STOTEN-10483; No of Pages 8

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a v a i l a b l e a t w w w. s c i e n c e d i r e c t . c o m

w w w. e l s e v i e r. c o m / l o c a t e / s c i t o t e n v

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Edward Toppa,, Sara C. Monteirob , Andrew Beckc , Bonnie Ball Coelhoa ,

Alistair B.A. Boxallb,d , Peter W. Duenke , Sonya Kleywegt f , David R. Lapeng ,
Michael Payneh , Lyne Sabourina , Hongxia Lii , Chris D. Metcalfei

OO
F

Agriculture and Agri-Food Canada, London, Canada ON N5V 4T3

Environment Department, University of York, YO10 5DD, UK
c
Health Canada, New Substances Assessment and Control Bureau, Ottawa, Canada K1A 0K9
d
Central Science Laboratory, Sand Hutton, York YO41 1LZ, UK
e
Department of Biology, University of Western Ontario, London, Canada ON N6A 5B7
f
Ontario Ministry of the Environment, Toronto, Canada ON M4V 1M2
g
Agriculture and Agri-Food Canada, Ottawa, Canada K1A 0C6
h
Ontario Ministry of Food, Agriculture and Rural Affairs, Stratford, Canada ON N5A 5T8
i
Worsfold Water Quality Centre, Trent University, Peterborough, Canada ON K9J 7B8
b

PR

Runoff of pharmaceuticals and personal care products

following application of biosolids to an agricultural field

ED

15

AR TIC LE I N FO

ABS TR ACT

24

Article history:

Municipal biosolids are a source of nutrients for crop production. Beneficial Management

25

Received 22 August 2007

Practices (BMPs) can be used to minimize the risk of contamination of adjacent water

26

Received in revised form

resources with chemical or microbial agents that are of public or environmental health

27

4 February 2008

concern. In this field study, we applied biosolids slurry at a commercial rate using either

28

Accepted 5 February 2008

subsurface injection or broadcast application followed by incorporation. Precipitation

RE

was simulated at 1, 3, 7, 22, 36 and 266 days post-application on 2 m2 microplots to

29
30

evaluate surface runoff of 9 model pharmaceuticals and personal care products (PPCPs),

31

atenolol, carbamazepine, cotinine, gemfibrozil, naproxen, ibuprofen, acetaminophen,

32

35
36
37
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47

Q1

model PPCPs were generally below the limits of quantitation. In contrast, in the broadcast

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34

sulfamethoxazole and triclosan. In runoff from the injected plots, concentrations of the
application treatment, the concentrations of atenolol, carbamazepine, cotinine, gemfibrozil,
naproxen, sulfamethoxazole and triclosan on the day following application ranged from 70
1477 ng L 1 in runoff and generally declined thereafter with first order kinetics. The total
mass of PPCPs mobilized in surface runoff per m2 of the field ranged from 0.63 g for atenolol
to 21.1 g for ibuprofen. For ibuprofen and acetaminophen, concentrations in runoff first
decreased and then increased, suggesting that these drugs were initially chemically or
physically sequestered in the biosolids slurry, and subsequently released in the soil.

UN

33

CT

17

Carbamazepine and triclosan were detected ay low concentrations in a runoff event 266 days
after broadcast application. Overall, this study showed that injection of biosolids slurry
below the soil surface could effectively eliminate surface runoff of PPCPs.
2008 Elsevier B.V. All rights reserved.

Corresponding author.
E-mail address: toppe@agr.gc.ca (E. Topp).
0048-9697/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.scitotenv.2008.02.011

Please cite this article as: Topp E, et al, Runoff of pharmaceuticals and personal care products following application of
biosolids to an agricultural field, Sci Total Environ (2008), doi:10.1016/j.scitotenv.2008.02.011

ARTICLE IN PRESS
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1.

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2.1.

Site description

109

PPCPs are excreted or discarded into urban wastewaters

and these residues eventually make their way into wastewater
treatment plants (WWTPs). Within WWTPs, some of these
substances may be relatively resistant to elimination (Joss
et al., 2005), and may be sequestered into biosolids (Golet et al.,
2002; Gbel et al., 2005; Ternes et al., 2005; Xia et al., 2005;
Kinney et al., 2006). Heberer (2002) and Sacher et al. (2001)
observed that PPCPs were transported into underlying groundwater when municipal biosolids were applied onto agricultural land. Some pharmaceuticals have been detected in fields
that had been irrigated with treated wastewater (Pedersen
et al., 2005). Veterinary pharmaceuticals can be transported in
runoff from land receiving animal manures (Kay et al., 2005;
Kreuzig et al., 2005; Davis et al., 2006). On this basis, PPCPs
associated with biosolids that are applied to agricultural fields
have the potential to be transported in surface runoff.

