Online Monitoring of Priority and Dangerous Pollutants in Natural and Urban Waters: A State-Of-The-Art Review

See discussions, stats, and author profiles for this publication at: https://www.researchgate.
net/publication/304570982
Online monitoring of priority and dangerous pollutants in natural and urban

waters: A state-of-the-art review
Article in Management of Environmental Quality An International Journal · June 2016

DOI: 10.1108/MEQ-01-2015-0009
CITATIONS READS
33 2,440
3 authors:
Andrea G Capodaglio Arianna Callegari

University of Pavia University of Pavia
145 PUBLICATIONS 2,690 CITATIONS 70 PUBLICATIONS 1,331 CITATIONS
SEE PROFILE SEE PROFILE
Daniele Molognoni
Leitat Technological Center
48 PUBLICATIONS 706 CITATIONS
SEE PROFILE
Some of the authors of this publication are also working on these related projects:
sustainability of the urban water cycle View project
Energy and materials recovery from water & wastes for sustainable urban metabolism: strategies and technologies View project
All content following this page was uploaded by Andrea G Capodaglio on 22 July 2018.
The user has requested enhancement of the downloaded file.

Management of Environmental Quality: An International Journal
Online monitoring of priority and dangerous pollutants in natural and urban
waters: A state-of-the-art review
Andrea G Capodaglio Arianna Callegari Daniele Molognoni
Downloaded by UNIVERSITA DEGLI STUDI DI PAVIA, Doctor Daniele Molognoni At 08:20 26 August 2016 (PT)
Article information:
To cite this document:
Andrea G Capodaglio Arianna Callegari Daniele Molognoni , (2016),"Online monitoring of priority
and dangerous pollutants in natural and urban waters", Management of Environmental Quality: An
International Journal, Vol. 27 Iss 5 pp. 507 - 536
Permanent link to this document:
http://dx.doi.org/10.1108/MEQ-01-2015-0009
Downloaded on: 26 August 2016, At: 08:20 (PT)
References: this document contains references to 64 other documents.
To copy this document: permissions@emeraldinsight.com
The fulltext of this document has been downloaded 45 times since 2016*
Users who downloaded this article also downloaded:
(2016),"Perceptions, attitudes and behaviours toward urban surface water quality in Accra, Ghana",
Management of Environmental Quality: An International Journal, Vol. 27 Iss 5 pp. 491-506 http://
dx.doi.org/10.1108/MEQ-07-2015-0122
(2016),"Design of a risk assessment methodology for the introduction of invasive species from ship
ballast waters: The case of Arzew port", Management of Environmental Quality: An International
Journal, Vol. 27 Iss 5 pp. 474-490 http://dx.doi.org/10.1108/MEQ-02-2015-0023
(2016),"Optimization of biological transesterification of waste cooking oil in different solvents using
response surface methodology", Management of Environmental Quality: An International Journal, Vol.
27 Iss 5 pp. 537-550 http://dx.doi.org/10.1108/MEQ-06-2015-0118
Access to this document was granted through an Emerald subscription provided by

Token:JournalAuthor:681FC770-C06B-4438-922C-61DCA1975BED:
For Authors
If you would like to write for this, or any other Emerald publication, then please use our Emerald
for Authors service information about how to choose which publication to write for and submission
guidelines are available for all. Please visit www.emeraldinsight.com/authors for more information.
About Emerald www.emeraldinsight.com
Emerald is a global publisher linking research and practice to the benefit of society. The company
manages a portfolio of more than 290 journals and over 2,350 books and book series volumes, as
well as providing an extensive range of online products and additional customer resources and
services.
Emerald is both COUNTER 4 and TRANSFER compliant. The organization is a partner of the
Committee on Publication Ethics (COPE) and also works with Portico and the LOCKSS initiative for
digital archive preservation.
*Related content and download information correct at time of download.

