Arch Environ Contam Toxicol (2013) 64:208–218
DOI 10.1007/s00244-012-9833-9
Influences of Sampling Methodologies on Pesticide-Residue
Detection in Stream Water
Zisheng Xing • Lien Chow • Herb Rees •
Fanrui Meng • Sheng Li • Bill Ernst •
Glenn Benoy • Tianshan Zha • L. Mark Hewitt
Received: 7 July 2012 / Accepted: 22 October 2012 / Published online: 15 November 2012
Ó Her Majesty the Queen in Right of Canada 2012
Abstract Traditional grab sampling (GS) used widely in
the study of water quality has been found lacking in spatial
and temporal resolution for pesticide residue monitoring in
stream water. The objectives of this article are to present a
hydrograph-based sampling approach and compare it with
traditional GS according to sensitivity at temporal and
spatial scales and maximum concentrations of pesticide
residues detected in-stream. Data collected from streams
receiving water from three nested watersheds located in
northwestern New Brunswick, Canada, were used in this
study. The results showed that the hydrograph-based
sampling method detected 20 to 30 % more pesticide cases
than GS for rainfall events causing runoff. Grab sampling
significantly underestimated average concentrations of
pesticide residues by 50 % and maximum concentrations
by 1 to 3 orders of magnitude. Using a modified sampler
design, the spatial and temporal variability of pesticide
Z. Xing  L. Chow  H. Rees  S. Li  G. Benoy
Potato Research Centre, Agriculture and Agri-Food Canada,
Fredericton, NB, Canada
Z. Xing  F. Meng
Faculty of Forestry and Environmental Management,
University of New Brunswick, Fredericton, NB, Canada
B. Ernst  L. M. Hewitt (&)
Aquatic Contamination Research Division, National Water
Research Institute, Environment Canada,
Burlington, ON, Canada
e-mail: mark.hewitt@ec.gc.ca
G. Benoy
Environment Canada, Fredericton, NB, Canada
T. Zha
School of Soil and Water Conservation, Beijing Forestry
University, Beijing, China
123
residues was more accurately captured by hydrograph-
based sampling, and therefore its use in monitoring pro-
grams is recommended.
Pesticide contamination in surface and subsurface waters
draining from agricultural land has become a prominent
research focus in the past few decades (Ernst et al. 2009;
Kolpin et al. 2006; Lakshminarayana et al. 1992; Milburn
et al. 1990; Peruzzo et al. 2008; Smith et al. 1990). It is
well-known that accurately detecting contamination levels
is highly influenced by rainfall-runoff characteristic, rate
and timing of pesticide application, pesticide properties,
soil characteristics, and crop types (Kanazawa 1989; Willis
and McDowell 1982; Schulz et al. 1998). However, the
impacts of the sampling approach on the assessments of
contamination are often overlooked (Madrid and Zayas
2007).
Because of the high cost and difficulties associated with
analyzing water samples for pesticide residues, collecting
the minimum number of representative samples is eco-
nomically and scientifically important to both researchers
and risk assessors. Although regular or irregular grab
sampling (GS) is typically used to obtain contamination
levels (Day 1990; Harris et al. 2000; Kanazawa 1989;
Laabs et al. 2002; Lakshminarayana et al. 1992; Williams
et al. 1995), Ernst (2007, 2009) showed that this sampling
approach may not correctly capture the concentration and
delivery patterns of pesticide residues in recipient stream
waters. In fact, sampling was often considered a source of
uncertainty, and traditional sampling frequently had several
limitations (Madrid and Zayas 2007). After application,
pesticides may be transported to streams through either
aerial deposition or runoff and soil drainage driven by wind
or rainfall events, respectively (Scholtz and Bidleman
Arch Environ Contam Toxicol (2013) 64:208–218
2007; Willis and McDowell 1982). Aerial deposition is
often minor during dry seasons or base flow periods (Ernst
2007, 2009; Environment Canada 1982; Yao et al. 2006);
transport of residues by runoff is much more important
(Ernst 2007; Laabs et al. 2002; Stephenson and Solomon
2007). Although regular GS may collect more samples than
required during dry seasons, this approach may in turn
result in fewer samples than required during wet seasons
and may not accurately reflect the hydrologic pattern of
pesticide contamination, a function of rainfall and water-
shed characteristics. GS is also ineffective because of the
so-called ‘‘first-wash’’ effect, meaning that the first rainfall
event or the initial phase of a rainfall event after applica-
tion may flush the greatest proportion of residues (Willis
and McDowell 1982). The nature of GS and its intrinsic
inconsistency means that this type of sampling is difficult
to conduct repetitively and collect representative samples
to compare temporal trends (Laabs et al. 2002). This is
compounded by the large volumes of water necessitated for
some pesticide-residue analysis.
A more representative picture of water quality for risk
assessment may be obtained through a more comprehen-
sive approach that goes beyond simply increasing GS fre-
quency. Automatic time-sequential sampling can be used to
produce composite samples, but this does not necessarily
capture hydrographic variations of stream flow over time
and may miss not only the maximum residue concentra-
tions but also the highest number of detectable pesticides
associated with the peak flow in a storm runoff (Kimbe-
rough and Litke 1996). Passive-sampling has been pro-
moted for its potential to become a reliable, robust, and
cost-effective tool because it generates a time-integrated
average analyte concentration (Madrid and Zayas 2007). If
the water flows do not vary significantly, this approach can
be useful; however, because pesticides typically show
temporal variability coinciding with the hydrograph, this
approach is therefore limited in its ability to capture the full
range of pesticide residues. The accurate calculation of
pesticide transport through runoff can only be obtained
through the hydrography of pesticide concentration tracked
over the entire runoff event. With the development of
computation technology, it is now possible to develop
process-based models of pesticide movement over runoff
flow to obtain more accurate risk assessments of pesticide
contamination in the environment. Because the toxicity of
a given pesticide residue in stream water is governed by the
concentration and duration of the residue, it is necessary to
capture the concentration profile to obtain an accurate
loading and assess any environmental risks. GS may not
able to provide such detailed information because of low
sample frequency and, potentially, sampling at the wrong
time. Our hypothesis is that a continuous, hydrograph-
based sampling system that collects water samples
209
according to hydrograph conditions represents the best
potential option for obtaining the complete range of con-
centrations present in recipient waters. This study explored
this hypothesis using two data sets concurrently collected
in a pesticide residue project (from 2003 to 2006) in the
Maritime region of Canada that used both GS and hydro-
graph-based sampling.
Material and Methods
Research Sites and Operating Dates
The monitored sites in this study (from 2003 to 2006)
include: (1) Little River Watershed (LRW, 47°020 to
47°200 N, 67°310 to 67°470 W), which is 380 km2 in size and
under a mixture of agricultural (16.2 %), forest operation
(77 %), and residential (6.8 %) land uses; (2) Black Brook
Watershed (BBW, 47°050 to 47°090 N, 67°430 to 67°480 W),
which is 14.5 km2 in size and a subwatershed of LRW with
agricultural land use constituting 65 % of the land base of
the watershed with the remainder either forested or under
urban and residential uses; and (3) subwatershed #9
(sub#9) of the BBW, with 93 % of the total 0.8 km2 under
agricultural production that had contour diversion terraces
and grassed waterway soil conservation systems installed
during 1996 to 200. The major crop in the study area was
potato in rotation with grain and hay, and the pesticides
monitored were associated with the major in-use com-
pounds at the time of the study (Chow et al. 2011); these
are listed in Table 1.
Equipment Set-Up and Sampling
In this research, two sampling systems were used: weekly
GS and hydrograph-based sampling. Hydrograph-based
sampling was performed only during non-ice covered
periods of the year (from late May to November for the
study region), whereas GS was performed year-round.
Grab Sampling
Grab samples were manually collected weekly from the
stream channel at each site in 2-L precleaned amber glass
bottles at 12 to 15 cm below the surface of the water at a
point with maximum water mixing.
Hydrograph-based sampling
Hydrograph-based sampling (Fig. 1) was automatically
performed at constructed monitoring stations for each
rainfall event or base flow period. The sampling system
consisted of a modified ISCO 2900 sampler (Teledyne
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210 Arch Environ Contam Toxicol (2013) 64:208–218