Liquid municipal biosolids (LMB) were obtained from a storage

lagoon in southern Ontario that holds the discharge from four
municipal sewage treatment plants that serve a total population of about 300,000 people. The LMB obtained from the
primary settling tank had been stored anaerobically. The
control consisted of groundwater obtained from the site that
was briefly ozonated, and then stored in large polyethylene
plastic containers for about 12 h.
Table 1 lists the PPCPs evaluated in this study. In order to
ensure their detection, some selected analytes were added (i.e.
spiked) to the LMB or to water used in the control treatment
prior to application at the nominal concentrations listed in
Table 1. Based on preliminary experiments with the LMB
that showed that some of the analytes desorbed from
biosolids at concentrations detectable in water, several of
the target analytes were not spiked into LMB. Chemicals
spiked into the LMB were dissolved or suspended in 3 L of
methanol, and this was dispensed into the tanker (capacity

124

Table 1 Model analytes for field studies of the transport

of PPCPs in runoff, and the stable isotope-labeled
surrogates that were used for analytical quantitation

t1:1
t1:2

Analyte class

t1:3

The experiment took place at the field station of the University

of Western Ontario (latitude 434'47N, longitude 8120'24W)
from August 2005 to April 2006. The soil at the site is a silt loam
(grey brown Luvisol) belonging to the Bryanston soil association, with the following key properties: pH of 7.5, sand/silt/clay
composition of 18:67:15, and organic matter content of 3.4%.
The field was cropped to soybeans in 2004, and following
harvest was sown to winter wheat in the fall of 2004. The
wheat was harvested and straw removed in July of 2005 and
the LMB application took place on soil with wheat stubble
(about 15 cm in height). A topographic survey was conducted
to determine the slope of the field, which averaged 5%.
Antecedent tillage treatments contoured the slope.

110

2.2.

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In the province of Ontario Canada, about 40% of the biosolids (i.e.

treated sewage sludge) generated from domestic waste, or about
16,000 dry tonnes are applied annually to approximately 2000 ha
of agricultural land. About half of this material is applied as a
slurry, referred to as liquid municipal biosolids (LMB; M. Payne,
unpublished data). The risk of reduced water quality from the
transport of microbial or chemical contaminants carried in the
LMB is managed through regulations that specify suitable land
characteristics and soil conditions, application timing and rates,
and acceptable LMB composition, such as heavy metal content
(Walker et al., 1994; CTPBAL, 2002). Previous studies have shown
that overland transport from fields amended with biosolids can
impact the quality of surface water through runoff of heavy
metals (Alloway and Jackson, 1991) and nutrients (Withers et al.,
2001). Thus, there is interest in determining the transport of
contaminants of emerging interest, including pharmaceuticals and personal care products (PPCPs) from fields that are
amended with biosolids.

Field applications and runoff simulations

DP

55

108

TE

54

Materials and methods

RR
EC

53

2.

In this field study, we investigated the transport of PPCPs

entrained in overland flow from portions of a sloping agricultural field that had received LMB. Prior to application,
selected PPCPs were spiked into the LMB, but other drugs were
present at relatively high concentrations as a result of contamination of domestic sewage. Two common commercial
methods of LMB application were employed using identical
LMB application rates: i) surface broadcast plus subsequent
(within 24 h) incorporation of the material into surface soils by
cultivation; and ii) injection (10 cm depth) of LMB directly into
surface soils. For comparison, a control treatment consisted of
injected water supplemented with selected PPCPs. Postapplication, precipitation was applied to micro-plots using
rainfall simulators. Overland flow produced from the rainfall
events was collected and analyzed for PPCPs. Monitoring was
conducted at intervals over an initial post-application period
of 36 days, and again at 10 months (266 days) post-application.
Our specific study objectives were to: i) compare the two LMB
application methods for the capacity to mitigate the risk of
transport of contaminants in overland flow (i.e. runoff) under
typical sloping field conditions. ii) evaluate the nature of the
post-application decline in concentrations of contaminants
entrained in overland flow.

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Introduction

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Q2

SC IE N CE O F THE TOTA L E N VI RON ME N T XX ( 2 00 8 ) XXXX XX

Acidic drugs

Neutral drugs
Beta-blocker
drug
Sulfonamide
antibiotic
Bacteriocide

Analytes
Gemfibrozil
(10 g L 1)
Naproxen (10 g L 1)
Ibuprofen
Acetaminophen
(100 g L 1)
Carbamazepine
cotinine
Atenolol (10 g L 1)
Sulfamethoxazole
(10 g L 1)
Triclosan

Labeled surrogates

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121
122

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135
136
137
138
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140
141

Gemfibrozil-d6

t1:4

Naproxen-13C1, d3
Ibuprofen-13C3
Acetaminophen-d3

t1:5
t1:6
t1:7

Carbamazepine-d10
cotinine-d3
Atenolol-d7

t1:8

Sulfamethoxazole-13C6

t1:10

Triclosan-13C12

t1:11

Analytes that are underlined were spiked into the LMB and water
(i.e. the control treatment) prior to field application at the nominal
concentrations shown in brackets.

