides IDL (ng/L) % rsdDI Spike

(N=5)Sulfathiazole 0.23 2.7% 35%Trimethoprim 0.21 4.0% 81%Sulfamethazine 0.14 2.3% 88%Sulfamethoxazole 0.15 2.3% 83%Sulfadimethoxine 0.10 1.5% 95%Sulfaquinoxaline 0.13 1.9% 69%Dalapon 0.10 0.7% 9%Picloram 1.85 13.3% 3%Dicamba 0.20 1.5% 23%2,4-D 0.13 1.0% 53%Dicloroprop 0.29 2.0% 109%2,4,5-T 0.31 2.0% 54%2,4-DB 0.29 1.9% 110%2,4,5-TP 0.34 2.2% 104%Enoxacin 0.96 11.6% 4%Norfloxacin 1.12 11.6% 3%Ciprofloxacin 1.17 10.2% 1%Danofloxacin 1.16 11.1% 15%Enrofloxacin 1.20 7.4% 12%Sarafloxacin 0.92 3.6% 9%Cotinine 0.45 1.5% 77%Roxarsone 1.23 4.4% 60%Acetaminophen 0.17 0.5% 42%Caffeine 0.84 2.8% 123%Penicillin G 0.38 1.4% 40%Amoxicillin 0.18 0.7% 87%Tylosin 0.41 1.4% 67%Atrazine 0.31 1.1% 129%

Cedar Run Sampling

-100

100

300

500

700

900

1100

1300

1500

7/22/06 10/30/06 2/7/07 5/18/07 8/26/07

Disc

harg

e (ft

3/se

c)

Discharge Sample Date

Date Picloram Dicamba 2,4-D Dicloroprop 2,4,5-T 2,4-DB 2,4,5-TP23-Sep-06 7.0 4.2 25.2 0.8 0.0 4.9 0.06-Oct-06 0.0 0.0 5669.4 0.0 0.0 314.8 0.0

15-Apr-07 12333.6 8.4 20235.4 828.8 0.0 2357.9 0.014-May-07 0.0 0.0 1052.0 12.0 0.0 55.0 4.33-Jun-07 0.0 0.0 86.2 3.4 0.0 0.0 0.0

13-Jun-07 0.0 0.0 43.5 1.8 0.0 0.0 0.020-Jul-07 0.0 0.2 7.5 0.7 0.0 0.0 0.07-Aug-07 14.9 3.9 3.8 0.4 0.0 0.8 0.0

21-Aug-07 26.5 9.3 9.7 0.0 0.0 2.1 0.026-Aug-07 64.5 14.4 6.6 0.0 0.0 3.3 0.015-Sep-07 3.9 0.0 2.2 0.0 0.0 1.4 0.0

13-Oct-07 0.6 0.0 0.0 0.0 0.0 0.0 0.025-Oct-07 1695.9 0.0 209.5 18.1 83.7 168.1 41.327-Oct-07 0.0 0.0 20.6 0.0 7.0 7.7 11.5

DateSulfa-

thiazole TrimethoprimSulfa-

methazineSulfa-

methoxazoleSulfa-

dimethoxineSulfa-

quinoxaline23-Sep-06 17.5 0.1 0.0 0.0 0.0 0.06-Oct-06 0.6 0.0 0.0 559.0 0.5 0.0

15-Apr-07 516.8 0.0 0.0 0.0 0.0 1477.314-May-07 5.5 0.0 0.0 0.0 0.0 4.93-Jun-07 5.3 0.0 0.0 0.0 0.0 1.0

13-Jun-07 0.2 0.0 0.0 0.0 0.0 7.819-Jul-07 0.0 0.0 0.0 0.0 0.0 4.77-Aug-07 2.7 0.2 0.0 0.0 0.0 0.0

21-Aug-07 2.8 0.7 0.0 0.0 0.0 0.026-Aug-07 3.9 0.3 0.3 0.0 0.0 0.015-Sep-07 0.7 0.0 0.1 0.1 0.1 0.0

DateAtrazine-

desisoprAtrazine-

desethyl Simazine Atrazine Propazine Diazinon Acetochlor Metolachlor Hexazinone23-Sep-06 3.74 2.32 2.78 6.28 0.00 0.00 0.00 0.00 3.346-Oct-06 0.00 1736.84 265.61 1842.80 0.00 0.00 149.68 1128.82 0.00