Table 1 CCME guidelines for freshwater aquatic life, estimated safe levels of pesticides in surface water, and drinking water quality
Pesticide MDL (lg L-1)a Classb Chemical FAL guideline Estimated safe level Drinking water
family (lg L-1) guideline (lg L-1) guideline (lg L-1)

Azinphos-methyl 0.03/0.005 I OP 0.2b 0.023 20

Carbofuran 0.04/0.00024 I Carbamate 1.8 – 90
Chlorothalonil 0.02/0.00144 F Nitrile 0.18 – 70
Dimethoate 0.04/0.0066 I OP 6.2 – 20
Imidacloprid 0.02/0.0066 I Chloronicotinyl 0.2b 6.83 –
Linuron 0.06/0.00999 H Sulfonylurea 7 – –
b
Metalaxyl 0.03/0.00042 F Acylalmine 0.2 25003 500
Metribuzin 0.03/0.005 H Triazine 1 – 80
FAL freshwater aquatic life, OP organophosphates
a
DL number before ‘‘/’’ was used in ALET, whereas the number after ‘‘/’’ was used in NLET
b
No CCME guideline available. Estimated ‘‘safe’’ level at 0.2 of the lowest LC50 or 0.4 of the lowest chronic toxicity end point. If both types of
data were available, the lowest of these two numbers was used