Please cite this article as: Topp E, et al, Runoff of pharmaceuticals and personal care products following application of
biosolids to an agricultural field, Sci Total Environ (2008), doi:10.1016/j.scitotenv.2008.02.011

t1:9

t1:12

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201

204

Naproxen, ibuprofen, gemfibrozil, acetaminophen, cotinine,

carbamazepine, sulfamethoxazole and atenolol were supplied
by Sigma-Aldrich (Oakville, ON, Canada), and triclosan was
obtained from Wellington Laboratories (Guelph, ON). Acetaminophen-D3, gemfibrozil-D6, cotinine-D3 and atenolol-D7 were
supplied by C/D/N Isotopes Inc. (Pointe-Claire, QC, Canada).
Carbamazepine-D10, naproxen-13C1, D3, ibuprofen-13C3, sulfamethoxazole-13C6 and triclosan-13C12 were supplied by Cambridge Isotope Laboratories (Andover, Maryland, USA). The
purity of all chemicals wasN98% according to the suppliers.

205

2.4.

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Chemicals

Sample preparation

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All samples of runoff (2 L) were processed immediately after

collection. Suspended particulates were removed from the
aqueous phase by centrifuging 150 mL aliquots for 10 min
(Sorvall RC2-B, SLA-1500 rotor, 4600 g). The aqueous samples
were decanted from the centrifuge bottles, pooled, and stored
in the dark at 4 C for less than 48 h before extraction. Each
aqueous sample was divided into five aliquots of 250 mL, with
each aliquot corresponding to five different classes of PPCPs
(Table 1). After adjustment of the pH of the sample (see below),
the stable-isotope labeled surrogates were spiked into the
samples at nominal concentrations of 100 ng L 1.
Acidic drugs, neutral drugs and sulfamethoxazole were
extracted essentially as described by Miao et al. (2002),
Metcalfe et al. (2003) and Miao et al. (2004), respectively. To
extract triclosan from aqueous samples, the pH was adjusted
to 6.0 by adding 3.5 M H2SO4. After conditioning the Oasis SPE
cartridge with sequential additions of 6 mL ethyl acetate/
acetone (50:50), 6 mL methanol, and 6 mL HPLC grade water
adjusted to pH = 6.0, the sample was passed through an HLB
Oasis cartridge at a rate of approximately 5 mL/min. The
sample container was rinsed with 10 mL of pH = 6.0 distilled
water and the rinsings were passed through the cartridge. Two
mL of ethyl acetate/acetone (50:50) were added and allowed to
remain in the cartridge for 10 min. This step was repeated
twice, for a total elution volume of 6 mL of 50:50 ethyl acetate/
acetone. To extract atenolol, the pH was adjusted to 3.0 by
adding 3.5 M H2SO4. After conditioning the HLB Oasis MCX SPE
cartridge with 6 mL methanol and 10 mL HPLC grade water at
pH 3.0, the sample was passed through the cartridge at a rate
of approximately 10 mL/min. The sample container was
rinsed with 10 mL of pH 3.0 distilled water and the rinsings
were passed through the cartridge. The cartridge was then
washed with 6 mL methanol (discarded). 3 mL of 5%
ammonium hydroxide in methanol were added, and allowed
to remain in the cartridge for 10 min. This step was repeated
twice, for a total elution volume of 9 mL of 5% ammonium
hydroxide in methanol.

216

2.5.

253

PR

147

2.3.

