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