The current issue and full text archive of this journal is available on Emerald Insight at:
www.emeraldinsight.com/1477-7835.htm
Online monitoring of priority Monitoring of

priority and
and dangerous pollutants dangerous
pollutants
in natural and urban waters
507
A state-of-the-art review
Received 27 January 2015
Andrea G. Capodaglio, Arianna Callegari and Daniele Molognoni Revised 26 June 2015
Department of Civil Engineering and Architecture, 7 August 2015
12 August 2015
University of Pavia, Pavia, Italy 20 August 2015
Accepted 17 September 2015
Abstract
Purpose – Advancements in real-time water monitoring technologies permit rapid detection of water
quality, and threats from waste loads. Water Framework Directive mandating the establishment of
Member States’ water resources monitoring, presence of hazardous contaminants in effluents, and
perception of vulnerability of water distribution system to attacks, have spurred technical and
economic interests. The paper aims to discuss these issues.
Design/methodology/approach – As alternative to traditional analyzers, chemosensors, operate
according to physical principles, without sample collection (online), and are capable of supplying
parameter values continuously and in real-time. Their low selectivity and stability issues have been
overcome by technological developments. This review paper contains a comprehensive survey of
existing and expected online monitoring technologies for measurement/detection of pollutants in water.
Findings – The state-of-the-art in online water monitoring is presented. Application examples are
reported. Monitoring costs will become a lesser part of a water utility budget due to the fact that
automation and technological simplification will abate human cost factors, and reduce the complexity
of laboratory procedures.
Originality/value – An overview of applicable instrumentation, and forthcoming developments, is given.
Technological development in this field is very rapid, and astonishing advances are anticipated in several
areas (fingerprinting, optochemical sensors, biosensors, molecular techniques). Online monitoring is
becoming an ever-important tool not only for compliance control or plant management purposes, but also
as a useful approach to pollution control and reduction, minimizing the environmental impact of discharges.
Keywords Contaminant warning systems, Instrumentation, Liquid and gas chromatography,
Online monitoring, Photometry, Priority, Dangerous, Emerging pollutants
Paper type Literature review
1. Introduction
With constant advancements, real-time water monitoring and sensing technologies will
become a progressively more important tool for evaluating water quality. Recent
technologies are permitting rapid detection of water quality changes, environmental
threats induced by waste loads, and other impacts. Starting point for their diffusion
was the EU Water Framework Directive 2000/60, mandating that Member States
establish requirements for quality and quantity monitoring of water resources, and
implement such programs. Use of traditional technologies would have implied high
monitoring stations installation costs, and high operational and maintenance (O&M)
expenses: an estimate for Italy, considering river bodies only, indicated the requirement
Management of Environmental
of over 400 additional monitoring stations (Capodaglio et al., 2002). Quality: An International Journal
An alternative to chemical analyzers, traditionally adopted for this purpose, is the use Vol. 27 No. 5, 2016
pp. 507-536
of chemosensors, which operate according to physical principles (e.g. light measurement), © Emerald Group Publishing Limited
1477-7835
without sample collection (directly online) and can supply (surrogate) parameter values DOI 10.1108/MEQ-01-2015-0009
MEQ in real-time. Therefore, sensors can be used in those instances where fast changes are
27,5 foreseen, there are site accessibility problems, and collection of the samples could itself
because of disturbance. Traditional grab sampling followed by laboratory analysis only
allows capture of small data sets, mostly unrepresentative of the variance at the source,
and allows potentially important events to occur undetected (Copetti et al., 2014).
Remotely acquired, continuous, in-situ monitored data may provide important early
508 warning information (Glasgow et al., 2004).
During the last two decades, studies revealed the presence of hazardous
contaminants in urban discharges due to “normal” anthropic activities, including
pesticides (Öllers et al., 2001), natural and synthetic hormones (Kolpin et al., 2002),
plasticizers, personal care products and pharmaceuticals (Daughton and Ternes, 1999;
Jones et al., 2002). Since surface water resources may serve as water supply, there is a
clear need to be able to rapidly detect instances of accidental (deliberate) contamination,
due to their potential consequences to human health. These data might not be
measurable during routine offline monitoring at drinking water treatment plants, and
various distribution system locations.
Existing laboratory methods are too slow to develop operational responses, cannot
provide a sufficient level of public health protection in real-time, hence the need for better
online monitoring of water systems is clear (Storey et al., 2011). Furthermore, safety of
water distribution systems has lately become of primary concern to governments, as
those may be targets of terrorist groups. Research related to distribution systems water
quality monitoring has increased significantly since September 11, 2001, when security of
water infrastructure suddenly became a major priority in the USA.
In view of the above mentioned risks and the need for safe and reliable water supply,
traditional monitoring routines can no longer be considered satisfactory, especially
since online relatively cheap monitoring technologies, available for a larger number of
parameters than previously thought possible, are becoming affordable (Capodaglio and
Callegari, 2009; O’Halloran et al., 2009). Many utilities around the world are already
using some form of online monitoring to warn of drinking water contamination, in
anticipation of yet-to-be specified regulations. In the USA, turbidity is currently the
only indicator for bearing a regulatory requirement for continuous online monitoring
(AWWA, 2002); in Europe, regulations (Council Directive 98/83/EC) do not specifically
require online measurements, although good practice rules suggest that, at least in
critical situations, some basic continuous monitoring should be implemented.
Traditionally, sensors were afflicted by low selectivity and stability problems;
however, developments have turned these instruments into “competitive” tools,
compared with traditional analyzers. Some sensors applications in surface and ground
waters monitoring are illustrated in the paper.
2. Online monitoring definition and rationale