maximum water mixing within the water column in the

Fig. 1 A water-level monitoring and hydrograph-based sampling
system for pesticide contamination study in the BBW, New Bruns-
wick, Canada. Top system housing; Right stage height monitoring;
Bottom modified sampler with 2L bottles
ISCO, NB, USA) and a flow-monitoring system. The flow-
monitoring system was located in an instrument hut with a
stilling well connected to the stream through a polyvinyl-
chloride pipe.
The standard ISCO 2900 automated water sampler in
12-bottle model was modified to accommodate 12 2-L
amber bottles by replacing the sample bottle tub with a
wood box (Fig. 1 [bottom left panel]) and installing a
custom-made sample-dispatching port ring on the top of
the box and fitted to the central section of sampler. The
dispatching ring had 12 ports lined along a ring, and each
port led to a plastic tube that was connected to the rubber
lid of each sample bottle. The ports were numbered from 1
to 12 and located exactly at the point where the outlet of
the distributor arm pointed to during each sampling stop.
The sampler in-take strainer was placed at a point with
stream through extended Teflon sucking tubing. The
modified sampler had a capability to collect a 2-L water
sample each time when activated by a CR10X data logger
(Campbell Scientific, Logan, UT, USA) triggered by the
stream stage height changes obtained by the stream stage
height-monitoring system and, totally, a maximum of 12
samples could be collected during a storm event or a
sample for every 72-hour period if there was no rainfall
during the period. The sampler was operated in flow mode,
and the sampling number was fed back to the data logger
for recording.
The stream stage height-monitoring system consisted of a
10-turn precision potentiometer operated using a float-
counter weight arrangement (Lakewood Systems, Edmon-
ton, Alberta, Canada). The stage height was monitored at a
5-minute scanning intervals and recorded on an hourly basis
if the change in stage height was \ 2 mm compared with the
previous recorded value. Additional height data were
recorded if the change in stage height was C 2 mm (Chow
et al. 2011; Xing et al. 2012). The discharge rate was then
computed from the stage height using a predetermined, site
specific rating curve. The rating curves for the BBW and
sub#9 were first established based on a composite culvert
configuration-4-to-1 V-notch sharp-crested weir and rect-
angular-1-to-1 V-notch sharp-crested weir, respectively,
and improved gradually through calibrations based on area
velocity using a current meter along a transect at 30-cm
intervals and 0.6 cm depth from the water surface (Xing et al.
2012). The rating curve for the LRW was also based on the
area velocity method measured at different stage heights. To
decrease power consumption and time required for compu-
tation by the data logger, the conversion of stage height to
discharge rate was performed during post-data processing
using a laboratory computer (Xing et al. 2012). Due to the
unavailability of real-time flow information and because of

