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Abstract: Storm-water monitoring generally uses flow-weighted automatic composite samplers to collect a representative sample of an
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entire storm event. Automatic samplers are convenient but unfortunately they can be expensive, especially for temporary sampling needs
or for short-term research projects. An alternative method is to use a series of grab samples. This paper examines the accuracy of event
mean concentrations 共EMCs兲 and mass first flush ratios calculated from a finite number of grab samples, and compares them to results
from flow-weighted automatic samples. Both sampling techniques were evaluated using data collected from a three-year investigation of
three highway sites. A large number of grab samples is needed to approach the accuracy and precision of flow weighted composite
samples, and 30 grab samples per storm event generally estimated the EMCs within 20% average error. To detect a first flush, it is
necessary to take even more grab samples or to adjust the timing of the sample collection toward the beginning of the storm. The
superiority of automatic sampling for estimating EMCs for constituents compatible with automatic sampling is demonstrated.
DOI: 10.1061/共ASCE兲0733-9372共2009兲135:3共118兲
CE Database subject headings: Stormwater management; Composite materials; Regression analysis; Sampling; Runoff; Urban
areas.
w9
Sampling Point
0.6 w8
w7
0.4 w6
0 w1
0 0.2 0.4 0.6 0.8 1 storm event were determined using a previously developed COD
Time Fraction regression model 共Ma 2002兲, developed using regression analyses
with 393 grab sample COD concentrations from the three high-
Fig. 1. Determination of flow weights 共w1 to w10兲 for grab samples
way sites during the 1999–2001 wet seasons. The mathematical
expression of the model is as follows:
Vi 兺 jqij⌬tij E共log CODi兲 = 6.08 − 0.60 log CumRFi + 0.40 log ADD
wi = = 共5兲
兺iVi 兺i兺 jqij⌬tij − 0.16 log AntRF 共7兲
where Vi = discharge volume corresponding to the ith concentra-
tion measurement 共L3兲, qij = jth flow measurement in the ith in- i ⬃ N共0,0.592兲 共8兲
terval of the concentration measurement 共L3 / T兲; and ⌬tij where E共log CODi兲 = mean value of log transformed chemical
= length of time in the jth interval of the flow measurement in the oxygen demand concentration given independent variables for ith
ith interval of the concentration measurement 共T兲. This mid- grab sample 共mg/L兲; CumRFi = cumulative rainfall at the time of
discharge splitting method can also be applied for measurements the ith grab sample 共1 mm increments兲; ADD= antecedent dry
at unequal time-interval bases. Alternatively, if the concentration days before the monitored event 共days兲; AntRF= previous event’s
measurements are based on constant discharge volume, the precipitation before the monitored event 共1 mm increments兲; and
weighted average of wici reduces to the arithmetic average. Ide- i = error of prediction having normal distribution. Only a very
ally, automated samplers can collect samples in proportion to dis- short lag between rainfall and runoff was observed and the impact
charge volume. of time of concentration has been discussed elsewhere 共Kang et
The MFF ratio is defined as the ratio of the normalized dis- al. 2008兲. Fig. 2 shows the model’s fitted values versus the obser-
charge mass of pollutants to the normalized runoff volume in the vations. Eqs. 共7兲 and 共8兲 were used to generate COD concentra-
first portion of the total runoff volume and mathematically ex- tions at 1-min intervals, which is the shortest possible sampling
pressed as follows 共Ma et al. 2002; Kim et al. 2004兲: frequency, since the rainfall and flow data are collected at 1-min
冕
tn
C共t兲Q共t兲dt 冒 M 冕
tn
C共t兲Q共t兲dt 冒冕 tn
Q共t兲dt
intervals. Since the regression model predicts mean values of log-
transformed COD, which is median values in arithmetic scale
distribution, the mean value of COD is obtained using the rela-
冒
0 0 0
冕
MFFn = = tionship of lognormal distribution 共Aitchison and Brown 1957兲 as
tn
Q共t兲dt V
M V Ⲑ follows:
0 2/2
E共CODi兲 = eE共log CODi兲+ 共9兲
共6兲
where E共CODi兲 = mean value of COD given independent vari-
where MFFn = mass first flush ratio for the first n% of total runoff ables for ith grab sample; and 2 = variance of prediction errors
volume; tn = elapsed time corresponding to the first n% of total 共=0.592兲. The EMC and MFF20 were then calculated using Eqs.
runoff volume. In this study, the MFFn for 20% of total runoff 共2兲 and 共7兲, respectively, and used as the reference values of EMC
volume 共MFF20兲 was used for the first flush effect simulation. To or MFF20. The EMCs and MFF20s generated represent the most
calculate MFF20 using Eq. 共6兲, continuous functions of pollutant precise estimates, as if a grab sample for COD could be collected
mass discharge and pollutant concentrations are needed, and the and analyzed each minute.
same techniques used to develop approximate continuous func-
tions for the EMC were used.
