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Real-time contaminant detection and

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Article in Journal of Environmental Management · June 2009

DOI: 10.1016/j.jenvman.2009.01.021 · Source: PubMed

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 Journal of Environmental Management 90 (2009) 2494–2506

Contents lists available at ScienceDirect

Journal of Environmental Management

journal homepage: www.elsevier.com/locate/jenvman

Real-time contaminant detection and classification in a drinking water pipe

using conventional water quality sensors: Techniques and experimental results
Y. Jeffrey Yang*, Roy C. Haught, James A. Goodrich
U.S. Environmental Protection Agency, National Risk Management Research Laboratory, Water Supply and Water Resources Division,
26 West Martin Luther King Dr., Cincinnati, OH 45268, USA

a r t i c l e i n f o a b s t r a c t

Article history: Accurate detection and identification of natural or intentional contamination events in a drinking water
Received 10 October 2007 pipe is critical to drinking water supply security and health risk management. To use conventional water
Received in revised form quality sensors for the purpose, we have explored a real-time event adaptive detection, identification and
24 December 2008
warning (READiw) methodology and examined it using pilot-scale pipe flow experiments of 11 chemical
Accepted 21 January 2009
Available online 6 March 2009
and biological contaminants each at three concentration levels. The tested contaminants include pesti-
cide and herbicides (aldicarb, glyphosate and dicamba), alkaloids (nicotine and colchicine), E. coli in
terrific broth, biological growth media (nutrient broth, terrific broth, tryptic soy broth), and inorganic
Keywords:
Contaminant detection chemical compounds (mercuric chloride and potassium ferricyanide). First, through adaptive trans-
Contaminant identification formation of the sensor outputs, contaminant signals were enhanced and background noise was reduced
Drinking water security in time-series plots leading to detection and identification of all simulated contamination events. The
Detection threshold improved sensor detection threshold was 0.1% of the background for pH and oxidation–reduction
Adaptive monitoring potential (ORP), 0.9% for free chlorine, 1.6% for total chlorine, and 0.9% for chloride. Second, the relative
Water quality sensors changes calculated from adaptively transformed residual chlorine measurements were quantitatively
related to contaminant-chlorine reactivity in drinking water. We have shown that based on these kinetic
and chemical differences, the tested contaminants were distinguishable in forensic discrimination
diagrams made of adaptively transformed sensor measurements.
Published by Elsevier Ltd.

1. Introduction applications, conventional water quality sensors measure the

Accurate real-time detection of chemical and biological contami-
nants is often required for planning and implementing mitigation
measures to protect water supplies (Hasan et al., 2004; ILSI, 1999; U.S.
EPA, 2005; Jain and McLean, 2006). As highlighted in the incidental
contamination of potable water in Scotland (Gavriel et al., 1998),
poisoning of water supplies in Japan (Yokoyama, 2007), and domestic
bioterrorist acts (Stern, 2000), intentional sabotage remains a signifi-
cant threat to the public health (WHO, 2004; Greenfield et al., 2002).
The urgency to protect water supplies as noted in Burrows and Renner
(1999) has prompted numerous investigations into methodology in
detection, decontamination, public health preparedness, and threat
scenario analysis (e.g., Murray et al., 2006; Iqbal et al., 2000; Greenfield
et al., 2002; Khan et al., 2001; Meinhardt, 2005; Morse et al., 2003).
A practical contaminant detection and warning system must
balance detection accuracy, range, and the cost of system deploy-
ment and operation; such a trade-off, for example, is common in
design of chemical sensor systems (NRC, 1995). In drinking water
* Corresponding author. Tel.: þ1 513 569 7655.
E-mail address: yang.jeff@epa.gov (Y. Jeffrey Yang).
general parameters such as free chlorine, total chlorine, tempera-
ture, pH, oxidation–reduction potential (ORP), specific conductivity,
dissolved oxygen (DO), total organic carbon, nitrogen (nitrate,
nitrite and ammonia), turbidity and particle counts. These sensors
are advantageous in operational economics and for potential use in
both drinking water security and water quality monitoring. On the
other side, a sensor output is a composite of electronic signal
contribution from contamination, natural background, instrument
noise and drift, and other irregularities during operation and data
communication. Source water and treatment process changes in
water plants, flow of aged water from a storage reservoir, water
demand variation, and quality deterioration in water distribution
are examples of non-contaminant events (e.g., Harding and Walski,
2000; Powell et al., 2000; Kroll and King, 2006), which can generate
variations in real-time sensor outputs that can resemble some or
many characteristics of intentional contamination. This gives rise to
the challenge of distinguishing them from those of a contamination
event. The disadvantage in poor selectivity of a conventional water
quality sensor can lead to a high rate of false detections, both false-
negative and false-positive, that must be characterized and reduced
to an acceptable level (McKenna et al., 2006; U.S. EPA, 2005).

0301-4797/$ – see front matter Published by Elsevier Ltd.