Online monitoring is defined as unattended sampling, analysis and reporting of
parameters, producing data sequences at greater frequency than permitted by manual
(grab) sampling, and allowing real-time feedback for process control, water quality
characterization for operational or regulatory purposes, and alert/alarm.
Online monitoring of pollutants and dangerous substances is important for plant
management purposes, pollution control and reduction, and to diminish the environmental
impact of discharges. It can occur on-site and at remote locations, and will deliver
measurements at intervals of seconds-to-minutes. Online instrumentation must be placed
at representative locations in water system networks, and must be periodically maintained.
Monitoring requirements, in general, can be defined with relationship to (CapodaglioMonitoring of
and Callegari, 2009): priority and
(1) Monitored water type: dangerous
• variability, in space and time (very low for groundwater, low for lakes, high pollutants
for rivers, very high for discharge channels and urban or industrial
drainage, or in-plant monitoring); and 509
• vulnerability (type and location of possible contaminating activity),

time-of-travel of contaminants to intake, barriers’ effectiveness, control
options after alarm.
(2) Water treatment: process optimization options, response times, sampling
frequency, must allow adequate process control.
(3) Distribution systems: minimization of water quality deterioration over time and
distance, early detection of cross-connections and water losses. In addition,
online monitors could have different sensitivity and selectivity according to the
matrix and range of concentrations analyzed.
For drinking water protection, multi-barrier approaches, such those commonly used
worldwide, are based on the concept that contaminants must be subject to as many
points of control/treatment (barriers) as possible, prior to tap (O’Halloran et al., 2009).
The ideal location for control of contaminants is as close to the source as possible.
Source water with low vulnerability is characterized by few potential contaminant
activities, transit times longer than those required for laboratory analysis, presence of
multiple physical barriers between contaminating activities and point of intake. In a
source with moderate vulnerability, online monitoring of surrogate parameters (such as
TOC, DOC, UV254, pH and conductivity) should be considered. In high vulnerability
water sources, online monitoring of chemical-physical-biological parameters (turbidity,
pH, conductivity, redox, fish toxicity) and surrogate parameters, in addition to specific
indicators (e.g. volatile organic compounds (VOCs), phenols and specific toxicity tests)
may be preferred. This is summarized in Table I.
Availability of real-time information is one of the key benefits of online monitoring:
this information must, however, be conveyed to the appropriate user by means of data
collection and transmission systems which are often referred to as supervisory control
and data acquisition (SCADA) systems. These consist of individual online instruments,
connected to programmable logic controllers or remote telemetry units, that
convert outputs to desired units, compare them to criteria set by users, and generate
signals for alarm or control to other process equipment. A host computer that can be
used to visualize, store, or to further utilize data for specific purposes, complements
these systems (Figure 1). When used in water conveyance systems (waste or supply),
online monitoring probes may provide a “head start” in detecting relevant abnormal
pollution events and can be employed to localize origin and causes of contamination
peaks and loads.
2.1 Online monitoring instrumentation overview