Simulations of Sampling Strategies
Simulations of Different Sampling Strategies In order to simulate the collection of a varying number of grab
samples, Eq. 共7兲 was used with a random component 共white
noise兲 having mean zero, and a variance equal to the variance in
Reference Value for EMC
the original data 关Eq. 共8兲兴. In this way, collecting any number of
To evaluate different sampling strategies, a best estimate or ref- grab samples with measurement errors can be simulated. To com-
erence value of pollutant concentration is needed for comparison. pare different sampling strategies, five types of simulation were
The reference value will be used when simulating various sam- performed using different numbers and different strategies for
pling strategies. The reference pollutant concentrations for a collecting samples during typical storm events as described in
Table 1. A total of 35 different rainfall patterns, corresponding to ignored. Type 3 and 4 strategies usually require automated sam-
actual observed patterns in our monitoring program, were used. plers, and Type 4 is often used to collect flow-weighted composite
The hydrographs were smoothed before simulation to correct samples, as shown in Fig. 1. Type 5 was a simulation of more
short-term fluctuations in the original data. Table 2 is a statistical frequent sampling in the earlier part of a storm in order to im-
description of the 35 events. prove the characterization of the first flush. In the first flush en-
In order to estimate the variability that might occur when hanced sampling, five samples are taken in the first hour. The first
using white noise to simulate storm variability, each type of simu- sample is taken at time zero and the remaining samples are taken
lation was performed 1,000 times to generate a mean value and at 15-min intervals. Next, four samples are taken in the following
distribution of the EMCs and MFF20s. It was expected that strat- 2 h at 30-min intervals and afterward, one sample is taken every
egies that collected more grab samples will produce the EMCs or 1 h. The results of all sampling types were compared with each
MFF20s that are closer to the reference values. By comparing the other and to the reference sampling.
number or timing of grab sample collection, each strategy can be Fig. 3 illustrates the results of Type 2 sampling 共equally
compared. The influence of sample size on calculated EMCs or timed兲, showing the frequency distribution of 1,000 simulated
MFF20s was evaluated by simulating 10, 20, 40, 60, and 100 EMCs using different sample sizes for one event 共1/25/2,000, site
samples per event using five timing strategies, which will be re- 1, total rainfall depth= 17 mm, storm duration= 19.4 h兲. The
ferred to as Types 1 to 5, described in Table 1 and the following 1-min sampling simulation was used for producing a reference
paragraphs. These strategies were compared to ideal or reference value of true COD measurement per storm event 共EMCR兲. More-
sampling, where samples are collected every minute. These strat- over, the 1-min sampling was not just simulated once but 1,000
egies all examine errors in concentration measurements and ig- times for each storm event to generate a sample set consisting of
nore potential errors in flow measurements. Measurements in flow 1,000 reference values and the average of them was used as
can also occur, but their impacts were not considered in this work, EMCR. For the same storm event under less frequent sampling
and is a subject for future work. strategies 共i.e., Type 2 sampling as n = 5, 10, 20, 40, and 60 as
Type 1 uses randomly timed grab sampling. The required num- illustrated in Fig. 3兲, each sampling simulation generates a set of
ber of samples 共n兲 is collected at random points of time during EMCs from the 1,000 runs. The error of each sampling strategy is
each storm event. Theoretically, this is the most general case for a estimated by comparing the distribution of the EMCs generated
sample set with fixed size. Type 2 uses equally timed or spaced from 1,000 runs to the EMCR obtained from 1-min simulation.
sampling. The required number 共n兲 of grab samples is collected at Specifically it is estimated by the root-mean-square error 共RMSE兲
equal time intervals during the runoff. To avoid unique results that that analyzes the bias of sample mean as well as the variance of
might occur because of a specific sample sequence, each sample target distribution. The RMSE result was then normalized by con-
sequence is shifted forward or backward based upon a random verting into percentage 共mathematical expression is shown in the
time, ranging from −5 to +5 min. Type 3 simulations used equal next section兲. In Fig. 3, EMCR is 116.26 共mg/ L兲, and the means
rainfall depth sampling. A specified number of samples are col- of each of the 1,000 simulations for n = 10, 20, 40, 60, and 1-min
lected at equal intervals of rainfall depths. Type 4 simulations interval samples are 149.15, 121.48, 117.91, 117.12, and
used equal discharge volume sampling. A specified number of 116.22 共mg/ L兲, respectively. The results indicate that smaller
samples are collected at each point of time when an equal runoff sample size produces larger deviation from the true EMC, which
volume is discharged. Any error in flow measurement error is is expected since the COD is log normally distributed.