15-Apr-07 2058.52 2832.25 1061.20 5264.05 481.16 0.00 369.36 6303.84 878.9314-May-07 48.90 70.56 59.76 247.99 13.95 0.00 22.49 166.58 18.333-Jun-07 0.00 35.56 8.38 15.29 0.00 0.00 0.00 0.00 0.0013-Jun-07 41.42 59.02 42.74 182.03 11.24 0.00 15.92 137.27 16.1119-Jul-07 0.00 3.35 2.28 10.11 0.00 0.00 0.00 4.55 0.007-Aug-07 0.95 0.56 0.66 1.58 0.00 0.00 0.00 0.00 0.7921-Aug-07 61.48 30.43 0.00 9.65 0.00 0.00 0.00 11.02 52.9526-Aug-07 5.47 3.90 2.97 8.56 0.00 0.00 0.00 0.00 3.9315-Sep-07 0.00 1.99 3.49 2.75 0.00 0.00 0.00 0.83 3.2613-Oct-07 0.68 0.03 0.00 0.11 0.00 0.00 0.00 0.00 0.0725-Oct-07 74.09 23.53 18.73 24.42 0.00 0.00 0.00 0.00 0.0027-Oct-07 287.85 58.46 36.19 76.83 0.00 0.00 0.00 0.00 55.19

Date Cotinine Acetaminophen Caffeine Penicillin G Amoxicillin Tylosin Atrazine23-Sep-06 0.0 0.0 0.5 0.0 0.2 0.0 8.96-Oct-06 0.0 0.0 108.0 0.0 0.0 0.0 2150.1

15-Apr-07 150.1 0.0 2486.9 0.0 0.0 0.0 2204.914-May-07 9.8 0.0 0.0 0.0 0.0 0.0 108.03-Jun-07 2.4 0.0 12.6 0.0 0.0 0.0 19.6

13-Jun-07 4.7 1.7 20.6 0.0 0.0 0.0 162.319-Jul-07 0.8 0.6 7.4 0.0 0.0 0.0 7.47-Aug-07 0.2 0.2 0.5 0.0 0.0 0.0 1.8

21-Aug-07 0.7 0.0 3.5 0.0 0.0 0.0 4.326-Aug-07 1.4 0.6 3.1 0.0 0.0 0.0 6.615-Sep-07 0.4 0.2 1.6 0.0 0.0 0.0 1.7

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Cedar Run ‘Instantaneous’

Fluxes

μg analyte per second

at USGS gaging

station 01656000 Near Catlett, VA

There are over 1800 approved animal drug formulations used in agriculture. Antibiotics make up a major subset of those drugs. Of the 23 million kilograms of antibiotics used in the United States annually, over 11 million kilograms are used in agriculture (UCS 2001). Over 90% of antibiotics used each year in poultry, beef and swine production are administered prophylactically in sub-therapeutic doses on a nearly constant basis through their addition to food and water (Barlam 2002). Antibiotics have also been thought to act as growth promoters and have been used extensively to boost production in livestock operations (Feighner

and Dashkevicz

1987).Many of the pharmaceuticals administered to animals are excreted

through their waste, often by as much as 75 to 100% (Lindberg, Wennberg

et al. 2005). In 1992, it was reported that animal production throughout the US produced over 130 million dry tons of waste compared to 10 million dry tons of human waste per year (US EPA OWSASD, 1999). This waste is typically applied to crops as a fertilizer and soil conditioner. Runoff and leachate

from that waste introduces antibiotics and other contaminants into surface and ground water (Pedersen, Soliman

et al. 2005). Environmental antibiotics may alter the ecology of watersheds (Halling-Sorensen 2000; Wollenberger

2000) and may produce hazardous strains of antibiotic-

resistant bacteria (Hirsch 1999). Although preliminary studies have documented the presence of antibiotics in surface and ground water in many locations (Kolpin

2002), little is known about the long-term extent of the incidence and transport of environmental antibiotics (Loffler, Rombke

et al. 2005). The first step to understanding the environmental impact of antibiotics is to quantify their levels in the watersheds where they are likely to occur.

The goal of this pilot study is to develop a utile protocol for sampling surface water samples, filtering the suspended particulates, extracting analytes and deteriming

fluxes in areas deemed worthy of study

Cedar Run

Site

Cedar Run Basin

Flow

The protocols developed in this study proved useful in determining river fluxes of compounds associated with agriculture land-use practices. Herbicides were detected in samples during storm water runoff and during seasonal application periods. This

is consistent with the historical land use in the Cedar Run drainage basin.

Acknowledgements:Vikas

Chandhoke, Dean, College of Sciences, George Mason University. Thanks to research assistants Mike Gaal, Ishan

Baradin, Sophia Yuon. Special thanks to Riverman

Nathan Huff, age 5, without whom this work would have been much less fun.

ON & OP Pesticides