doi:10.1016/j.jenvman.2009.01.021
 Y. Jeffrey Yang et al. / Journal of Environmental Management 90 (2009) 2494–2506
Numerous publications are devoted to discuss advanced tech-
niques for improving source separation in a composite sensor
signal and thus enhancing the sensor detection capability (e.g.,
Choi et al., 2005; Feintuch, 1990; Lin et al., 2007). In the case of
conventional water quality sensors, better detection accuracy and
contaminant selectivity are achieved by using advanced sensor
data processing techniques or through developing hardware such
as the new generations of optical sensors for bacterial and
chemical contaminations (e.g., U.S. EPA, 2005; NRC, 1995). The
first approach relies on data mining and other similar statistical
techniques such as multi-variant cluster analysis (Klise and
McKenna, 2006), adaptive data treatment (Yang et al., 2007), and
control chart-based robust statistics (Kroll and King, 2006). Szabo
et al. (2007) reported detectable sensor responses to the presence
of various contaminants in pilot-scale pipe flow experiments.
Haught et al. (2005) reported from bench-scale testing the
minimum concentration threshold of contaminants above which
their presence can be registered in water quality sensors. Recently,
Yang et al. (2007) proposed a real-time event adaptive detection,
identification and warning (READiw) method using an iterative
detection procedure (Fig. 1). In a field application, water quality
measurements are transmitted to a process unit where the sensor
signals are analyzed in real-time to differentiate anomalies
between contamination and natural background. The real-time
anomaly detection is governed by statistical comparison of new
measurements against the adaptively back-tracked background in
a moving time window.
In this paper, we will describe the READiw techniques in sensor
data treatment for enhanced contaminant detection and contami-
nant property assessment. The objective is to establish a method-
ology for background noise suppression and better anomaly
detection, to evaluate the relations between contaminant-chlorine
reactivity and the measured water quality changes, and finally to
classify contaminants using reaction kinetics and chemical
discrimination techniques. These principles and techniques will be
examined in pilot-scale drinking water distribution experiments
for 11 selected chemical and biological contaminants under
turbulent flow conditions.
Sensor measurements in
schedule update
water pipes
Sampling
Change detection and
1 anomaly identification
Local adaptive
Background update background data
Detection verification,
2 contaminant classification
Background update
Contaminant intrusion
warning
Fig. 1. Simplified READiw process for event detection and contaminant identification
(after Yang et al., 2006). Sensor signal from field sensors is adaptively processed to
compare against the background in a moving time window for change point and
anomaly detection, followed by anomaly verification and contaminant classification.
Techniques used in the process are numbered: (1) distance-based statistical coarse
filter for change point and anomaly detections; (2) detection verification and
contaminant identification by chemical and kinetic property analysis using the
observed Dc values in multiple parameters, classification in forensic discrimination
diagrams, and by mass transport modeling.
2495
2. Experiments
2.1. Experimental setup and test materials
Transport testing of the contaminants was conducted using
a 365.9-m long and 7.6-cm diameter pilot-scale ductile iron water
distribution pipe (Fig. 2). Because of the fiberglass-lined pipe inte-
rior, chlorine wall demand and contaminant-wall interactions were
assumed negligible. In all experiments using chlorinated tap water
from the Greater Cincinnati Water Works, the flow rate and linear
velocity were 83.3 L/min and 0.305 m/s, respectively (Re w 25 000).
Contaminant intrusion was simulated by injecting contaminant
solution into the pipe flow at 0.5 L/min for 20 min. Subsequent water
quality changes were measured at two real-time sensor stations 24.4
and 335.4 m downstream from the injection port. Used sensor
instruments included a reagent-free membrane-covered polar-
organic free chlorine sensor (ATI 15/B-2-1, Analytical Technology,
Inc.) with a 0.5% or 0.02 mg/L measurement accuracy, a total chlorine
Hach Cl-17 panel using the n,n-diethyl-p-phenylenediamine color-
imetric method with a 0.035 mg/L detection limit and a 5% accuracy,
and the YSI-6920 multi-probe instrument for other parameters
(ORP, pH, dissolved oxygen, turbidity, specific conductivity and
chloride). Hydraulic residence time was 1.33 min and 18.33 min at
the 24.4-m and 335.4-m monitoring stations, respectively.
Tested contaminants were pesticide (aldicarb), herbicides
(dicamba, glyphosate), alkaloid nuerostimulants (nicotine, cochi-
cine), bacterium and biological growth media (Escherichia coli in
terrific broth, nutrient broth, tryptic soy broth), and inorganic
laboratory chemicals (mercuric chloride, and potassium ferricya-
nide). Tested RoundupÒ solution (Monsanto Corp., St. Louis) con-
tained 18% glyphosate [N-(phosphonomethyl) glycine], a principal
chemical ingredient in the widely used non-selective herbicide. The
compound, containing a phosphonate [-PO(OH)2], a carboxylate
and an amine functional group, has a maximum contaminant level
0.7 mg/L on the U.S. EPA national primary drinking water
contaminant candidate list. Aldicarb and dicamba in the tests were
pure compounds from Sigma–Aldrich. Aldicarb [2-methyl-2-
(methylthio) propionaldehyde 0-methylcarbmoyloxime], a principle
active N-methylcarbamate compound in pesticide TemikÒ, is
oxidized in chlorinated drinking water to produce reaction inter-
mediates aldicarb–sulphoxide and aldicarb–sulphone (Mason et al.,
1990; Miles, 1991). In a different chemical class, the chlor-
ophosphous herbicide dicamba (5-methoxyl benzoic acid) has
a stable phenyl benzoic ring, a carboxyl (-COOH) and a methoxyl
(-OMe) function group. The OMe functional group and neighboring
chlorine in spatial proximity are resonance-stabilized making
dicamba persistent and bioaccumulative in the environment.
Laboratory-grade colchicine and nicotine were tested as model
alkaloids known as neuron-stimulants and as poisons at high
concentrations. Characteristic of a three-ring molecular structure,
colchicine has 3 OMe functional groups attached to the trimethy-
phenyl A-ring, one OMe to the tropolone C-ring, and one NHAc
group bound into the B-ring with antimitosis functionality (see Ray
et al., 1981). For nicotine, Hua et al. (2006) and Gibs et al. (2007)
indicated that the bicyclic alkaloid is oxidized to form cotinine in
drinking water disinfection.
Investigated biological materials include Escherichia coli in
terrific broth, nutrient broth, and tryptic soy broth from Sigma–
Aldrich. Escherichia coli K-12 (ATCC25204), a common surrogate
indicator for pathogenic strains linked to outbreaks, was tested as
a model vegetative cell suspension. The cells were cultured in
terrific broth, a mixture of large-molecule tryptone, yeast extract
and glycerol. Principal ingredients are peptone and sodium chloride
for nutrient broth, casein and soy peptone for tryptic soy broth.
These growth media are potentially associated with the use of
2496 Y. Jeffrey Yang et al. / Journal of Environmental Management 90 (2009) 2494–2506

Cincinnati tap water

Dimensions:

426.8 m – Total pipe length

V=2841 L 7.62 cm – Inside pipe diameter

24.4 m – From location 0 to 1

Injection port 335.4 m – From location 0 to 2
0 Qp= 83.2 L/min
Qi=0.5 L/min 1

To sensor stations
To drain

Fig. 2. Experimental setup of a pilot-scale distribution pipe device for the testing of 11 chemical and biological contaminants. Water flow rate was maintained at 83.4 L/min by the
use of a 2841-L hydraulic surge tank. Following contaminant injection at location 0, changes in water quality parameters were measured in two sensor stations at locations 1 and 2.

biological agents and, along with the E. coli surrogate, can represent It ¼ Ict þ Ibt þ Int þ Idt þ s (1)
a wide range of potential biological threats to a water system (Szabo
et al., 2007). Other tests materials are laboratory-grade (>99%
Ict ¼ b,Cit þ qi (2)
purity) inorganic mercuric chloride and potassium ferricyanide
both from Sigma–Aldrich. In Eq. (2), the time-independent instrument response factor (b) and
the intercept ðqi Þ yield sensor output statistically centered at
2.2. Composite dataset for event detection a target concentration (e.g., chlorine residual) that consist of the
introduced contaminants and a weighted mean of background
Table 1 shows experimental results for the 11 contaminants, measurements in a locally adaptive time window. Use a time-series
each at three initial concentrations. Detailed experimental data and b
polynomial function½ mFðtÞ to approximate both Itb and the time-
testing conditions are described in Szabo et al. (2007). Sensor dependant instrument drift (Itd), where m
b is a matrix of coefficients,
outputs for individual tests were arbitrarily combined into a single and further assume normal distribution for the instrument noise
composite dataset in time series without correction of the differ- and operation-related random errors ½nðInt ; sÞ. Then a water quality
ence in baselines and individual sensor calibrations. This leads to sensor output in Eq. (1) can be written in a general form of:
baseline fluctuations between experiments; some are abrupt and  
substantial (Fig. 3) resembling sudden changes in water quality and It ¼ b,Cit þ mFðtÞ
b þ n Int ; s (3)
sensor operations in field application. For the composite dataset,
Eq. (3) presents a concept for source separation of a water quality
background noise mostly due to the sudden baseline changes is
sensor output. Similar forms of expression in signal superposition
measured as one standard deviation of the sensor outputs equal to
and decomposition can be found in acoustic sensor signal process-
7.9% for pH, 8.6% for ORP, 8.7% for free chlorine, 8.9% for total
ing, medical imaginary analysis, and sensor-based process engi-
chlorine, and 42.1% for chloride.
neering controls (e.g., Aichner et al., 2004; Choi et al., 2005; Yan et al.,
2005; Feintuch, 1990). Methods are sought to identify the contam-
3. Sensor data treatment for anomaly detections
inant signal in form of water quality changes and separate it from
b
background variations ½ mFðtÞ and instrument noises ½nðInt ; sÞ. Yang
The iterative READiw process regulates anomaly detection,
et al. (2007) described an adaptive monitoring process for signal
detection confirmation and contaminant classification (Fig. 1). This
separation using sensor output normalized against those in an
section illustrates the detection principles and techniques in
adaptive time window (T). When ½mFðt þ 1Þ  mFðTÞ  IiT and is set
application to the experimental composite dataset.
at a constant, the relative change (Dc) in sensor output between at
time t and the adaptive time window is obtained. From Eq. (3),
3.1. Adaptive data transformation
Iit bðCt  CT Þ b
mFðtÞ b
 mFðTÞ
As a measurement of electronic energy from multiple sources to Dc ¼ 1  ¼   or
which a chemical sensor is exposed, its output can be decomposed IiT IiT IiT
through signal treatment for principal source estimations and ðCt  CT Þ 1
physical representations (e.g., NRC, 1995; Choi et al., 2005; Lee et al., Dcy  ð4Þ
CT 1þk
2004; and Lin et al., 2007). Similarly in drinking water monitoring,
a conventional sensor output at time t (It) can be considered as
a composite of instrument response to a target substance (Itc), effect  
of the natural background variation (Itb), instrument noise (Itn) and
b
mFðTÞ þ n InT ; s
k ¼ and lim ðkÞ/0 (5)
drift (Itd), and operation-related random variance (s). Itb equals zero bCiT T/N
for a selective compound-specific sensor and can vary for non-
selective water quality sensors, for which signal output and target In background monitoring, the relative change of sensor outputs
concentration (Cti ) are related by: converges to zero. Dc < 0 for parameters of a reactant, and Dc > 0
 Y. Jeffrey Yang et al. / Journal of Environmental Management 90 (2009) 2494–2506 2497

Table 1
Relative change (Dc) of 5 parameters determined at two sensor stations for the 11 biological and chemical contaminants.