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the elapsed time required for the sampler to collect 2 L of
sample, it was found that hydrograph-based sampling based
on stage height was just as favorable as true flow proportional
sampling and provided acceptable data. The sampler was
activated by the data logger to take a sample at every 3- to
5 cm change in stage height. These numbers were selected
based on the size of the drainage area and the most probable
rainfall amount and intensity and could be easily adjusted
based on the predicted storm from weather forecasts so that a
maximum of 12 samples could be collected during any major
rainfall-runoff event. The reference stage height used for
sampling was readjusted to the new height automatically if
the difference between the current reading and the previous
sampling height was B-3 cm during the recessing phase of
the hydrograph. In additional to triggering the water sampler
to collect water samples, the data logger also captured the
sample number generated by the sampler and stored the
information with a time stamp. To synchronize the output
frequency of the sampler to the CR10X logger, a 20 kX
resistor was required between the ‘‘pulse channel’’ and
‘‘ground’’ when it was configured for high-frequency pulse
input from the sampler. With the slower operating frequency
of the CR10 data logger, no resistor was needed. To mini-
mize pesticide adsorption, all tubing in the hydrograph-
based sampling system, except for the silicone tubing used
for the peristaltic pump, was replaced by Teflon.
All pesticide samples were preserved in the field with
5 ml methylene chloride. They were collected and put
through a preprocessing procedure in the soil laboratory of
the AAFC research centre as described in Laboratory
Analysis. They were then packed on ice and shipped by
courier to the National Laboratory for Environmental
Testing (NLET), National Water Research Institute
(NWRI), Burlington, ON, Canada, for further analysis.
Pesticide samples collected in 2006 were preserved in the
field with methylene chloride, packed on ice, and shipped
by courier for next-morning delivery to the Atlantic Lab-
oratory for Environmental Testing (ALET), Environmental
Quality Laboratory, Environment Canada, Moncton, NB,
Canada, where they were analyzed for pesticide concen-
tration. Because we did not have comparable GS data, the
data collected in 2006 with the hydrograph-based sampling
method were only used for sensitivity analysis of the
hydrograph-based sampling method.
Weather Information
Weather data (rainfall) used for this study were collected
from two automated weather stations, one located approx-
imately 200 m from the outlet of the BBW (WS no. 5) and
the other one located approximately 5 km from the outlet
of the LRW at a permanent runoff-erosion study site (WS
no. 8). Both weather stations were run year-around, except
211
for precipitation amount and intensity (WS no. 5), which
were only monitored with heated (WS no. 8 [Rimco heated
gauge; McVan Instrument, Mulgrave, Victoria, Australia])
and nonheated (WS no. 5 [Texas Electronics, Dallas, TX])
tipping-bucket rain gauges. Because of the extremely low
ambient temperature during the winter, an additional
200 W heater controlled by a thermostat (closed at 4 °C
and open at 16 °C) was wrapped around the collection
funnel to accelerate snow melting before funneling it into
the tipping bucket. This modification was found to be
essential for the severe winter conditions in northwestern
New Brunswick, Canada. The sampling frequency was set
at 1-minute intervals during precipitation events to capture
the temporal pattern of the rainfall event, whereas only
hourly output was sent to storage during dry periods. Data
were retrieved on a weekly basis by way of telephone line
using an answering modem in conjunction with the data
logger.
Laboratory Analysis
NLET Analysis Procedures in the NWRI
Samples collected before 2006 were spiked with 1.0 ml
240 ppb carbaryl 13C and shaken well to ensure thorough
mixing. The samples were then stored (normally not [2 d)
at 4 °C for further filtration and extraction. Whatman glass
microfibre filters (0.45 lm; Whatman, Toronto, ON,
Canada) were used to filter samples through a specialized
pressure-filtration system. The solids recovered from
filtration were funneled into a small bottle and stored at
-20 °C. The aqueous samples were further extracted using
a solid phase extraction (SPE) manifold and Supelco 2-ml
reversible tubes with SPE frits and 500 mg ENVI-Carb C
cartridges (Supelco, Supelco Park, Bellefonte, PA, USA).
SPEs containing pesticide residues were placed in self-
sealing polyethylene bags and frozen at -20 °C. The SPEs
and filtered solids were then shipped on ice overnight to the
NWRI laboratory for analysis. Cartridges were eluted by
gravity in the reverse direction with 10 ml DCM and
methanol (80:20). The eluents were then dried under
nitrogen and diluted in methanol for analysis by liquid
chromatography with tandem mass spectrometry detection
(MS/MS; Sciex API 2000; Thornhill, ON, Canada) as
described in Chow et al. (2011). Detection limits for the
methods used in this study are listed in Table 1.
ALET Analysis Procedures in Environment Canada
The samples collected in 2006 were analyzed in the
Environment Canada Laboratory. Within 24 hours of
receipt, the 1-L water sample was filtered, using positive
pressure, through Whatman glass filters (GF)/C
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212
(N 14.2 mm; 1.2-lm pores) and GF/D (N 12.5 mm; 2.7 um
pores; Whatman, Fisher Canada, Oshawa, ON, Canada).
The water fraction was then extracted with 3 9 50 mL
methylene chloride (pesticide grade). The extract was
concentrated to 5 mL and then passed through a gel-per-
meation chromatography column (200 to 400 mesh; Bio-
Beads S-X3, Fisher) to remove coextractives. The extract
was again concentrated, with the solvent exchanged to
toluene, to a final volume of 0.5 mL. The extract was
subsequently analyzed for pesticides using GS-MS
(GC-5890/MS-5973; Agilent, Lexington, MA, USA)
operating in the selected ion monitoring mode.
Results and Discussion
Detection Frequency and Concentration
Hydrograph-based sampling generally obtained higher
detection rates of the listed pesticides (2 to 26 %) compared
with GS (1 % [Table 2]). When the method detection limit
(MDL) (Table 1) threshold was used on 3 years of col-
lected samples in the BBW (2003 to 2005) using GS, no
cases were detected that exceeded the MDL for metribuzin,
metalaxyl, and azinphons-methyl, whereas only one case
each was detected that exceeded the MDL for imidacloprid
and linuron.
Although the maximum detection rate among pesticides
was \27 % for both approaches, differences between the
two methods were apparent. There were no detections of
pesticides under normal (base) flow conditions regardless
of sampling approach. However, with samples during and
immediately after major rainfall events, it was found that
there were some detections of pesticides in excess of the
MDL but below available water-quality guidelines for
aquatic life for both methods. Careful examination at the
individual detection rates of pesticide obtained using hyd-
rograph-based sampling in the BBW indicated detection
rates from 30 % for linuron to 0 % for metribuzin (average
9 %) for 2005.
Table 2 Detection rates higher than MDL and corresponding concentrations obtained through HBS and GS from 2003 to 2005 at the outlet of
BBW
Sampling No. of Parameters Imidacloprid
method samples
HBS 163 % [MDL 7.36
Mean concentration (lg L-1) 0.46 ± 0.05
GS 105 % [MDL 1.0
-1
Mean conentration (lg L ) 0.22 ± 0.00
Mean concentration (±SE) was calculated from measurements greater than MDL
HBS hydrograph-based sampling
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Arch Environ Contam Toxicol (2013) 64:208–218
Mean concentration differences between both methods
were also apparent. Mean concentrations obtained through
GS were at least 50 % less using hydrograph-based sam-
pling (Table 2). Although these concentrations were well
below drinking water-quality guidelines (Table 1) and
would not represent any risk to human health, the GS
method clearly underestimated the presence of pesticides in
stream water.
The higher percentage of detections and higher con-
centrations obtained through hydrograph-based sampling
can be attributed to the better sampling design, i.e., addi-
tional samples were collected when the stage height
increased or decreased by 3 cm compared with the stage
height of the previous sample. With this sampling
approach, B12 samples could be collected for any single
storm event (e.g., July 21, 2006 [Fig. 2]). With hydro-
graph-based sampling, temporal variations in the stream
hydrograph during rainfall-runoff events were properly
delineated by the flow-controlled samples, and therefore a
complete representative hydrograph of pesticide concen-
trations with event progress could also be accurately cap-
tured (Fig. 2). In contrast, GS provided only a general
representation of the stream water hydrograph through
regularly collected samples. The probability of capturing
pesticides had a 1-week resolution, and runoff sampling
occurred mainly by chance because our results clearly
demonstrate that the primary route of pesticides entering
these streams is by way of rainfall runoff events (e.g.,
Fig. 3).
Maximum Concentration
As part of sampling comparison, data collected for imi-
dacloprid during the growing season of 2005 are provided
in Fig. 3. It was found that both methods generally cap-
tured the base flow variations of imidacloprid; however, the
concentrations obtained through the hydrograph-based
method showed greater concentrations (by 1 to 3 orders of
magnitude) than those obtained by way of GS. The one
exception to this was when GS occurred during a rainfall
Metribuzin Metalaxyl Linuron Azinphos-methyl
2.45 3.68 26.38 9.20
0.09 ± 0.02 0.69 ± 0.02 0.25 ± 0.03 1.88 ± 0.7
0 0 1.0 0
– – 0.09 ± 0.00 –
Arch Environ Contam Toxicol (2013) 64:208–218 213