Err%
n = 40
Count
n = 20 40
300 n = 10
n= 5
20
200
100 R
0
EMC
80
0
(b)
0 100 200 300 400 500 60
Err%
Simulated EMC (mg/L)
40
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Err%
To quantify the average error between the simulated EMC and 40
EMCR, the RMSE was used. The RMSE is equal to the bias and
20
the variance of the estimate, noted by EMC* and simply calcu-
lated using Eq. 共10兲 0
冑兺
80
Ⲑ
(d)
RMSE共EMC*兲 = i=1共EMCi
N * − EMCR兲2 N
60
The Err% for the 1-min sampling is caused only by its variance. O ut lie r low e r qua rt ile Uppe r qua rt ile O ut lie r
(25%) (75%)
The Err% of the 1-min sample EMC for the case in Fig. 3 is 3%.
It should be noted that all the Err% calculations were focused on Fig. 4. Percentage errors in the EMCs calculated with different
the prediction errors originating from only sampling 共flow mea- sample sizes for different simulation types with a prediction error of
surement errors were not considered兲 by using the same flow data N共0,0.592兲: 共a兲 randomly timed sampling 共Type 1兲; 共b兲 equally timed
for both the sampling simulations and the reference value calcu- sampling 共Type 2兲; 共c兲 equal-rainfall depth sampling 共Type 3兲; and
lations. 共d兲 equal-discharge sampling 共Type 4兲
Results and Discussion quired larger than 40 samples for 75% of the EMC estimates to
have less than 20% error; 60 samples estimate the EMCs within
20% error in most cases.
Estimation Errors in EMC
Fig. 4共b兲 shows the Err% distributions from the Type 2 simu-
The calculated values of Err% from the various simulations for lations. The worst case was n = 10 with Err% less than 60% ex-
different types of sampling strategies are presented in a series of cept three points of outliers, which reflects an improvement over
box plot figures, showing medians and 50% interquartile ranges Type 1 simulation 共randomly timed sampling兲. The mean values
with outliers. Fig. 4 shows the Err% distribution of simulated of Err% at n = 10, 20, 40, 60, and 100 were 36.3, 21.3, 15.2, 12.6,
EMCs for varying numbers of samples. Fig. 4共a兲 shows the re- and 9.8%, respectively. The median values of Err% were gener-
sults from Type 1 simulation. The largest Err% was approxi- ally less than the mean values. The corresponding standard devia-
mately 80% at n = 10. The mean values of Err% at n = 10, 20, 40, tions were 13.5, 4.1, 4.2, 2.9, and 1.9%. These statistics imply an
60, and 100 were 46.2, 28.4, 19.3, 15.4, and 11.9%, respectively. improvement over randomly timed sampling. When this sampling
The median values of Err% were slightly lower than the average strategy is used, approximately 40 samples are required to esti-
values. The corresponding standard deviations were 12.5, 6.1, 4.0, mate the EMCs within 20% error.
3.3, and 2.3%. The Type 1 simulation can serve as a benchmark Fig. 4共c兲 shows the Err% distributions from Type 3 simulation.
on the influence of sample size for estimating the EMCs, and is At n = 10, the worst case is approximately 30%, which reflects a
the most general sampling strategy. Random sampling inherently large improvement over Type 1 or Type 2 simulation. The mean
produced large errors in the estimated EMCs and, therefore, re- values of Err% at n = 10, 20, 40, 60, and 100 were 22.9, 17.5,
40
Err%
Accuracy in MFF Estimation
0
the medians and the line of equivalence. A larger number of
samples routinely produced more accurate MFF20 with less statis-
45-Min First Flush 1-Min
Enhanced tical dispersion of random trials 共distance between 25 and 75%
quartiles兲.