ED

146

place on Days 1, 3, 7, 22 and 36 post-application. In addition, a 202

simulation was done the following spring on day 266.
203

CT

145

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144

15,400 L) immediately before it was filled with LMB at the

WWTP so that the chemicals would be uniformly mixed during transit to the experimental site.
Two different LMB application methods (subsurface injection, and surface broadcasting followed by shallow incorporation, both at a standard commercial rate of 10,000 US gal ac 1
(i.e. 93,500 L ha 1) were each applied to individual plots
measuring 15 m wide by 40 m long. Water was applied to a plot
of equal size in the control treatment by injection at the same
rate. The injection toolbar system consisted of seven Vibroshanks (Kongskilde Ltd., Strathroy, ON, Canada), spaced 38 cm
apart, set behind coulters and in front of levelling harrows.
Slurry drop tubes, connected to a slurry distributor fed by a
tanker nurse hose, were fitted behind the tines to facilitate
slurry injection along furrow bottoms. The toolbar was drawn
behind a tanker of 2650 L capacity equipped with in-tank
mixing (Nuhn Industries, Sebringville, ON). The rate and the
uniformity of application was assured with a SkyTrak GPS
velocity sensor (Squibb Taylor, Dallas TX) in combination with
a flowmeter (IFC 010 signal converter, Krohne Inc., Peabody,
MA) and a flow controller (SCS 660 serial interface, Raven
Industries, Sioux Falls, ND). The tines/drop tubes were poised
20 cm above the soil surface for the broadcast application, or
pulled through the soil at a depth of 10 cm for the injection.
LMB was incorporated into the broadcast macroplot the day
after surface application (i.e. Day 1) at a depth of 15 cm using a
Kongskilde vibro-shank cultivator.
On Day 1 post-application, 25 three-sided rectangular
galvanized steel frames (2.0 m 1.0 m, Spencer Steel Ltd.,
Ilderton ON) were inserted within each of the 3 plots to a depth
of 10 cm into the soil to delineate and contain the areas for
each rainfall simulation. Overland flow from these microplots was directed, via galvanized steel weirs, into 10 L Teflon
lined jerry cans (Fisher Scientific, Ottawa ON) inserted into the
ground at the down slope end of each micro-plot. Simulations
were continued until a minimum of 10 L of runoff was collected in the jerry cans, so the total rainfall applied to each
microplot varied. Samples were transferred to 10 L Teflon
carboys for immediate transport to the laboratory. Carboys
were washed with 95% ethanol and thoroughly rinsed with
water 3 times prior to each runoff sampling event.
Portable field microplot rainfall simulation units were
constructed using 45 mm angle iron to form a frame 2.5 m
long 1.5 m wide and 1.0 m high. Vinyl Bristol boards were
attached to the sides of the frame to minimize wind distortion
of the rainfall pattern and evaporation. Water was supplied to
the simulation unit from a polyethylene 100 L reservoir
equipped with a 8 L min-1 capacity pump (LG-25-P, Delaware
Pump and Parts, Delaware, ON), delivered through clear vinyl
tubing (8 mm I.D.) at a pressure of 4 PSI and delivered through
two square nozzles (SS Fulljet 3/8HH27WSO and 3/8HH24WSO,
HJV equipment, Hensall ON) attached to a motorized motion
track device (Model SA P/N 4002-008, Ontario Grower Supply,
London, ON) to allow for even rainfall distribution over the
area. Travel time of the motor end-to-end was approximately
75 s. Simulations used groundwater obtained from the site
that was briefly ozonated, and then stored in large polyethylene plastic containers for about 12 h. The measured water
application rate was 7.0 + 0.7 L min 1. Following the application of LMB or water on August 8, 2005, rain simulations took

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Analysis

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229
230
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233
234
235
236
237
238
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240
241
242
243
244
245
246
247
248
249
250
251
252

Acidic drugs were analyzed by liquid chromatography with 254

electrospray ionization tandem mass spectrometry (LC-ESI- 255

Please cite this article as: Topp E, et al, Runoff of pharmaceuticals and personal care products following application of
biosolids to an agricultural field, Sci Total Environ (2008), doi:10.1016/j.scitotenv.2008.02.011

ARTICLE IN PRESS
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264
265
266
267
268
269
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273
274
275
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277
278
279
280
281
282
283

t2:2

Table 2 Multiple reaction monitoring (MRM) ion transitions, approximate chromatographic retention time (min), optimized
collision energies (eV) and optimized cone voltages (V) for LC-MS/MS analysis of model PPCPs and their labeled surrogates

t2:3

Compound

t2:4
t2:5
t2:6
t2:7
t2:8
t2:9
t2:10
t2:11
t2:12
t2:13
t2:14
t2:15
t2:16
t2:17
t2:18
t2:19
t2:20
t2:21
t2:22
t2:23
t2:24
t2:25
t2:26
t2:27
t2:28
t2:29
t2:30

Acidic drugs
Gemfibrozil
Naproxen
Ibuprofen
Acetaminophen
Gemfibrozil-d6
Naproxen-13C1,d3
Ibuprofen (propionic)-13C3
Acetaminophen-d3

t2:31

Note that triclosan was analyzed by LC-MS/MS using selected reaction monitoring (SRM).