Fig. 2 An example of 80
Stage HT (cm)
hydrograph-based sampling Stage HT change (cm)
data. Data were collected at the Sample #
outlet of the Black Brook Rainfall Acc. (mm)
Watershed, NB, Canada. Rainfall amount (mm)
Sample # series number of the 60 in 30 minutes
samples collected, Rainfall Acc
accumulative rainfall amount

Measurement
since the start of the rainfall
event, Stage HT stage height
40

20

0
13:00:00 14:00:00 15:00:00 16:00:00 17:00:00
Time (July 21, 2006)

Fig. 3 Monitored 4
Imidacloprid (ng L-1, log transformed)

concentrations of the pesticide Daily rain amount (mm)(log transformed)

imidacloprid measured during Grab sampling
2005 at the outlet of the BBW 3 Hydrograph-based sampling
using both sampling
approaches. RF rainfall
2

1 10 mm RF

0 1 mm RF

-1
120 140 160 180 200 220 240 260 280 300 320
May 20 Day of year 2005 Oct 27

event as indicated on day 142 (Fig. 3). It should also be
noted that [10 mm daily rainfall could make relatively
large differences in terms of maximum concentrations. It is
possible that grab samples might have mostly been col-
lected either before or after major rainfall events when
concentrations of pesticides in the stream were very low. In
contrast, the hydrograph-based sampling method sampled
mostly during rainfall events and could capture both ‘‘first
wash’’ and the subsequent dilution effect of rainfall on
pesticide residues running into stream water.
Accumulated Pesticide Transportation
Data collected using both methods from the BBW during
May to October 2005 were used to derive a cumulative
loading (concentration 9 flow discharge) of pesticide
residues. Grab sampling was weekly during this period;
however, for the hydrograph-based sampling method, data
were not continuous but event-triggered. In such cases, if
there was no rainfall and thus no data for hydrograph-based
sampling, the data from GS were used for the calculations
of the base flow period. For rainfall events, calculating
accumulative pesticide from hydrograph-based sampling
was expressed as the integration of real measurements of
water discharge multiplied by measured pesticide concen-
tration. The results showed an average of 43 % underesti-
mation using the GS method (Table 3). However, the
difference will be pesticide-dependent. For frequently
detected pesticides, the differences between the two
methods were relatively lower and insignificant (p [ 0.05
for imidacloprid, metalaxyl, and azinphos-methyl
[Table 3]), whereas the differences were greater and

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214 Arch Environ Contam Toxicol (2013) 64:208–218

Table 3 Comparison of accumulated pesticide amount detected in BBW during May through Oct 2005 by way of two sampling methods
Sampling method Imidacloprid (kg) Metribuzin* (kg) Metalaxyl (kg) Linuron* (kg) Azinphos Methyl (kg)