Contaminants Experiment Observed Dc % (22.4-m station) Observed Dc % (335.4-m station)

a b
Day c(F,S) Clf Clt Chloride ORP pH Clf Clt Chloride ORP pH
Aldicarb 3 2.2 88.2  0.6 82.1  0.7 1.8  0.4 9.4 ND 87.1  0.0 80.1  1.1 2.3  0.2 0.6 0.1  0.0
MW 24 2.2 93.7  0.9 85.4  0.9 3.8 9.6 ND 86.5  0.7 82.5  1.4 2.8  0.2 ND 0.2  0.0
190.39 3 1.1 44.5  0.7 42.5  1.3 ND 3.6 ND 43.1  0.4 41.6  0.1 0.9  0.1 ND ND
24 1.1 45.3  0.5 44.1  0.6 ND 6.5 ND 42.1  0.7 42.9  0.0 1.4  0.2 ND ND
3 0.2 8.0  0.5 8.1  0.5 ND ND ND 8.7  0.1 7.7  0.1 ND ND ND
24 0.2 8.4  0.6 8.6  0.4 ND 1.2 ND 8.1  0.1 8.4  0.6 ND ND ND

Dicamba 67 2.6 ND ND ND 1.1  0.0 0.7  0.1 ND ND ND 0.5  0.0 0.8  0.1
MW 71 2.6 ND ND ND 1.2  0.0 0.7  0.0 ND ND ND 0.7  0.0 0.8  0.0
221.04 67 1.3 ND ND ND 0.5  0.0 0.4  0.1 ND ND ND ND 0.3  0.1
71 1.3 ND ND ND 0.7  0.1 0.2  0.1 ND ND ND ND 0.3  0.1
67 0.8 ND ND ND ND ND ND ND ND ND ND
71 0.8 ND ND ND ND ND ND ND ND ND 0.2  0.1

Glyphosate 22 3.0 96.6  0.0 52.2  0.5 4.1 14.0 2.9  0.0 95.1  0.0 51.6  4 2.5  0.2 1.4 4.9  0.1
MW 23 3.0 97.3  0.6 51.5  2.0 4.1 20.0 2.4  0.1 95.2  0.0 48.7  0.5 2.2  0.1 1.2 4.1  0.1
169.08 23 1.5 62.5  2.1 30.5  0.8 2.1  0.2 8.8 0.5  0.1 58.7  0.8 29.1  0.9 1.3  0.1 ND 0.7  0.0
22 0.4 31.7  0.7 16.5  0.4 1.3  0.0 1.9 ND 31.0  0.9 15.4  0.4 ND ND 0.4  0.1
23 0.4 36.2  0.5 18.0  0.0 1.4  0.3 3.4 ND 33.4  0.3 17.5  0.3 ND ND 0.4  0.1

K Ferricyanide 11 3.2 ND 21.8  3.6 24.7 ND ND ND 21.6  0.7 ND 0.7  0.0 ND

MW 21 3.2 ND 24.1  3.1 19.9 ND ND ND 23.4  1.9 22.7  3.6 ND ND
422.39 11 1.6 ND 10.0  0.3 15.3 0.7  0.0 ND ND 9.8  3.4 ND ND ND
21 1.6 ND 12.1  0.4 ND ND ND ND 10.8  0.4 13.7  0.2 ND ND
11 0.6 ND 2.7  0.3 ND ND ND ND 2.9  0.3 ND ND ND
21 0.6 ND 3.9  0.6 ND ND ND ND 3.9  0.3 10.1  0.4 ND ND

Mercuric chloride 52 2.2 ND ND ND 2.2  0.0 1.5  0.1 1.1  0.2 ND 2.1  0.2 0.9  0.2 1.4  0.0
MW 53 2.2 ND ND ND 1.8  0.0 1.2  0.1 1.1  0.0 ND 1.3  0.2 0.8  0.0 1.2  0.0
271.52 52 1.1 ND ND ND 0.7  0.1 0.7  0.0 ND ND 1.1  0.1 0.5  0.0 0.7  0.0
53 1.1 ND ND ND 0.6  0.0 0.7  0.1 ND ND 0.9  0.1 0.4  0.0 0.6  0.0
52 0.4 ND ND ND ND ND ND ND ND 0.2  0.0 0.2  0.0
53 0.4 ND ND ND 0.3  0.0 ND ND ND ND 0.1  0.0 0.2  0.0

Nicotine 25 3.8 39.2  0.4 23.0  1.1 ND 8.1 0.7  0.1 79.7  0.5 43.9  0.9 ND 3.8 0.9  0.0
MW 28 3.8 48.0  0.5 30.0  0.5 ND 14.6 0.9  0.1 88.5  0.6 48.0  0.6 ND 3.9 1.1  0.0
162.23 25 1.9 24.9  0.3 15.2  0.7 ND 5.8 ND 44.9  0.4 26.4  0.7 ND 2.0 0.5  0.0
28 1.9 29.3  0.6 19.8  0.5 ND 7.5 ND 51.7  0.6 30.4  0.7 ND 2.4 0.5  0.1
25 0.4 7.9  0.2 5.5  0.3 ND 1.3 ND 13.0  0.4 9.3  0.4 ND 0.5 ND
28 0.4 9.6  0.1 6.9  0.4 ND 2.5 ND 15.9  0.0 10.0  0.5 ND 0.4 ND

Colchicine 3 3.6 88.2  0.6 82.1  0.7 2.1 9.5 ND 87.1  0.0 80.6  0.7 ND 0.6 ND
MW 24 3.6 91.2  0.7 85.3  0.9 3.8 17.2 ND 86.4  0.7 83.1  0.3 ND 1.0 ND
399.44 3 1.8 44.5  0.7 43.2  0.8 1.0  0.1 3.4 ND 43.2  0.5 41.6  0.5 ND ND ND
24 1.8 45.3  0.5 43.9  0.5 1.8  0.2 6.5 ND 42.2  0.3 42.6  0.6 ND ND ND
24 0.4 8.3  0.7 8.8  0.0 ND 1.2 ND 8.2  0.1 19.2  0.4 ND ND ND

E. coli in terrific broth 1 0.14 89.9  0.5 7.7  0.5 3.2 10.0 ND 88.2  0.0 9.4  0.4 8.6 5.2 1.2  0.0
2 0.14 89.7  0.5 7.6  0.5 3.6 13.0 1.0  0.1 89.5  0.6 9.2  0.4 8.4 5.8 1.2  0.0
1 0.07 66.5  0.9 7.4  0.3 1.6  0.2 7.8 1.3  0.7 71.0  0.7 12.8  0.3 ND 4.5 0.5  0.0
2 0.07 63.6  0.5 8.0  0.1 1.5  0.2 8.6 0.4  0.1 69.0  1.0 12.8  0.3 ND 4.4 0.5  0.1
1 0.01 15.2  0.5 ND ND 2.2 ND 16.7  0.8 5.6  0.6 ND ND ND
2 0.01 ND ND ND 0.4(0.0) ND ND 2.0  0.0 ND ND ND