Retention time
(min)

Collision energy
(eV)

Cone voltage
(V)

249 N 121
229 N 170
205 N 161
152 N 110
255 N 121
233 N 174
207 N 163
155 N 111

12.9
7.41
10.41
3.00
12.9
7.4
10.43
3.02

12
6
9
18
12
6
9
18

25
25
25
30
25
25
25
30

10.9
7.1
10.9
7.1

40
40
25
40

28
40
30
40

RR
EC

MRM transition
(precursor N product)

CO

Neutral drugs
Carbamazepine
Cotinine
Carbamazepine-d10
Cotinine-d3

UN

t2:1

Triclosan was analyzed by LC-ESI-MS/MS using the Micromass instrument as described by Chu and Metcalfe (2007).
Selected reaction monitoring (SRM) in negative-ion mode was
employed to analyze triclosan, which in this case involved
monitoring the deprotonated molecular ion (Table 2).
The neutral pharmaceuticals were analyzed by liquid
chromatography with atmospheric pressure chemical ionization and tandem mass spectrometry (LC-APCI-MS/MS), essentially as described by Zhao and Metcalfe (in press). An APCI
source was used because this ionization source is less
susceptible to matrix-induced suppression of the ion signal
in comparison to the ESI source (Miao and Metcalfe, 2007). The
analytical system consisted of an Agilent 1100 series binary
pump and autosampler and a QTrap mass spectrometer (MDS
Sciex, Toronto, ON) equipped with an APCI source. Using the
Analyst 1.4 system software, MRM with unit resolution on
both of the first and second mass analyzer was selected for
data acquisition in positive-ion mode. The ion transitions
selected for MRM are listed in Table 2.
Sulfamethoxazole was also analyzed by LC-APCI-MS/MS
using the same analytical system described for analysis of
neutral drugs. Data acquisition was in positive-ion mode and
the transition ions selected for MRM are listed in Table 2. The
mass spectrometric parameters were optimized as follows:
curtain gas 15 psi, nebulizer gas 70 psi, auxiliary gas 15 psi,
corona discharge needle current 2.0 A, probe temperature
460 C, interface heater on, CAD gas 5. The collision energy and
declustering potential determined for each compound are

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MS/MS), essentially as described by Miao et al. (2002). The

acidic pharmaceuticals were analyzed with a Micromass
(Manchester, U.K.) Quattro LC triple quadrupole mass spectrometer fitted with a Z-spray electrospray interface and
operated in negative ion mode with multiple reaction
monitoring (MRM) of the transition ions listed in Table 2
(Micromass, Manchester, U.K.).
Atenolol was also analyzed by LC-ESI-MS/MS with the
instrument operated in positive-ion mode. Multiple reaction
monitoring (MRM) was employed, using the transition ions
listed in Table 2. The source temperature was 90 C and the
desolvation temperature was 300 C. Nitrogen was used as
both the nebulizing and the desolvation gas at flow rate of 70
and 500 L h 1, respectively. In MRM, the collision-induced
dissociation (CID) was carried out using 2.5 10 3 mbar of UHP
argon as collision gas. The cone voltage and the collision
energy were optimized to the values presented in Table 2. A
dwell time of 200 ms per ion pair was used and the interchannel delay was 0.01 s. Chromatographic separation was
conducted on a Waters model 2690 HPLC system with a
Genesis C18 column (150 2.1 mm i.d., 4 m) at a flow rate of
0.2 mL min 1. The mobile phase A and B consisted of
acetonitrile and 20 mM aqueous ammonium acetate, respectively, which were degassed by an in-line vacuum degasser.
The applied gradient elution was as follows: mobile phase A
was increased from 20% to 95% within 5 min, held at 95% for
1 min and then decreased to 20% over 2 min. The column was
kept at room temperature and the injection volume was 20 L.

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SC IE N CE O F THE TOTA L E N VI RON ME N T XX ( 2 00 8 ) XXXX XX

237 N 194
177 N 80
247 N 204
180 N 80

Sulfonamide antibiotic
Sulfamethoxazole
Sulfamethoxazole-13C6

254 N 156
260 N 162

8.65
8.64

20
20

25
25

Beta-blocker drug
Atenolol
Atenolol-d7

267 N 145
274 N 145

3.1
3.1

24
24

33
33

Bacteriocide
Triclosan
Triclosan-13C12

287
299

8.8
8.8

20
20

Please cite this article as: Topp E, et al, Runoff of pharmaceuticals and personal care products following application of
biosolids to an agricultural field, Sci Total Environ (2008), doi:10.1016/j.scitotenv.2008.02.011