HBS 41.66 1.61 2.09 56.17 0.56

GS 36.05 0.22 2.00 12.50 0.43
% 13.48 86.22 4.23 77.74 23.11
p value for ANOVA 0.411 0.027 0.922 0.021 0.243
% = (HBS-GS)/GS*100
HBS hydrograph-based sampling, ANOVA analysis of variance
* Significant difference (p \ 0.05) between sampling approaches
Weather variables
Fig. 4 Relationships between
50
(a) rainfall characteristics,
40 a
(b) hydrographs, and Accumulative. Rainfall (mm)
30 since day 180
(c) dimethoate concentrations 20 30 minute rain intensity (mm)
detected using hydrograph- 10
based sampling from three 0
watersheds of different size.
Watershed sizes are 76.7, 1450, 180.0 180.5 181.0 181.5 182.0 182.5 183.0
and 38,000 for sub#9, BBW,
River stage height (cm)

and LRW, respectively

100
Sub#9
80
b BBW
LRW
60

40

20

0
180.0 180.5 181.0 181.5 182.0 182.5 183.0
Dimethoate (µg L-1)

.35
.30 c Sub#9
.25 BBW
LRW
.20
.15
.10
.05
0.00

180.0 180.5 181.0 181.5 182.0 182.5 183.0

Julian Day of 2006

significant (p \ 0.05, Table 3) for pesticides associated
with events. This indicates the weakness inherent in GS in
that it captures pesticide residue by chance.
Spatial Sensitivity
Figure 4 shows the spatial and temporal changes in rainfall,
river stage height, and dimethoate concentrations measured
at the outlets of sub#9, BBW, and LRW during a series of
rain storm runoff events from June 28 to 30, 2006. As
shown in Figure 4a, the accumulative rainfall since day
180 was 41.4 mm with corresponding 30-min maximum
rainfall intensities of 16.3, 12.2, 14.2, 5.6, and 6.6 mm h-1,
respectively, for the five rainfall events. Accordingly, the
stage heights (Fig. 4b) recorded by hydrograph-based
sampling clearly reflected each event at the outlets of sub#9
(solid line), BBW (dotted line), and LRW (dashed line). It
should also be noted that the peak time of stage heights
measured at BBW were generally behind those of sub#9 by
1 to 2 hours, and those of LRW were behind by an addi-
tional 1 to 2 h. For instance, the first peak for sub#9
occurred at 180.747 day compared with 180.795 day for
BBW and 180.875 day for LRW. The time lag between
sub#9 and BBW was 69 minutes, whereas it was 115
minutes between BBW and LRW. This difference is due to
watershed characteristics including topography, geology,
and land use of the watersheds and illustrates the ability of
the hydrograph-based sampling to measure hydrological
differences between watersheds.
Similarly, Figure 4c shows the dimethoate concentra-
tions of samples collected during these events. Dimethoate
was not detected at the outlet of any of the monitored

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Arch Environ Contam Toxicol (2013) 64:208–218 215

watersheds during base flow or before the rain event at
approximately 17:00 (Julian day 180.7). With event pro-
gression, concentrations varied with different watershed
sizes, rainfall intensity, and rainfall duration. Dimethoate
concentrations measured from the LRW showed very little
variation and no observed stage height changes (Fig. 4c),
whereas concentrations from the BBW displayed only one
peak response associated with the largest stage height
change. However, dimethoate concentrations from sub#9
had several peak periods corresponding to the peaks of
stage heights. These observations may reflect a relationship
between crop intensity, pesticide-application rates, and
resultant pesticide concentrations detected between
watersheds.
Pesticide concentrations in runoff from the nonagricul-
tural portion of the watershed were considerably less than
those of the agricultural areas (Fig. 4). Land-use propor-
tions for agricultural production in LRW, BBW and sub#9
were 16, 65, and 93 %, respectively, and may be the pri-
mary factor for lower concentrations at the outlets in the
LRW than in the BBW. Furthermore, sub#9 was the
smallest watershed, and its outlet was the closest to the
fields/pesticide source and less impacted by any attenuation
in runoff path and therefore incurred a less net loss of
pesticide residues transported by runoff.
Other factors, such as land-management patterns, crop
cover type, cropping intensity, soil drainage condition, and
topographic configuration, may also be responsible for
spatial variations in pesticide residues in surface water
among different watersheds. Land fragmentation, grassed
waterways, and riparian buffer strips may prevent pesticide
residues from reaching streams as seen in sub#9. All of
these processes potentially decouple the linear relationship
between rainfall intensity, duration, and pesticide transport
amount and patterns. However, the degree of the decouple
may varied with watershed characteristics. Therefore,
determining the appropriate sample collection time is
critical for capturing the ‘‘first wash’’ phenomenon of
pesticide residue transportation and, in particular, the
maximum concentration of pesticide residues in stream
water during a rainfall event for different watersheds.
Temporal Sensitivity
To demonstrate the sensitivity of the hydrograph-based
sampling method in capturing pesticide concentrations and
stream flow resulting from different rainstorms, data col-
lected from three rainfall events in 2006 (June 27, July 21,
and August 15) in the BBW are provided in Fig. 5. Both
stage height and total suspended sediment concentrations