Fig. 5. Comparison of percentage errors in the EMCs from equal- As shown in Figs. 6共a兲 and Fig. 6共b兲, equally timed sampling
time sampling and first flush enhanced sampling simulations 共Type 5兲 tends to overestimate 共most medians lie above the equivalence
line兲 the MFF20 values with larger deviations from reference val-
ues for fewer numbers of samples. This is because the limited
numbers of grab samples cannot capture the rapid decline in COD
concentration in the initial runoff. In contrast, Figs. 6共c and d兲
14.2, 13.1, and 12.2%, respectively. The median values of Err%
show that equal-discharge sampling tends to underestimate 共all of
were generally the same as the mean values. The corresponding
median values lie under the equivalence line兲 the MFF20 values.
standard deviations were 2.2, 2.6, 3.8, 4.4 and 4.8%. As shown in
In the equal-discharge sampling strategy, initial sampling occurs
Fig. 4共c兲, the interquartile range increases with an increase in the
after observing a specified amount of runoff, and, therefore, the
number of samples for Type 3, which contradicts intuition. This
delay of sampling initiation, especially in low initial runoff rate,
results due to the stepwise nature of the recorded cumulative rain-
misses the high concentration of the initial runoff, underestimat-
fall depth. The data logger only receives a signal when a unit
ing mass first flush. A larger number of samples reduced this
amount of rainfall depth 共0.01 in兲 is accumulated in the tipping
underestimation problem 共values of R2 at n = 20 and n = 40 are
bucket of the rainfall gauge. As the sample number increases for
0.39 and 0.84, respectively兲, and the variation in MFF20 values
a given storm duration, the time interval between two consecutive
from 1,000 runs. When an automatic sampler is used, a shorter
sampling points becomes smaller than the time required to detect sampling pace will provide better MFF estimation.
the increment of rainfall depth, resulting in duplicate sampling By comparing the results from Type 2 and Type 4 simulations
points in the simulation and, thereby, increasing variation among with same numbers of samples in Fig. 6 关i.e., Figs. 6共a and c兲 or,
different storm events that have different rainfall characteristics Figs. 6共b and d兲兴, one can observe that equally timed sampling
共intensity and duration兲. This sampling strategy was better than can estimate the MFF20 more accurately than equal-discharge
random or equal-time sampling in terms of accuracy in EMC sampling when a relatively small number of sample size is used
estimation. Less than 20 samples were required for 75% of the 共values of R2 for equally timed and equal discharge sampling at
EMC estimates to be within 20% error. n = 20 are 0.84 and 0.39, respectively兲. The opposite results oc-
Fig. 4共d兲 shows the Err% distributions from the Type 4 simu- curred for EMC estimation; equal-discharge sampling is always
lations. It is obvious from the plots that Type 4 simulation has the superior to equally timed sampling for the EMC estimation, re-
best result from the aspect of outliers, averages, and variances. gardless of the number of samples. This can also be explained
The mean values of Err% at n = 10, 20, 40, 60, and 100 were 23.4, because the equal-discharge sampling collects fewer samples in
17.0, 12.2, 10.0, and 7.8%, respectively. The median values are the early runoff, when the flow is still increasing. The first flush
generally the same as the mean values. The corresponding stan- enhanced sampling strategy overcomes this problem; Fig. 6共e兲
dard deviations are 1.4, 1.3, 1.1, 0.9 and 0.7%. Compared to equal shows better estimates compared to Fig. 6共c兲 for almost the same
rainfall interval sampling, equal discharge volume sampling esti- number of samples.
mates the EMCs more accurately and precisely. The EMCs were
estimated with less than 20% error in most cases using only 20
samples. Approximately twice the number of samples was re- Potential for Improving Sampling Procedures
quired for similar accuracy using equally timed sampling, and
three times as many samples were required for randomly timed Effect of Prediction Error
samples. It is burdensome and expensive to collect so many grab samples,
Fig. 5 shows the Err% distributions from the Type 5 simula- and it is natural to ask what improvements can be made to reduce
tion. The average numbers of samples taken are 19 for first flush this burden. If the prediction error 共i兲 could be reduced, perhaps
enhanced sampling and 18 for the 45-min interval sampling by using an alternative analysis with less intrinsic variability, how
共equally timed sampling兲. The corresponding means and standard could the number of samples be reduced? According to the simu-
deviations of Err% are 21.3 and 3.8% for first flush enhanced lation results, if the error were reduced by 50% 共standard
sampling, and 27 and 9.9% for 45-min interval sampling, respec- deviation= 0.30兲, the means and medians of Err% can also be
tively. Although the average sample numbers of both methods reduced by about 50% in Type 2, Type 3, and Type 4 sampling
differs only by one sample, the accuracy of the estimated EMC simulations. When using a small number of samples 共n = 10, 20兲
was greatly improved using the first flush enhanced sampling in the Type 1 simulation, a reduced amount of the prediction error
Simulated MFF20
2
1.5
Type 2
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Type 2
n = 20 n = 40
2 2
(R = 0.84) (R = 0.94)
1
3
(c) (d)
(Median with 25%, 75% quartiles)
2.5
Simulated MFF20
1.5
Type 4 Type 4
n = 20 n = 40
2 2
(R = 0.39) (R = 0.84)
1
3
(e) (f)
(Median with 25%, 75% quartiles)
2.5
Simulated MFF20
1.5
First Flush Enhanced
Avg n = 19 1-min Sampling
2
2
(R = 0.96) (R ~ 1)
1
1 1.5 2 2.5 3 1 1.5 2 2.5 3
Reference MFF 20 Reference MFF 20
Fig. 6. Comparison between simulated and reference values of MFF20 for different sampling strategies 共values of R2 were calculated using
median values and equivalent line兲
could not proportionally reduce the Err% estimation. Fig. 7 shows provide a dramatic improvement in EMC estimation 共note that
the Err% distribution of simulated EMCs for varying numbers of larger than 20 samples were required for less than 20% of Err% at
samples with 0.3 of for different sampling strategies. Twenty = 0.59兲. This indicates that in order to obtain accurate EMCs,
samples provide less than 20% errors in 75% of the cases even in reducing the prediction error can also be important.