Online monitoring instrumentation can be divided in:
• physical monitors (turbidity, particles, color, conductivity, TDS, streaming
current, radioactivity, temperature, redox potential);
MEQ Activity Monitoring strategy Objectives
27,5
Contaminant source Surrogate parameters (TOC, Define potential contamination
identification DOC, UV254, pH, in relation to vulnerability of source water
conductivity)
Specific parameters (related
to known sources of
510
contamination)
Biotests and toxicity tests
Monitoring of Specific organic/inorganic Identify water pollution
discharges into the contaminants accidents
source water
Best management Hydrological parameters Prevent source deterioration
practices/protection ofEnvironmental parameters Environmental management
water source (solar radiation, O2, Chl)
Drinking water quality Specific organic/inorganic Allow appropriate responses to contaminant
protection contaminants presence (intake shut-up, additional
Treatment-related treatment, treatment adjustment)
parameters (Q, turbidity, pH,
TOC, DOC, etc.)
Table I. Biotests/toxicity
Online monitoring Emergency response Specific organic/inorganic Drinking water pollution control
objectives and contaminants Risk management treatment modification
strategies in water Biotests/toxicity
distribution systems Source: Modified from AWWA (2002)
• inorganic monitors (pH and DO, hardness, acidity, alkalinity, disinfectants, such
as chlorines and ozone, metals, fluoride, nutrients, cyanide);
• organic monitors (carbon and hydrocarbons, UV adsorption, VOCs, pesticides,
disinfection by-products);
• biological monitors (non-specific, algae, protozoa, pathogens); and
• hydraulic monitors (flow, level and pressure).
This paper will focus on the four former classes, discussing basic operating principles,
state-of-the-art, and evaluation of technology for online applications in water and
wastewater monitoring.
2.1.1 Physical monitors. A wide array of well-established technologies are used for
monitoring physical parameters, among them: light scattering/blocking (turbidity,
particles, SS), light absorbance (color), electrochemical (conductivity, redox),
electrophoretic (streaming current) and other (radioactivity, temperature) (Table II).
Most of these have been commercially available as online instrumentation for some time.
2.1.2 Inorganic monitors. Inorganic monitors are used in online mode to detect
influent and effluent water quality, and for treatment process control; applicable
technologies are listed in Table III. Except for chemical titration (alkalinity, acidity,
hardness), online monitoring of inorganic constituents is still in early phases for many
elements of interest to drinking water. For metals, typical available technology is
an adaptation to automatic mode of complex colorimetric methods developed for
laboratory applications, and therefore expensive and/or complex to operate, nor still
suitable for installation in remote or unmanned sites. For many metals of interest
Monitoring of
Central data priority and
storage
dangerous
pollutants
511
Data
line
Operator
monitoring Reporting &
station statistics
Alarm forwarding
to oncall
network manager
Alarm line/
Data
GPS/Radio
line/
GPS
Online PC
TCP/IP
running
Interface
alert/alarm/
anomalies
software
IN PIPE DEVICES
Figure 1.
Structure of
SCADA system
for environmental
FLOW (Pressure) Physicochemical Dedicated Dedicated Dedicated monitoring
measurement parameters sensor 1 sensor 2 sensor n
(As, Cd, Pb, Hg, Se, Zn), online monitoring technologies did not exist until very recently.
Online instrumentation based on anodic stripping or cathodic stripping voltammetry
methods (ASV, CSV) was developed and launched on the market quite recently
( Jothimuthu et al., 2011; Yue et al. 2012), with detection limits down to 0.5-10 μg/L
(clean water), depending on sample type and actual analyte (Modern Water, 2015).
Stripping voltammetry indicates a class of electro-analytical techniques used in high
sensitivity applications due to a pre-concentration step accumulating an analyte on
the electrode’s surface by electrodeposition or physical adsorption, depending on the
analyte, and on the stripping method. Once adequate pre-concentration is achieved, the
electrode potential is swept to strip the analyte the surface, and the associated faradaic
current is measured to determine concentration (Kissinger and Heineman, 1996). ASV is
a common form of stripping voltammetry, in which the analyte, typically a metal ion,
is pre-concentrated on the electrode surface by reductive electrodeposition.
The electrode potential is swept in the positive direction, oxidatively liberating metal
ions from the electrode surface. CSV is the reverse of ASV, where the analyte is
MEQ Application Most appropriate technology Other technologies
27,5
Low turbidity raw Single beam (tungsten or LED) Particle counters, particle monitors
water turbidimeter
Clarified water, Modulated four-beam turbidimeter
filter effluent
High turbidity Ratio turbidimeter
512
raw water Modulated four-beam turbidimeter

Filter backwash Transmittance turbidimeter Laser light source (660 nm) and
Surface scatter improved optics turbidimeters
Ratio turbidimeter
Modulated four-beam turbidimeter
Color Online colorimeter
Spectrophotometer
Table II. TDS Two-electrode conductivity probe
Physical online electrode-less (toroidal) probes
monitor technology Source: Modified from AWWA (2002)
Parameter Currently applied technology Other technologies
DO, pH Ion-selective electrodes (IESs) Fiber-optics chemical sensors (FOCS)