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325

A series of external standards were prepared with different

concentrations of the target analytes and fixed concentrations
(50 ng mL 1) of the analyte surrogates. The concentrations of
the analytes were determined by comparing the response to
each analyte in the samples to the responses to each analyte
in the external standards over the range of a calibration curve.
These response data were adjusted according to the relative
ratios of the responses to the stable isotope surrogates in the
sample and external standard. Both ESI and APCI ionization
sources are susceptible to signal suppression and/or enhancement as a result of interference from matrix materials present
in the extracts from complex environmental samples (Miao
and Metcalfe, 2007). The use of stable isotope surrogates for
analyte quantitation compensates for these matrix effects,
as well any losses due to incomplete recovery during sample
extraction and preparation. Sample blanks were prepared for
groups of samples collected at each day post-exposure. Blanks
were prepared by spiking Milli-Q water with labeled surrogates, and extracting analyzed them as described above. In the
sample blanks, all analytes were below detection limits,
except for cotinine, which was occasionally detected at concentrations less than the LOQ.
The Limits of Detection (LODs) and Limits of Quantitation
(LOQs) were determined for each analyte in an aqueous
matrix. These parameters were estimated by preparing simulated runoff samples in the laboratory in triplicate experiments. Samples of 10 g of the soil from the field plots were
added to a 2 L separatory funnel, and then 1800 mL of
dechlorinated tap water added to the funnel. The mixture was
shaken for 2 5 min. When most of the soil component had
settled out, the aqueous phase from the separatory funnel was
filtered through glass fiber filters and 250 mL aliquots of the
filtrate were spiked with the labeled surrogates and extracted
by the SPE method appropriate for each class of analytes. The
extracts were analyzed as described above, and the LODs and
LOQs were calculated as, respectively, 3x and 10x the standard
deviation (n = 3) of the baseline LC-MS/MS response monitored
at the retention time for each analyte. The LODs and LOQs
(LOD, LOQ; in ng L 1) were: naproxen (4.4, 14.6), gemfibrozil
(4.7, 15.6), ibuprofen (6.4, 21.3), acetaminophen (10.6, 35.3),
sulfamethoxazole (4.3, 14.3), triclosan (5.7, 19.0), atenolol (2.4,
7.8), cotinine (0.8, 2.7) and carbamazepine (1.5, 4.9).
Unfortunately, standard reference materials are not currently available to evaluate the precision of the analysis.
However, the methods for the analysis of selected analytes in

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Quantitation and quality control

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Results and discussion

The volume of applied water required to collect 10 L of runoff

from the micro-plots ranged from 110 to 470 L over the study
period, with an average of 275 + 116 L (n = 60). The 10 L of
collected runoff therefore represented an average of only
4.25 + 1.74% of the applied water, the remainder having
infiltrated into the microplot soil. The volume of water
required to collect 10 L of runoff was moderately correlated
with the angle of the micro-plot slope (R = 0.3), and uncorrelated with antecedent soil water content (R = 0.02). The LMB or
water application method (inject, or broadcast incorporated)
had no significant effect on the volume of water required
to collect 10 L of runoff. Runoff contained 1.63 + 1.19 g wet
weight sediment L 1, (mean + std. dev.; n = 60). The amount of
entrained sediment was significantly higher for the broadcast
treatment on day 1 than on subsequent dates (data not shown;
p b 0.05). Otherwise, there were no significant differences
between treatments or with sampling dates with respect to
the amount of water required to promote 10 L of runoff, and
with the mass of entrained sediment in runoff samples (data
not shown). Natural rainfall during the first 36 days was
minimal (a total of 33 mm in August and 9 mm in September)
and failed to produce runoff.
The day following application and through the remainder
of the experiment, in runoff from the plot that received LMB
injected into the soil, mean concentrations (mean + st. dev. in
ng L 1; n = 5) of gemfibrozil, naproxen, carbamazepine and cotinine were all below the LOQs (data not shown). The concentrations on day 1 of atenolol (18.0 + 13.9) and triclosan (25.6 +
12.1) in runoff from plots receiving injected LMB were above
the LOQs, but fell below the LOQs thereafter (data not shown).
In contrast, runoff on Day 1 from the broadcast incorporated
plots contained the PPCPs at much higher concentrations
(mean + st. dev. in ng L 1; n = 5), including atenolol, 70 + 17.8;
acetaminophen, 114 + 44; ibuprofen, 1477 + 771; naproxen,
509.5 + 256; cotinine, 83 + 32; carbamazepine, 221 + 88; gemfibrozil, 597 + 296; and triclosan, 258 + 39 (Fig. 1). With the exception of ibuprofen and acetaminophen, concentrations of
PPCPs in runoff declined thereafter with varying kinetics that
approximated first order (Fig. 1, Table 3). Unlike the other
PPCPs, the acetaminophen concentration (ng L 1) increased
on day 36 to 146 + 89 from 47 + 17 on day 22, and the ibuprofen
concentration (ng L 1) likewise increased on day 22 to 599 +
310 from 356 + 74 on day 7, further increasing on day 36 to
1023 +199.
Sulfamethoxazole was distinct from all the other PPCPs in
its distribution across the three treatments, and the high temporal and spatial variability in runoff concentration (Fig. 1).
The day following application, concentrations (mean + st. dev.
in ng L 1; n = 5), in runoff from plots receiving broadcast LMB,
injected LMB, and injected water were 93 + 99, 272 + 488 and

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water were validated through inter-laboratory comparisons

conducted with two other laboratories in Europe. Analysis of
surface water collected from the Rhine River in Germany and
extracted within 96 h of collection gave results for carbamazepine and atenolol which were within 5% of the concentrations reported by the two other laboratories.