Fig. 5 Stage height, total 40

sediment concentration, and
a Rainfall (14.22 mm) Chlorothalonil ( g L )
-1

June 27 Metribuzin ( g L )
-1

pesticide measurements 30 -1
Linuron ( g L )
(chlorothalonil, metribuzin, and Stage height (x10cm)
-1
20 TSSC (g L )
linuron) obtained at the outlet of
sub#9 of the BBW during three 10
rainfall events (a–c) during
2006. Stage height stream stage 0
height recorded by data logger, 03:30 04:00 04:30 05:00 05:30 06:00 06:30
TSSC total suspended sediment Time (June 27 2006)
concentration
2.5
b Rainfall (11.68 mm)
July 21
-1
Chlorothalonil (mg L )
2.0 -1
Metribuzin (mg L )
Measurements

-1
1.5 Linuron (mg L )
Stage height (x10cm)
-1
1.0 TSSC (g L )

.5

0.0
13:30 14:00 14:30 15:00 15:30 16:00
Time (July 21 2006)

4
c Rainfall (9.4mm) Chlorothalonil (x100 g L )
-1
August 15 -1
3 Metribuzin ( g L )
-1
Linuron ( g L )
Stage height (x10cm)
2 -1
TSSC (g L )

0
16:30 17:00 17:30 18:00 18:30 19:00 19:30 20:00 20:30
Time (August 15 2006)

123
216 Arch Environ Contam Toxicol (2013) 64:208–218

displayed polynomial curve patterns skewed significantly
to the left, indicating the increasing configuration of the
hyetograph, thus reflecting rainfall characteristics. It must
be noted that the impacts of the phenologic development of
crop canopy on runoff and pesticide transport were also
inherent in the data set because the rainfall events occurred
in different crop-development phases. From these data, it is
interesting to see that the total suspended sediments
reached their peak fluxes approximately half an hour later
than the corresponding stage height (Fig. 5) and were less
related to the measurement dates (rainfall characteristics).
Pesticide concentrations throughout the rainfall events
showed similar patterns to the suspended sediments
(Fig. 5); however, they were pesticide-dependent. The
maximum concentrations of chlorothalonil had a bell-
shaped curve, except for August 15, during most of the
rainfall events (Fig. 5c). Pesticide concentration peaks
mostly corresponded with peaks in total suspended sedi-
ments. Then the concentrations of the pesticides showed
either a decay curve pattern with decrease in rainfall
amount, a demonstration of ‘‘first wash’’ effect of rainfall
(as in Fig. 5c), or normal distributions (Fig. 5a, b), which
may be attributed to pesticide characteristics, such as water
solubility and soil absorption. The ‘‘first wash’’ effect is
mostly affected by the intensity and duration of the rainfall.
As shown in Fig. 5, concentrations varied greatly from
June (\35 lg L-1) to July (500 to 1000 lg L-1), and
August (\100 lg L-1), possibly caused by the amount of
pesticide applied, number elapsed days since the dates of
pesticide application, and rainfall characteristics at each
measurement date. Furthermore, in this region, chlorot-
halonil was mainly used in July and early August for
controlling late potato blight. The variations from June to
August clearly demonstrate the application pattern of the
pesticide in this region. This hydrographic temporal pattern
shown by hydrograph-based sampling could not be cap-
tured by GS because it has a coarse resolution (±1 week).
The known behavior of metribuzin is consistent with the
data obtained from June 27 to August 15 2006 (Fig. 5a–c).
Because it is a pre-emergence herbicide, metribuzin was
applied only in late May or early June. Metribuzin is mainly
removed from soil by microbial degradation with leaching to
groundwater. Its half-life in soil ranges between 2.5 and
4 months, but it was found to be only approximately 7 days
in pond water (see http://dsp-psd.pwgsc.gc.ca/collection/
H48-10-1-58-1989E.pdf). Given the previously mentioned
characteristics, the concentration gradients from approxi-
mately 5 to 10 lg L-1 in June to very close to zero in August
(Fig. 5a–c) was evidence of the accuracy and sensitivity of
the hydrograph-based sampling approach in capturing long-
term temporal variation of pesticide residues.
Linuron is an herbicide and did not show much vari-
ability with different rainfalls except for the rainfall on
June 27. It is well known that in the environment, linuron is
moderately persistent in soils and is broken down, mainly
by microbes, into a much less active metabolite with a half-
life of 75 days (see http://pmep.cce.cornell.edu/profiles/
extoxnet/haloxyfop-methylparathion/linuron-ext.html).
Furthermore, linuron is only slightly to moderately soluble
and is not readily broken down in water (Kalkhoff et al.