Nutrient broth 136 0.95 12.0  0.1 3.3  0.0 1.5  0.3 4.9 ND 15.5  0.5 5.3  0.5 ND ND ND
137 0.95 13.5  0.5 2.8  0.3 ND 3.7 ND 25.6  0.7 6.8  0.1 2.7 2.9 ND
136 0.47 6.6  0.0 2.4  0.1 ND 3.8 ND 6.7  0.0 3.3  0.0 ND ND ND
137 0.47 1  0.0 2.0  0.1 ND 7.0 ND 12.6  0.5 4.2  0.1 1.1  0.2 1.4  0.1 ND
136 0.12 2.3  0.3 3.0  0.6 ND 1.7 ND 2.8  0.3 1.6  0.5 ND ND ND
137 0.12 2.3  0.4 ND ND ND ND ND 1.7  0.1 ND ND ND

Terrific broth 102 0.95 21.1  0.3 3.7  0.0 ND 2.1 ND 26.0  0.3 7.4  0.3 ND 0.7 ND
112 0.95 21.4  0.1 3.3  0.1 ND 1.9 ND 25.4  0.5 7.4  0.5 ND 0.6 ND
102 0.47 10.6  0.0 2.2  0.1 ND 1.1 ND 12.9  0.5 4.2  0.4 ND ND ND
112 0.47 11.7  0.0 2.4  0.1 ND 0.9 ND 14.2  0.1 4.5  0.5 ND ND ND
112 0.12 3.4  0.0 ND ND ND ND 4.0  0.1 2.0  0.0 ND ND ND

Tryptic soy broth 141 0.95 17.8  0.3 4.4  0.4 0.9  0.2 3.8 ND 23.3  0.1 9.2  0.9 ND 3.1 ND
176 0.95 15.6  0.3 6.7  0.1 2.7  0.2 2.7 ND 22.7  0.6 16.7  0.8 ND 4.6 ND
141 0.47 9.7  0.6 ND ND 2.3 ND 12.6  0.0 5.7  0.4 ND 1.9  0.0 ND
176 0.47 10.1  0.3 4.3  0.5 1.7  0.2 1.7  0.1 ND 14.1  0.8 10.2  0.1 ND 1.8  0.0 ND
141 0.12 3.5  0.5 ND ND 0.8  0.0 ND 3.8  0.5 2.7  0.4 ND 0.5  0.0 ND
176 0.12 3.1  0.3 ND ND 0.5  0.0 ND 4.7  0.4 3.3  0.1 ND 0.2  0.1 ND

Note: ND – No quantitative detection.

15.2  0.7: Mean and standard deviation of percentage relative changes (Dc%) calculated using Eq. (4).
a
In day sequence since the start of 176-day testing period.
b
Initial fast-reacting (F) or slow-reacting (S) contaminant concentration in mg/L or ml/L for E. coli in terrific broth.
2498 Y. Jeffrey Yang et al. / Journal of Environmental Management 90 (2009) 2494–2506

1.2
(mg/L) 0.8
Clf
0.4
0.0 0.2
-0.2

Δc
-0.4
1.5 -0.8
(mg/L)

1.0
Clt

0.5
0.0 0.5
0.0

Δc
-0.5
-1.0
Chloride

60
(mg/L)

40
20 0.3
0 0.2

Δc
0.1
0.0
9.5 -0.1
(S.U.)

8.5
pH

7.5 0.05
6.5

Δc
0.00

900 -0.05
(mV)
ORP

700

500 0.3

Δc
0.0

-0.3
AL AL DI DI GL GL PF PF MC MC NC NC CC CC EC EC NB NB TB TB TSB TSB

0 5 10 15 20 25 30 35
Time (hour)

Fig. 3. Time-series plots of the experimental composite dataset (blank line) for free chlorine (Clf), total chlorine (Clt), chloride, pH and ORP at the 22.4-m sensor station; plots for the
other parameters are not shown. Dc–t plot of adaptively treated sensor outputs is attached below each of the experimental dataset. Note that the adaptive sensor output treatment
has significantly reduced background noise (green line) and enhanced contaminant signals (red line) for each of the injection events: aldicarb (AL), dicamba (DI), glyphosate (GL),
potassium ferricyanide (PF), mercuric chloride (MC), nicotine (NC), colchicine (CC), E. coli in terrific broth (EC), nutrient broth (NB), terrific broth (TB), and tryptic soy broth (TSB).

for parameters of a reaction product. The monitoring operator k is
a small constant in design of an adaptive monitoring program,
a condition that can be difficult to satisfy for excessive background
variations and instrument drift or failure.
3.2. Concentration–time patterns and anomaly detection
The composite sensor dataset after adaptive treatment using Eq.
(4) shows small background variations and the enhanced
contaminant signals (Fig. 3). Consistent patterns in the Dc–t plot
correspond to the contaminant injection events and have the
marked difference in geometry among the water quality
parameters.
3.2.1. U-shape loss pattern
Typical of chlorine residual loss at a reactive contaminant
‘‘slug’’, the U-shape residual loss pattern is readily detectable and
quantifiable (Fig. 3). In curve geometry (Fig. 4), the opening width
in segment BB0 marks the time-equivalent pipe length where
residual loss has occurred; the relative change (Dc) is uniform in
the flat curve bottom (segment bb0 ) within the ‘‘slug’’. Sharp-sided
curvature suggests a rapid recovery of concentration to the
background level where Dcy0. In pH sensor outputs (Figs. 3 and
4), the U-shape pattern is also observed indicating more acidic
conditions in the contaminant ‘‘slug’’. It has a wider opening
width (segment DD0 ) than the bottom (segment dd0 ) likely due to
molecular diffusion and longitudinal dispersion of the reaction
product Hþ in the pipe flow.
3.2.2. Inversed U-shape pattern
The pattern is observed in chloride, in pH for nicotine and in total
chlorine for potassium ferricyanide (Fig. 3). Like hydrogen ion, chloride
is a conservative reaction by-product subject to longitudinal disper-
sion in pipe. This generates the inversed asymmetric U-shape pattern
as observed in the experiments of aldicarb, glyphosate, potassium
ferricyanide, colchicine, and biological contaminants. When the
dispersion effect is sufficiently large, the asymmetric pattern at the
upstream sensor stations is transformed into the dispersive inversed
V-shape along the flowing distance (Yang et al., 2007).
3.2.3. V-shape pattern
Commonly observed in ORP measurements (Fig. 3), the V-shape
pattern reflects the ORP reduction in the contaminant ‘‘slug’’ due to
chlorine residual loss. The ORP loss curve begins at the downstream
edge of a contaminant ‘‘slug’’ marked by the chlorine loss, and
recovers to the background level upstream of the contaminant-
water interface (Fig. 4). An inversed V-shape pattern is common in
the mercuric chloride experiments. For the V-shaped pattern and
its inversed counterpart, the relative change Dc ¼ jcmax jorjcmin j.
3.2.4. Detection and quantifications
The characteristic patterns of type curves were defined by the
curvature change point in a Dc–t plot (Fig. 4); their geometry
measurements (opening width, bottom width, and relative
concentration change) of the detections are listed in Table 1.
Change points were determined in a low statistical filter (a ¼ 90%)
to include all potential contaminant events and to reduce false-
negative detections. This initial detection was then confirmed and
 Y. Jeffrey Yang et al. / Journal of Environmental Management 90 (2009) 2494–2506 2499

By applying the above detection criteria to the composite dataset,

all contaminant injection events at different concentration levels
were identified (Fig. 3). For glyphosate, the injection event was
B B’ accurately detected at the lowest concentration 0.4 mg/L (Table 1)
below the U.S. EPA drinking water standard at 0.7 mg/L. One false-
C’
positive detection event occurred to total chlorine in one mercuric
Clt chloride experiment. For all experiments, the smallest Dc value for an
Clf
accurate detection is 0.1% of the background value in pH and ORP, 0.9%
in free chlorine, 1.6% in total chlorine and 0.9% in chloride (Table 1).