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listed in Table 2. Chromatographic separation was conducted

on a Genesis C18 (150 3 mm, 4 m) column at the flow rate of
0.5 mL min 1. The mobile phases consisted of 0.1% formic acid
aqueous solution (A) and acetonitrile (B), respectively. Sulfamethoxazole was separated from other sample constituents
using the following linear gradient elution profile at room
temperature: the mobile phase B was initially held at 3% for
0.5 min, increased to 24% at 1 min, then further increased to
43% at 10 min and held at 43% for 2 min. Finally, it reached 95%
at 13 min and was held for 3 min. Afterwards, B was ramped
back to 3% at 17 min. The column was kept at room
temperature and the injection volume was 20 L.

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Please cite this article as: Topp E, et al, Runoff of pharmaceuticals and personal care products following application of
biosolids to an agricultural field, Sci Total Environ (2008), doi:10.1016/j.scitotenv.2008.02.011

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Fig. 1 Concentrations of PPCPs in surface runoff from a field

at various times post-application of broadcast incorporated
liquid municipal biosolids. The days specified indicate when
runoff samples were obtained following rainfall simulations.

t3:2

DT50

DT90

DTLOQ

t3:3

0.99
0.97
0.87
0.96
0.99
0.87
0.99

4.23
3.97
10.37
18.95
2.37
23.16
2.00

14.04
13.19
34.45
62.96
7.86
76.94
6.65

23.2
21.4
53.8
104.0
8.5
110.5
6.4

0.164
0.174
0.067
0.037
0.293
0.023
0.346

t3:4
t3:5
t3:6
t3:7
t3:8
t3:9
t3:10

Shown is the coefficient of determination (r2) for the regression to

the first-order decay model (y = Ae kt), days to reduce the
concentration in runoff by 50% of initial (dissipation time; DT50),
days to reduce the concentration by 90% of initial (DT90), days to
reduce the concentration to LOQ (DTLOQ), for the compound in
question, and the first order rate constant (d 1).

t3:11

Compound
Gemfibrozil
Naproxen
Cotinine
Carbamazepine
Atenolol
Triclosan
Sulfamethoxazole

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t3:1

triclosan through to day 266 (DTLOQ 110.5 days), and carbamazepine through to day 266 (DTLOQ 104.0 days). Presumably
sorptive and diffusive processes in the soil sequestered a
portion of the chemicals, reducing their availability for biodegradation in the days following application. The significance
of residue aging with respect to the dissipation of pesticides
and other organic contaminants in soils is well-known
(Alexander and Scow 1989; Pignatello, 1989). Overall, in our
study some PPCPs (eg. triclosan and carbamazepine) were
relatively persistent in soil, especially during the cold winter,
and were detected 9 months post-application.
An interesting aspect of this study is the increase in ibuprofen and in acetaminophen concentrations in runoff drainage several weeks after broadcast LMB application (Fig. 1). We
hypothesize that this is due to the release following LMB
application of the parent compounds, either from chemicallybound species (e.g. Phase II conjugates) or from physicallysequestered material in the LMB. Ibuprofen forms glucuronyl
and thiol conjugates in the liver (Magdalou et al., 1990; Kuehl
et al., 2005). These conjugates should readily hydrolyze and
may be short lived in soil. However, the ibuprofen acyl glucuronide conjugate binds to serum albumin, suggesting that it
could associate with and be stabilized by organic materials
during sewage treatment (Castillo and Smith, 1995). Alternatively, the drugs could be physically sequestered in (for example) sustained-release formulations that may survive the
sewage treatment process, and once degraded in the soil,
could free the active ingredient for transport in water. For
example, various excipients, such as beeswax and colloidal
silicon dioxide can be combined in the manufacturing of
ibuprofen sustained-release formulations, extending the
time required for 50% dissolution of the drug to greater than
24 h (Niazi, 2004). The generality of this phenomenon with
respect to the environmental fate of PPCPs merits further
investigation.