worst sampling strategy 共i.e., Type 1 randomly timed sampling兲.
Most of the cases had less than about 15% of Err% in Type 2, Extended Sampling
Type 3, and Type 4 sampling simulations with n = 20. When using Another alternative is to collect extended grab samples, which
Type 3 or Type 4 simulation, only 10 samples provide less than can be collected over a short period of time to composite the
10% of Err% in most cases and larger than 40 samples did not concentrations. Extended sampling can average out the sampling
Err%
Err%
40 40
20 20
0 0
40 (b) Type 2, n = 20
80
(b)
60
30
Err%
Err%
20
40
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10
20
0
0 (a) Type 4, n = 10
80 30
(c)
25
60
Err%
20
Err%
15
40
10
20 5
0
0 (b) Type 4, n = 20
30
80
(d) 25
Err%
60 20
Err%
15
40
10
20 5
0
Non-Extended 5 min 10 min 20 min
0
10 20 40 60 100 1-Min
Sample Size, n Fig. 8. Percentage errors in the EMCs calculated with different sam-
pling time extension in Type 2 and Type 4 sampling strategies with a
Fig. 7. Percentage errors in the EMCs calculated with different prediction error of N共0,0.592兲: 共a兲 Type 2, n = 10; 共b兲 Type 2, n = 20;
sample sizes for different simulation types with a prediction error of 共c兲 Type 4, n = 10; and 共d兲 Type 4, n = 20
N共0,0.302兲: 共a兲 Type 1 共randomly timed sampling兲; 共b兲 Type 2
共equally timed sampling兲; 共c兲 Type 3 共equal-rainfall depth sampling兲;
and 共d兲 Type 4 共equal-discharge sampling兲
transportation and analysis would be the same, because the grab
samples collected during the extended time are composited into a
single bottle for analysis.
Simulated MFF20
2
1.5
Type 4
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Type 2
5 min Extended Sampling 5 min Extended Sampling
n = 20 n = 20
2
2
(R = 0.82) (R = 0.60)
1
3
(c) (d)
(Median with 25%, 75% quartiles)
2.5
Simulated MFF20
1.5
Type 2 Type 4
10 min Extended Sampling 10 min Extended Sampling
n = 20 n = 20
2 2
1 (R = 0.83) (R = 068)
3
(d) (f)
(Median with 25%, 75% quartiles)
2.5
Simulated MFF20
1.5
Type 2 Type 4
20 min Extended Sampling 20 min Extended Sampling
n = 20 n = 20
2 2
(R = 0.86) (R = 0.74)
1
1 1.5 2 2.5 31 1.5 2 2.5 3
Reference MFF 20 Reference MFF 20
Fig. 9. Comparison between simulated and reference values of MFF20 using 20-min extended grab sampling time for Type 2 and Type 4 sampling
strategies
being less desirable strategies. Reducing the sampling error can which can be programmed to collect several hundred subsamples
greatly improve the accuracy in EMC estimation. However, equal per storm, are far superior to collection by grab sampling, even if
discharge grab sample with relatively large sampling pace might 100 grab samples are used. If automatic samplers can be used
not be a good strategy for MFF estimation because the small without chemical or physical biases 共e.g., such as the concerns of
number of samples will underestimate mass discharge rate of the sample carry over when sampling for oil and grease, or the intro-
initial runoff. For MFF estimation, an automatic sampler with duction of artifactual toxicity兲, they should be used. A new con-
short sampling pace is the best choice and larger sample numbers cept, extended grab sampling, which uses several grab samples
or first flush enhanced sampling will be next best. collected over a short time is a promising way to reduce sampling
The results show that automatic flow weighted samplers, variability when composite samples are not practicable.