C C’
4. Kinetic relationships in sensor responses

Chloride The kinetic relationship between contaminant-chlorine reac-

b b’ tion and adaptively treated water quality parameters provides
a basis for the second READiw step in detection verification
and contaminant classification (Fig. 1). This principle is examined
using the experimental data of 11 contaminants each at three
A A’ initial concentrations. For the fiberglass-lined water pipe of
D’ assumed negligible wall demand, residual chlorine loss from
contaminant-introduced new bulk demand is given in two parallel
D
reactions:
pH kf ks
f ½F þ d1 ½D / p1 ½P1  s½S þ d2 ½D / p2 ½P2 
d d’
In successive oxidation steps, [P1] in the fast reaction is an inter-
ORP mediate and equals to [S] in the slow-reactions; f, s, d1, d2, p1, and p2
are reaction stoichiometric constants; and kf, ks are kinetic constant
a’ of fast- and slow-reactions, respectively. This type of successive
reactions can be found in chlorination of aldicarb, glyphosate, and
other pesticides and herbicides (Miles, 1991; Mason et al., 1990;
Brosillon et al., 2006; Huston and Pignatello, 1999), for which the
t competitive second-order kinetic model of Clark and Sivaganesan
(2002) applies. Theoretical chlorine residual loss (Dc*) within
Fig. 4. Examples of type Dc–t curves for total chlorine, free chlorine, chloride, ORP and
pH selected from the 1.1 mg/L aldicarb experiment. Change points are statistically a contaminant ‘‘slug’’ is given by:
determined to calculate Dc values and curve geometry for contaminant classifications. 1  e61 t 1  e62 t
Dc* ¼ Z R1 þ ð1  ZÞ R (6)
1  R1 e 61 t 1  R2 e62 t 2
designated of a contamination event under the assumptions d1 CF0 d2 CS0
below: R1 ¼ ; R2 ¼
fCD0 sCD0
- Dc measurements vary continuously with time for a contami- 61 ¼ kf R1 ; 62 ¼ ks R2
nant ‘‘slug’’ moving through a sensor station and in response to
Parameters CF0 ; CS0 ; CD0
are initial molar concentrations of fast-
longitudinal dispersion of the contaminants into the bulk
reacting, slow-reacting contaminant, and chlorine (or other disin-
water. The continuous variation in a Dc–t plot is consistent
fectants), respectively. Symbols kf, ks represent the chlorine
with contaminant transport in pipe flow that has been
reaction kinetic constant for fast-reacting and slow-reacting
extensively described in literature (e.g., Rossman et al., 1994;
contaminants, respectively; Z is the chlorine fraction consumed by
Ekambara and Joshi, 2004; Biswas et al., 1993). Discontinuities
the fast-reactions. For those fast-reacting contaminants,u1 >> u2 ,
in sensor measurements are unlikely a result of contamination,
eu1 t z0 and variable x is a small constant at a given t. Conversely
but sensor operational and data communication errors char-
the chlorination oxidation of slow-reacting contaminants proceeds
acteristic of the sharp asymmetric oscillation patterns in Fig. 3.
in a single step (Z ¼ 0). Under these conditions and by replacing Dc*
- An intentionally introduced contaminant ‘‘slug’’ has a finite
with the adaptively treated sensor measurement Dc in Eq. (4), the
volume and length in a distribution pipe, as shown by the U-
relationship in Eq. (6) becomes:
shape or V-shape patterns on a Dc–t plot. Systematic water
quality change in excess of days over a large portion of   0
d1 1 CF 0
a distribution network is likely the result of variations in water Dc ¼ Z þx fast-reacting contaminant (8)
f 1 þ k CD0
treatment and distribution operations. Daily changes due to
network operations are often cyclic in time-series plots (Kroll  0 " #
1 sð1 þ kÞ CD eu2 t
and King, 2006) and can be quantified in water distribution ¼   þ ð1 þ kÞ 
modeling. In contrast, contaminant intrusions are generally Dc  x0 d2 1  eu1 t CS0 1  eu2 t
the isolated events both in time and space by which the natural slow-reacting contaminant ð9Þ
cyclic oscillation patterns can be distinguished.
0 x
- For intentionally introduced contaminants, the associated x ¼
1þk
changes in water quality parameters are compatible with each
other and agree with known chemical reactions and physical In Eqs. (8) and (9), the linear and intrinsically linear relationships in
mixing as illustrated in the section that follows. sensor responses are shown in the Dc–C0F /C0D and 1/Dc0 –C0D/C0S plots
2500 Y. Jeffrey Yang et al. / Journal of Environmental Management 90 (2009) 2494–2506

as for the experiment results (Figs. 5 and 6). The large regression 1.0
correlation coefficients in Table 2 suggest that the adaptively Clf (22.4-m)
treated sensor data satisfy the kinetic relationships in Eqs. (8) and 0.8 Clt (22.4-m)
(9), based on which the contaminants can be classified into non-
Clf (335.4-m)
reactive, fast-reacting, and slow-reacting groups in reference to the
0.6 Clt (335.4-m)
1.33-min and 18.3-min hydraulic residence time. In field applica-

Δc
tions where the initial concentration ratios are rarely known, the
non-linear Eq. (6) is the basis to estimate the reaction kinetic 0.4
properties by matching the experimental data against Dc–t curves
of given R1, R2, kf, ks, Z values.
0.2
Aldicarb
0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
4.1. Fast-reacting contaminants
1.0
Free chlorine and total chlorine concentrations in aldicarb,
glyphosate, and colchicine experiments are consistent with the Clf (22.4-m)
linear relationship in Eq. (8) for fast-reacting contaminants at the 0.8 Clt (22.4-m)
two sensor stations (Fig. 5). A steady-state chlorine loss was Clf (335.4-m)
established before the contaminants reached to the 24.4-m sensor 0.6 Clt (335.4-m)
station at t* ¼ 1.33 min. No statistically significant changes in

Δc
correlation slope occurred in subsequent 17.0-min of water flow to
0.4
the 344.5-m sensor station (Table 2). Evidently in Eq. (8), the
correlation slope in the Dc–C0F /C0D plot is independent of time but
a function of the reaction stoichiometric constants and the molar 0.2
fraction of fast-reacting compounds in the tested materials. Colchicine
Experimentally determined correlation slope follows the order of 0.0
colchicine > aldicarb > glyphosate (Table 2). 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Previous studies (Brosillon et al., 2006; Mehrsheikh et al.,
2006; Ray et al., 1981; Arnstein et al., 1949; Mason et al., 1990; and 1.0
Miles, 1991) described chlorination pathways and molecular
structure changes that are consistent with the sensor measure- 0.8
ments and kinetic analysis results. In chlorinated water, aldicarb is
oxidized to yield aldicarb–sulphoxide and aldicarb–sulphone with
0.6
a half-life t*1/2 < 1 min (Miles, 1991; Mason et al., 1990) leading to
Δc

the rapidly established steady-state chlorine loss (Yang et al., Clf (22.4-m)
2007). On the other hand, glyphosate follows more complex 0.4 Clt (22.4-m)
oxidation pathways resulting in differential responses between Clf (335.4-m)
total and free chlorines. Brosillon et al. (2006) and Mehrsheikh 0.2 Clt (335.4-m)
et al. (2006) demonstrated in experiments that the carbamate
compound is oxidized to form monochloroglycine and then Glyphosate
dichloroglycine, followed by the rate-limiting dichloroglycine 0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
decomposition to form chloraldimine and hydrochloric acid (t*1/2 ¼
3.04 min), in which cyanogen chloride oxidation produces chlo- 1.0
ramines and cyanate (NCO) in three-branched reactions. Based on
Clf (22.4-m)
second-order reaction constants reported in Brosillon et al. (2006),
0.8 Clt (22.4-m)
calculations indicate that 40% reactions produce chloramines as
the final products, which would not be registered in the sensor as Clf (335.4-m)
total chlorine loss. This is demonstrated in the experiments in 0.6 Clt (335.4-m)
which the determined ratios between total and free chlorine
Δc