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TE

431

Table 3 Key kinetic parameters for the decline in

concentration of selected PPCPs in simulated surface
runoff from soil receiving a broadcast application of liquid
municipal biosolids

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127 + 138, and on day 3 runoff from these treatments contained

35.4 + 25.4, 23.9 + 27.1, and 35.6 + 63.2. On day 7 the sulfamethoxazole concentration in the broadcast LMB treatment
was below the LOQ, whereas it was 249 + 501 in runoff from the
injected LMB treatment, and 26.0 + 5.9 in runoff from the water
control. Thereafter sulfamethoxazole concentrations were all
below the LOQ.
The total amounts of PPCPs mobilized during the experiment from the plots receiving broadcast LMB were (on a m2
basis; using the concentrations in Fig. 1 and total volume of
water), 0.63 g of atenolol, 3.83 g of carbamazepine, 1.24 g of
cotinine, 6.65 g of gemfibrozil, 5.49 g of naproxen, 21.1 g of
ibuprofen, 2.6 g of acetaminophen, 0.6 g of sulfamethoxazole and 4.26 g of triclosan.
Every simulated rain event in this experiment was undertaken on a fresh plot that had not previously received any
artificial precipitation. The relative rates of decline of PPCP
concentrations in succeeding runoff events for the broadcast
applications were therefore most likely determined by the
relative rates of dissipation of each chemical in the soil at the
point of application (Fig. 1). Degradation through microbial,
chemical or photolytic mechanisms, or sequestration through
non-equilibrium sorption or covalent attachment to soil could
reduce the amount of chemical available in the aqueous phase
for entrainment through runoff. We attempted to measure soil
dissipation rates in this experiment, but the concentrations of
the PPCPs were generally at or below the LOQs in bulk samples
prepared from soil cores.
Atenolol was detected in runoff from the plot receiving
broadcast LMB only through to day 7, which is consistent with
the DTLOQ of 8.5 predicted on the basis of the estimated first
order rate constant (Table 3). In contrast, a number of the PPCPs
were detected for periods longer than expected on the basis of
their dissipation first order rate constant. Mean concentrations
of gemfibrozil remained above the LOQ through to day 266
(predicted DTLOQ 23.2 days), naproxen through to day 36 (DTLOQ
21.4 days), cotinine through to day 266 (DTLOQ 53.8 days),

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Conclusions

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Beneficial Management Practices (BMPs) that minimize the 502

risk of contamination of adjacent subsurface or surface water 503

Please cite this article as: Topp E, et al, Runoff of pharmaceuticals and personal care products following application of
biosolids to an agricultural field, Sci Total Environ (2008), doi:10.1016/j.scitotenv.2008.02.011

ARTICLE IN PRESS
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Acknowledgements

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This study was funded by Agriculture and Agri-Food Canada,

Health Canada, the Ontario Ministry of the Environment, and
the Ontario Federation of Agriculture. The European Union 6th
Framework supported the participation of S. Monteiro in this
study, and provided in-kind support for the inter-laboratory
analytical chemistry comparison exercise through the ERAPharm research consortium. We thank J. McNeil for the
topographical survey of the experimental site, and X. Zhao
for assisting in the development of the analytical methods. M.
Figueroa Cano, J. Hendel, A. Scott, S. Verhoeven, L. Coates, K.
McCleary, K. Henning, M. Edwards and C. St-Denis provided
invaluable field and laboratory assistance.

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from organic chemicals in biosolids rely fundamentally on the

dissipation of contaminants in soils through degradation or
sequestration processes. These processes are time dependent,
and therefore the greatest risk to adjacent waters from surface
runoff of PPCPs is shortly after application of LMB, when they
are present at highest concentrations. Our results showed that
there were much higher concentrations of PPCPs in surface
runoff from the soil following broadcast application (followed
by incorporation), compared to the injection treatment. The
result is significant in two respects. First, injection into the soil
clearly leaves less material on the surface for rainfall to
interact with, and by extension, there will be fewer LMB
derived contaminants that will be entrained in a given runoff
event. Secondly, since tillage incorporation will never fully
eliminate the material from the soil surface, there is a greater
potential, relative to injection, for contaminants to interact
with runoff-producing rainfall. Some of the PPCP concentrations in runoff were high enough to be of potential biological
concern. For instance, triclosan was detected at 258 + 39 ng L 1
in runoff the day following the broadcast application of LMB.
Frogs (Rana catesbeiana) exposed to 150 ng L- 1 triclosan for
several days showed altered thyroid hormone-mediated gene
expression and development (Veldhoen et al., 2006). This
study shows the value of using BMPs to protect adjacent
surface water from chemical contaminants when applying
biosolids to agricultural fields.

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Please cite this article as: Topp E, et al, Runoff of pharmaceuticals and personal care products following application of
biosolids to an agricultural field, Sci Total Environ (2008), doi:10.1016/j.scitotenv.2008.02.011

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Please cite this article as: Topp E, et al, Runoff of pharmaceuticals and personal care products following application of
biosolids to an agricultural field, Sci Total Environ (2008), doi:10.1016/j.scitotenv.2008.02.011

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