Table 4 Statistical
Sampling dates Imidacloprid (lg L-1)* Linuron (lg L-1)*
comparisons of the
concentrations of two pesticides HBS GS HBS GS
measured during July 27 to
September 14, 2004, by HBS Julian day
and GS 208 0.4196 0.0042 0.3995 0.0107
216 0.0480 0.0060 0.1466 0.0051
222 0.0097 0.0063 0.0074 0.0029
229 0.0072 0.0025 0.0068 0.0009
236 0.0341 0.0019 0.0271 0.0007
243 0.0023 0.0023 0.0185 0.0009
251 0.0070 0.0025 0.0555 0.0008
257 0.0044 0.0035 0.0327 0.0054
Period mean 0.0665 0.0037 0.0868 0.0034
SE 0.0508 0.0006 0.0475 0.0012
Range of mean 0.4174 0.0044 0.3926 0.0100
HBS hydrograph-based
Minimum 0.0023 0.0019 0.0068 0.0007
sampling
Maximum 0.4196 0.0063 0.3995 0.0107
* Significant differences
(p \ 0.05) in Student t tests Range of real measurements 0.6202 0.0044 0.6844 0.0099
were found between two Relative difference (%) 94.5 96.0
sampling approaches for a Student t test p 0.028 \0.001
pesticide (log-transformed data)

123
Arch Environ Contam Toxicol (2013) 64:208–218
2003). Therefore, the concentration decrease from 5 lg
L-1 on June 27 (Fig. 5a) to \0.5 lg L-1 on August 15
(Fig. 5c) showed a time-related pattern and suggested that
the hydrograph-based sampling method reasonably cap-
tured the impacts of pesticide characteristics.
Statistical Comparisons
A data segment from day 208 to 257 in 2004 from BBW
was used to carry out statistic analysis as a demonstration.
The result (Table 4) showed that the two sampling
approaches were significantly different in terms of daily
mean, range, maximum, and minimum concentrations of
the pesticides imidacloprid and linuron. Student t test dis-
played a significant difference between the two methods
for imidaloprid (p = 0.014) and linuron (p = 0.028). GS
underestimated concentration means by 95 and 96 % for
imidacloprid and linuron, respectively. Maximum concen-
trations of imidacloprid and linuron detected by hydro-
graph-based sampling were two to three orders of
magnitude greater than those detected by GS, respectively.
This result also suggests that average- or median-based
parameters may not be appropriate to describe pesticide
contamination in stream water for risk assessment purposes
because of temporal-distribution patterns of pesticide
movement.
There is some concern that that hydrograph-based
sampling overestimates pesticide presence in stream water
because the method obtains pesticide concentrations during
high flow. In this study, we determined that pesticide
transport was mostly associated with runoff flow (verifying
the ‘‘first-wash’’ phenomenon) and that base-flow detec-
tions were generally zero or below detection limits.
Therefore, the exact ‘‘washing-time’’ that pesticides flow
into streams will be determined by the flow rate and rainfall
amount, which is normally unknown before a rainfall.
From this aspect, hydrograph-based sampling provides a
more accurate approach because this method captures this
all-important transport window.
Conclusion
The hydrograph-based sampling method aptly character-
ized pesticide pollution in stream water. It detected more
pesticide residues than GS by 20 to 30 %. The hydrograph-
based sampling method better obtained the maximum
concentration of pesticide residues in stream water,
whereas GS often missed peak concentrations. With GS, it
was possible to underestimate the impacts of pesticide
residues on stream water quality, generally underestimating
average pesticide concentration by B50 %, whereas the
underestimation of maximum concentrations could reach 1
217
to 3 orders of magnitudes. Hydrograph-based sampling
described the spatial and temporal variability of pesticides
in streams of various-sized watersheds more accurately
than did GS.
Statistical analysis displayed significant differences in
the means of pesticide measurements obtained with the two
methods. GS provided insufficient resolution to make
conclusions regarding the mobility, and, ultimately the risk
of pesticides in the environment.
Hydrograph-based sampling can be used for pesticide
contamination research and is a more precise tool for
gaining insight into contamination patterns and collecting
detailed information for modeling the environmental
impacts of pesticides. Hydrograph-based sampling showed
a profile-style resolution with the progress of rainfall and
displayed a reasonable pattern of pesticide-residue con-
centrations in stream water based on a maximum of 12
water samples for any given storm. However, the limited
number of samples for which the sampler was designed
may be inconvenient for consecutive rainfall events and
thus create more data gaps. To adapt the method to more
complicated rainfall patterns, composite sampling using the
hydrograph-based-flow proportional sampling scheme
(composite of a number of samples into one sample based
on a predetermined amount of discharge) may be a superior
approach to capturing the concentration per rainfall event
and decreasing sample number. This will make obtaining
mean concentrations over an entire year for a long-term
statistical analysis possible and meaningful.
Acknowledgments The authors acknowledge the work of John
Monteith, Lionel Stevens, Sylvie Lavoie, Suzanne Batchelor, and Yu
Yang for their contributions in maintaining the weirs, sample col-
lection, and analysis. This research project was financially supported
by Watershed Evaluation of Beneficial Management Practices
research project of AAFC, Canada.
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