residual loss remain indifferent: 51.5  2.3% (m  s, N ¼ 5) and

0.4
51.4  2.0% (m  s, N ¼ 6) at 22.4-m and 335.4-m sensor station,
respectively (Table 1).
The 3-ring structured colchicine (Arnstein et al., 1949) readily 0.2
affords oxygen addition to the tropolone C-ring, forming endo- and Nicotine
exo-peroxide in photochemical oxidation (Bentley, 1985). In the 0.0
early study of the alkaloid, Tarbell et al. (1946) proposed the prin- 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
cipal pathway of colchicine hydrolysis to colchiceine. If these CF0
transformation mechanisms apply to colchicine chlorination in CD0
drinking water, generated methyl radicals may have produced
chloride and chloramines after reacting with chlorine radicals or Fig. 5. Correlation plot Dc vs C0F /C0D for free and total chlorine in the experiments of
hypochlorite ions (Zhou et al., 2001). This is consistent with the aldicarb, glyphosate and colchicine. The correlation for these contaminants remains
fairly a constant between the 22.4-m and 335.4-m sensor stations indicating a steady-
increased chloride concentration, more free chlorine residual loss
state condition of chlorine residual loss as shown in Eq. (8) for fast-reacting contam-
than total chlorine, and decreased ORP levels observed in the pure inants. Differently, the slope changes in the nicotine experiments between the two
colchicine experiments (Table 1). stations. Linear regression results for the correlations are listed in Table 2.
 Y. Jeffrey Yang et al. / Journal of Environmental Management 90 (2009) 2494–2506 2501

10 50
E.coli in terrific broth Terrific broth
8 40

6 30

1/Δc
1/Δc
4 20
Clf (22.4-m) Clf (22.4-m)
2 10
Clf (335.4-m) Clf (335.4-m)
0 0
0 20 40 60 80 100 120 0 2 4 6 8 10

50 50
Nutrient broth Tryptic soy broth
40 40

30 30

1/Δc
1/Δc

20 20
Clf (22.4-m) Clf (22.4-m)
10 10
Clf (335.4-m) Clf (335.4-m)
0 0
0 2 4 6 8 10 0 2 4 6 8 10
CD0 CD0
CS0 CS0

Fig. 6. Correlation plot 1/Dc vs C0D/C0S for free and total chlorine in the experiments of E. coli in terrific broth and other biological growth media. The experimental data satisfies the
intrinsic linear relationship in Eq. (9) for the slow-reacting contaminants. Regression results are listed in Table 2.

4.2. Slow-reacting contaminants
For slow-reacting contaminants, the steady-state chlorine loss
condition was not achieved within the hydraulic residence time at
the two sensor stations. The correlation slope increases in the Dc–
C0F /C0D plot and decrease in the 1/Dc–C0D/C0F plot. This relationship is
evident in the experimental results of nicotine (Fig. 5), E. coli and
biological growth media (Fig. 6). From Eq. (9), a ratio between the
correlation slope at 22.4-m and 335.4-m sensor stations (st1, st2) is
a function of the reaction constant 62 and the hydraulic retention
time at the two stations (t1, t2):
st1 1  e62 t2
y (10)
st2 1  e62 t1
For nicotine, estimated 62 ð ¼ R2 ks Þ from Eq. (10) is 0.74 min1 in
free chlorine and 0.79 min1 in total chlorine. The kinetic constant in
free chlorine is 1.69, 1.47, 1.45, and 1.81 min1 for E. coli in terrific
broth, nutrient broth, terrific broth, and tryptic soy broth, respectively.
4.3. Non-reactive contaminants
The experiments on dicamba and inorganic compounds (lead
nitrate, mercuric chloride) showed no free chlorine residual loss, an
observation that is consistent with dicamba’s stable benzoic
structure and the chemical compositions of other contaminants. All
experiments showed detectable changes in pH, ORP and specific
conductivity (Fig. 3). For potassium ferricyanide, sensor signals
after adaptive treatment showed a prominent increase in total
chlorine and ORP (Fig. 3) possibly as an artifact of the yellow color

Table 2
Regression results between relative change (Dc) and the contaminant concentrations in the pilot-scale flow experiments.

Contaminant c0F ,c0S (mg/L) Sensor 22.4-m Sensor Stationa 335.4-m Sensor Stationa Type

m b R(N) m b R(N)
Aldicarb 0.2–2.2 Clf 1.21  0.02 0.01  0.01 0.999(6) 1.26  0.01 0.004  0.006 0.999(6) (a)
Clt 1.44  0.10 0.01  0.04 0.982(6) 1.33  0.04 0.01  0.02 0.997(6) (a)
Glyphosate 0.4–3.0 Clf 0.69  0.10 0.25  0.01 0.997(5) 0.86  0.01 0.03  0.01 0.999(5) (a)
Clt 0.43  0.01 0.12  0.01 0.997(5) 0.80  0.03 0.07  0.02 0.996(5) (a)
Colchicine 0.4–3.6 Clf 1.71  0.03 0.01  0.01 0.999(5) 1.65  0.02 0.01  0.01 0.999(5) (a)
Clt 1.77  0.03 0.01  0.01 0.998(5) 1.54  0.06 0.08  0.02 0.993(5) (a)
Nicotine 0.4–3.8 Clf 0.30  0.02 0.05  0.02 0.985(6) 0.60  0.02 0.07  0.02 0.995(6) (a)
4.46  0.26 1.34  0.36 0.986(6) 2.80  0.16 0.58  0.22 0.987(6) (b)
Clt 0.20  0.03 0.04  0.02 0.939(6) 0.36  0.02 0.06  0.01 0.989(6) (a)
5.28  0.53 2.53  0.83 0.960(6) 0.36  0.02 0.06  0.01 0.989(6) (b)

E. coli in terrific broth 0.01–0.14 Clf 0.0592  0.0003 0.72  0.01 0.999(5) 0.053  0.001 0.73  0.02 0.999(4) (b)
Nutrient broth 0.12–0.95 Clf 5.63  0.11 3.42  0.48 0.998(6) 4.84  0.56 1.54  1.92 0.962(5) (b)
Terrific broth 0.12–0.95 Clf 3.94  0.11 1.37  0.40 0.998(5) 3.37  0.08 0.96  0.29 0.998(4) (b)
Tryptic soy broth 0.12–0.95 Clf 3.23  0.78 6.72  3.76 0.813(6) 2.94  0.47 2.12  2.05 0.906(3) (b)

Potassium ferricyanide 0.6–3.2 Clt 0.60  0.04 0.00  0.01 0.985(6) 0.581  0.028 0.00  0.01 0.991(6) (a)
Mercuric chloride 0.4–2.2 pH 0.031  0.006 0.00  0.00 0.927(4) 0.031  0.002 0.00  0.00 0.987(6) (a)
ORP 0.052  0.007 3.6  40E-5 0.977(4) 0.020  0.002 3.6  40E-5 0.977(6) (a)
a
Least-square linear regression (y ¼ mx þ b) of the experimental data in Table using (a) Eq. (8) for fast-reacting contaminants and (b) Eq. (9) for slow-reacting contaminants.
m – slope; b – intercept; R2(N) – one standard deviation (number of data points).
2502 Y. Jeffrey Yang et al. / Journal of Environmental Management 90 (2009) 2494–2506

12 when the compound is dissolved in water producing interference

AL EC to the Hach CL-17 colorimetric sensor.
GL NB
10 NC TB
CC TSB 5. Discussions
Δ c(Clf) Δc(Clt)

8
Adaptive treatment of the experimental composite dataset has
reduced background noise and enhanced contaminant signals,
6 leading to accurate detection of all 22 contaminant injection events
(Fig. 3) and identification of the chlorine-contaminant reactivity (Figs.
4 5 and 6). Based on these results, the method detection false rates and
contaminant classification techniques are further discussed.
2
5.1. Contaminant detection and false rate
0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 Detection accuracy is important for the use of non-selective
water quality sensors to detect contaminant events in a noisy
Δ c(Clf)
environment (McKenna et al., 2006). In classic robust classification
Fig. 7. Discrimination diagram in the DClf/DClt vs DClf plot for 11 chemical and bio- as well as more advanced techniques such as principal component
logical contaminants, each at three initial concentration levels. The E. coli in terrific analysis (PCA) and multi-variant statistics and clustering analysis
broth and other biological growth media form a positive trend in the plot as indicated (Shyu et al., 2003; Takahashi and Kurita, 2002; Klise and McKenna,
in Eqs. (9) and (10), whereas the alkaloids and pesticide/herbicides have a fair constant
2006; Oh and Lee, 2003; Bacon, 1995), sensor outputs are classified
DClf/DClt approximately less than 2. Symbols: AL – aldicarb, DI – dicamba, GL –
glyphosate, PF – potassium ferricyanide, MC – mercuric chloride, NC – nicotine, CC – against a statistical reference (e.g., Euclidean or Mahalanobis
colchicine, EC – E. coli in terrific broth, NB – nutrient broth, TB – terrific broth, and TSB distance) or by using the partial least-square distance in regression.
– tryptic soy broth. Klise and McKenna (2006) quantitatively evaluated the false
detection rate using a multi-variant PCA cluster analysis technique.
Their results showed that the method detection accuracy was 75.1%
at 1.5 times and 84.5% at 2.5 times of the background signal

−10 Δ 0 Δ c(Childe)
− Δ c(Clt)
1.0

0.0
.2
.5

.3
.8

.4
.9

.6

.1
.7

0.0

1.0
.1
.9
.2
.8

.3
.7

.4
.6

.5
1:1

.5
7:3

.6
.4

.7
.3

.8
.2

.9
.1

1.0
Δ c(Clt) Δ c(Clf)
1.0

.9 .1

.8 .2

.7 .3
AL
.4 GL
.6
NC
.5 .5 CC
EC
.4 .6
NB
.7 TB
.3
TSB
.2 .8 KF
MC
.1 .9
1.0
0.0
10 Δ c(Chloride)

Fig. 8. Tetrahedron projections of the Dc (Clf) – Dc (Clt) – 10DcChloride system for the tested chemical and biological contaminants. Arrow indicates the change trend as chloride
accumulates while the DClf/DClt ratio increases for slow-reacting contaminants. Symbols: AL – aldicarb, DI – dicamba, GL – glyphosate, PF – potassium ferricyanide, MC – mercuric
chloride, NC – nicotine, CC – colchicine, EC – E. coli in terrific broth, NB – nutrient broth, TB – terrific broth, and TSB – tryptic soy broth.
 Y. Jeffrey Yang et al. / Journal of Environmental Management 90 (2009) 2494–2506 2503

0.04 MC method detection accuracy and sensitivity, background noise must

Δc (Chloride)

be suppressed for enhanced contaminant signals. In the READiw

method, this is achieved by using an adaptive data transformation
0.02
technique in Eq. (4) as it is applied to the experimental composite
dataset. By using the technique, 22 contamination events were
0.00 accurately detected for all the 11 contaminants at tested concen-
-0.05 0.00 0.05 0.10 0.15 0.20 0.25 0.30 trations (Fig. 3 and Table 1). The smallest change detected for
Δ c (ORP) a contaminant event is 0.1% of the absolute background value for
-0.02
pH, 0.1% for ORP, 0.9% for free chlorine, 1.6% for total chlorine, and
0.9% for chloride. These observed detection limits are substantially
-0.04 smaller than the background noise or one standard deviation of the
EC & untreated background sensor data.
GL, CC
Growth media
-0.08
-0.10 5.2. Contaminant classification in discrimination diagrams
-0.12
-0.14
AL After the adaptive treatment, the sensor data are consistent with
-0.16
DI the quantitative kinetic relationships in Eqs. (8) and (9) (Figs. 5 and 6)
GL and with known physiochemical properties of the contaminants.
0.06
Δ c (pH)

NC
This agreement indicates a potential for contaminant differentia-
CC
0.05 EC tion and classification with the assistance of discrimination
NB diagrams as forensic tools. Four discrimination systems are exam-
0.04 GL TB ined to differentiate the 11 tested contaminants.
TSB
0.03 PF 5.2.1. The D c (Clf)/D c (Clt)–D c (Clf) system
MC
Among the water quality parameter changes, free and total
0.02 chlorine residual losses are the most direct indicator of contami-
DI, MC
nant reactivity. The ratio of relative changes as shown in the Dc
0.01 (Clf)/Dc (Clt)–Dc (Clf) diagram reflects the reaction kinetic differ-
EC & Growth media
ences between total and free chlorine (Table 2). As expected from
Eq. (9), fast-reacting contaminants are associated with a narrow
-0.1 0.1 0.2 0.3 0.4 0.5 0.8 1.0
range of Dc (Clf)/Dc (Clt) values. The ratio is independent of time,
-0.01 Δ c*(ORP) - Δ c* (Chloride) but a function of stoichiometric constants and molar concentration
NC
ratios between contaminant and chlorine. In Fig. 7, this correlation
-0.02
is evident in pesticide/herbicides and alkaloids that form a broad
Fig. 9. Binary discrimination diagrams in the Dc (pH) – Dc(ORP) – Dc(Chloride) system band with Dc (Clf)/Dc (Clt) < 2 over the full range of free chlorine
showing different plotting areas and correlations among tested chemical and biological loss.
contaminants. Symbols: AL – aldicarb, DI – dicamba, GL – glyphosate, PF – potassium On the other hand, the slow-reacting contaminants E. coli in
ferricyanide, MC – mercuric chloride, NC – nicotine, CC – colchicine, EC – E. coli in
terrific broth and other biological growth media showed larger
terrific broth, NB – nutrient broth, TB – terrific broth, and TSB – tryptic soy broth.
relative loss ratios and a positive correlation in the plot. As shown
in Eqs. (9) and (10), the total and free chlorine residual loss and
strength, a better performance than the other distance-based their ratios are a function of time and relative magnitude of their
detection algorithms. reaction kinetic constants. This difference defines the range of Dc
While the statistical population distance is commonly used as (Clf) values and the slopes of correlations in the Dc (Clf)/Dc (Clt)–Dc
the judging criteria in robust anomaly detections, transitions (Clf) diagram.
between the populations are often neglected. This method
assumption has restricted the anomaly detection capability for 5.2.2. The D Cf–DCt–DCchloride system
a dynamic process, where significant changes between two process Relationships among the reactants (free and total chlorine) and
statuses are potentially small and overshadowed in background reaction product (chloride) are shown in a tetrahedron projection
noise. The detection capability is improved by introducing the rate (Fig. 8) where all tested contaminants are plotted in the area of
of changes as an independent criterion that contains rich infor- Dcf  Dct. Pesticide/herbicides and alkaloids are located in the area
mation characteristic of the populations. For example, Lee et al. 0.25  Dc(Clf)/Dc(Clt)  0.5 different from that of E. coli in terrific
(2004) introduced a dynamic independent component analysis broth and other biological growth media. On the other hand,
technique to improve process control by capturing the transitions inorganic compounds potassium ferricyanide and mercuric chlo-
of control parameters between two processing conditions. Simi- ride are associated with an increase in total chlorine and chloride,
larly, Lin et al. (2007) outlined a fast-algorithm for independent respectively (Table 1). Because of these properties, the contami-
component analysis and recovery (ICA-R) in anomaly separation nants are plotted in different projection planes separate from other
and detection. tested contaminants (Fig. 8).
In drinking water applications, the READiw method utilizes
a hybrid detection approach that combines both distance-based 5.2.3. The pH–ORP–chloride system
robust statistics and the analysis of the transition between the Water quality parameters chloride, ORP and pH are sensitive to
background and a contaminant event. It is observed that for non- the presence of tested contaminants in drinking water (Fig. 3).
compound specific conventional water quality sensors, the differ- Except for mercuric chloride for which simple dissolution can result
ence between background and the contamination can be small in in pH changes, other detected pH changes are related to chlorine-
magnitude and the transition is often overshadowed in the noisy contaminant reactions. The largest pH decrease was recorded in
background of a water distribution pipe. Thus to improve the glyphosate (2–4%), consistent with published kinetic studies
2504 Y. Jeffrey Yang et al. / Journal of Environmental Management 90 (2009) 2494–2506

0.2 0.2 0.2 0.2

Δc (Chloride, ORP, pH)

Δc (Chloride, ORP, pH)

0.0 0.0
0.1 0.1
Δc (Clf, Clt)

Δc (Clf, Clt)
-0.2 -0.2

-0.4 0.0 -0.4 0.0

-0.6 Clf -0.6 Clf

Clt -0.1 Clt -0.1
-0.8 Chloride -0.8 Chloride
Aldicarb ORP Nicotine
ORP
-1.0 pH -0.2 -1.0 pH -0.2

0.2 0.2 0.1 0.10

Δc (Chloride, ORP, pH)

Δc (Chloride, ORP, pH)

0.0 0.0
0.1 0.05
Δc (Clf, Clt)

Δc (Clf, Clt)
-0.2 -0.1

-0.4 0.0 -0.2 0.00

Clf
-0.6 Clf -0.3 Clt
Clt -0.1 -0.05
Chloride
-0.8 Chloride -0.4 ORP
ORP Glyphosate Colchicine
pH
-1.0 pH -0.2 -0.5 -0.10

0.2 0.015 0.2 0.2

Δc (Chloride, ORP, pH)

Δc (Chloride, ORP, pH)

0.0 0.010 0.0
0.1
Δc (Clf, Clt)

Δc (Clf, Clt)
-0.2 0.005 -0.2

-0.4 0.000 -0.4 0.0

-0.6 Clf -0.005 -0.6 Clf

Clt Clt -0.1
Dicamba
-0.8 Chloride -0.010 -0.8 Chloride E.coli with
ORP ORP
-1.0 pH -0.015 -1.0 pH Terrific Broth -0.2

Fig. 10. Characteristic Dc–t patterns for aldicarb, glyphosate, dicamba, nicotine, colchicine, E. coli in terrific broth constructed for the 22.4-m and 355.4-m monitoring stations. The
shape and assembly of Dc values are distinct between contaminants, reflecting the differences of their reactivity with chlorine and other physiochemical properties in water pipes.

(Mehrsheikh et al., 2006; Brosillon et al., 2006) that glyphosate
oxidization in chlorinated drinking water generates HCl as a reaction
intermediate in 10 of 26 reaction steps. Smaller degrees of pH
decrease were observed in E. coli, mercuric chloride, dicamba, and
aldicarb in the order of decreasing magnitude. Differently, a small pH
increase <1% was registered in nicotine (Table 1). The compound is
readily distinguishable for an increase in pH, a large decrease in ORP,
and the lack of change in chloride in the pH–ORP–chloride system
(Fig. 9). This property reflects fact that in chlorine solution, nicotine
is transformed to nicotinic acid producing changes in hydrogen and
ORP but not in chloride ions (Weijlard, 1945).
5.2.4. Discrimination patterns in Dc–t plots
Relative change in sensor outputs can be assembled into unique
patterns on a Dc–t plot (Fig. 10). These patterns reflect both the
contaminant reactive kinetics and its transport in pipe flows, and
clearly exhibit the geometric differences between the contaminants.
6. Conclusions
To detect and classify a contaminant event in a drinking water
distribution pipe, the READiw method begins with the anomaly
detection in a course statistical filter followed by the detection
confirmation and characterization. The anomaly detection relies on
adaptive transformation of time-series sensor outputs in a moving
time window to suppress background noises and enhance
contaminant signals. Initial anomaly detections are subsequently
verified and classified according to the inferred contaminant
properties. Multiple independent criteria are used in the verifica-
tion and classification, including quantitative relationships among
the observed Dc values of water quality parameters, contaminant
forensic analysis in discrimination diagrams, and contaminant
transport between monitoring stations.
The adaptive transformation and contaminant classification
techniques are examined on 22 pilot-scale distribution pipe
experiments for 11 selected contaminants including pesticide/
herbicides, alkaloids, E. coli in terrific broth, biological growth
media, and inorganic compounds. A composite dataset composed
of all 22 individual experiments of varying baseline variations is
analyzed. Major conclusions are:
- All contaminant injection events are detected in a paired
sensor station configuration along a straight water pipe. In the
glyphosate experiments, contaminant intrusion events were
correctly detected at 0.4 mg/L concentration below the U.S.
EPA drinking water standard of 0.7 mg/L. For the composite
dataset, the smallest Dc for an accurate detection is 0.1% of
background level for pH, 0.1% for ORP, 0.9% for free chlorine,
1.6% for total chlorine and 0.9% for chloride (Table 1). These
levels are substantially lower than the background noise
measured as one standard deviation of the background varia-
tion attributed to the different baselines of 22 individual
experiments.
- After adaptive treatment, the sensor data have small back-
ground noises and clearly show a set of characteristic and
consistent variation patterns in a Dc–t plot corresponding to
each of contaminant events. Free chlorine residual loss
measured from Dc–t patterns agrees well with a modified
second-order competitive kinetic model of Clark and Sivaga-
nesan (2002) in the fiberglass-lined experiment pipe, based on
 Y. Jeffrey Yang et al. / Journal of Environmental Management 90 (2009) 2494–2506
which 11 contaminants are classified as non-reactive, fast-
reacting and slow-reacting groups in reference to the hydraulic
residence time between the two monitoring stations. For the
fast-reacting contaminants (aldicarb, glyphosate, and colchi-
cine), a steady-state free chlorine loss was established in the
first 1.33 min before the water reached to the 22.4-m sensor
station. Other tested contaminants (nicotine, E coli with terrific
broth and 3 biological growth media, and nicotine in total
chlorine) displayed continuous increase in residual loss.
- Dicamba, mercuric chloride, and potassium ferricyanide
showed no reactivity with free chlorine in the drinking water.
These contaminants were detected by pH, specific conductivity
and ORP, and were distinguished in the four major types of
discrimination diagrams (Figs. 7–10) constructed a combina-
tion of Dc values.
- By using the READiw techniques, contamination events are
accurately detected in the pilot-scale pipe flow experiments
with negligible wall demand and contaminant-wall interac-
tions. Other simplified testing conditions, which can affect the
accuracy and robustness of a detection method, include the
absence of cyclic background variations, hydraulic and
mechanic mixing of the contaminant ‘‘slugs’’ in a field distri-
bution system.
Acknowledgement
The authors wish to acknowledge the contribution from the
following individuals: John Hall and Dr. Jeff Szabo of U.S. EPA’s
National Homeland Security Research Center (NHSRC) and Greg
Meiners of Shaw Environmental for experimental testing, Dr. Regan
Murray, Robert Janke, Dr. A. Joel Allen, John Hall and Dr. Jeff Szabo, all
of U.S. EPA, for their manuscript review and comments. Peer review
by 6 anonymous reviewers, and financial support to this project by
U.S. EPA National Homeland Security Research Center and U.S. EPA
National Risk Management Research Laboratory are acknowledged.
Conclusions and opinions presented in this paper are those of the
authors, and not necessarily represent the position of the U.S. EPA.
Mention of commercial products, trade names or services in the
paper does not convey, and should not be interpreted as conveying,
official EPA approval, endorsement, or recommendation.
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