Hardness EDTA titration online (FOCSs or optodes) for pH, DO
Ion-specific electrodes (ISE) Iodometric DO measurements
Alkalinity Online alkalinity tritrator ClO2: iodometry, amperometric meth. I, DPD,
amaranth, chlorophenol red, LGB dye, ion
chromatography
Iron, manganese, X-ray fluorescence (complex), CSV, ASV stripping voltammetry
metals colorimetry Graphene-based EC-sensors
Ammonia, nitrite Colorimetric, FOCS (ammonia)
Nitrate Ion sensitive gas membrane
Electrodes, UV spectrometry
Table III. Phosphorous, Colorimetric, FOCS (cyanide)
Online inorganic cyanide
monitor technology Source: Modified from AWWA (2002)
accumulated as an oxidized species, and is stripped by potential sweep in the negative

direction. CSV low-cost voltammetric method as a screening tool for the determination
of emerging contaminants in natural water prior to chromatography was reported
recently (Nunes et al., 2015). Developments in miniaturization technology and new
materials, like carbon nanotubes and others, recently allowed design of fully
automated, online metal monitors capable to provide continuous monitoring of metals
in liquid streams (Hanrahan et al., 2004). It is probably too early to assess these
instruments’ reliability and robustness.
Graphene-based electrochemical sensors were developed for detection of heavy
metal ions in environmental analysis. Graphene has recently attracted scientific and
technological interest, showing great promise in diverse applications, from electronics,
energy storage, fuel cells, to biotechnologies because of its unique physicochemical
properties, that include: high surface area (theoretically 2,630 m2/g for single-layer
graphene), excellent thermal and electric conductivity, mechanical strength
(Shao et al., 2010). However, no commercially available grapheme-based products for Monitoring of
environmental applications are available today. priority and
Some promise comes from developments in optode technology, coupled with
miniaturized spectrophotometry. Optodes are growing in popularity due to their
dangerous
low-cost, low power requirements and long-term stability. An optode (or optrode) is an pollutants
optical sensor device formed by a polymeric matrix coated onto the tip of an optical
fiber, capable of (optically) measuring a specific substance, usually with the aid of a 513
chemical transducer. Optodes may apply various measurement methods, such as:
reflection, absorption, evanescent wave, luminescence (fluorescence and
phosphorescence), chemiluminescence, surface plasmon resonance, but the most
popular is luminescence. Optodes may provide, especially in environmental monitoring,
viable alternatives to electrode-based sensors, or more complex instrumentation
(Tengberg et al., 2006; Xie et al., 2014) although, generally, they do not have a resolution
comparable to the most recent cathodic microsensors.
2.1.3 Organic monitors. Technology for monitoring organic compounds includes
TOC analyzers, UV absorption and differential spectroscopy, chip-based
micromachined devices and chromatographic techniques. Although not all of these
are suitable for online, on-site applications, this technology is much more developed
than that for inorganics. For this reason, in addition to use in mandatory monitoring,
and notwithstanding a lack of specific regulations, many water utilities routinely use
some online organics monitoring.
TOC methods (APHA, AWWA, WEF, 2012) measure carbon content of dissolved
and particulate organic matter in water, without information about the nature of
organic substances, and generally require a four-step process: sample treatment
(filtration), inorganic C removal (acidification to pH o 2), oxidation (with UV, catalyzed
UV, chemical oxidation, etc.) and CO2 determination (NDIR detectors, colorimetric,
conductivity). Detection limits depend on the specific technique’s operating
temperature (usually W 0.2 mg/L at low temperature, W 1 mg/L at high
temperature). Table IV shows different fractions measured by an OC analyzer.
Most organic compounds found in water absorb UV radiation: their concentration can
thus be estimated using spectrometry. Originally, a UV source with wavelength of
254 nm was used, however, recently, instrumentation reading the entire UV-VIS spectrum
(200-750 nm) was introduced (S::can, 2015). UV absorption is now a commonly used
methodology: evidence shows strong correlation between measurements and organic
carbon measured with standard methods (Figures 2 and 3). In addition, it was shown that
Carbon fraction Definition
Total carbon (TC) Sum of organically and inorganically bound carbon

(incl. elemental C) in water
Total inorganic carbon (TIC) Sum of elemental carbon, CO2, CO, CN, CS, CCl4, etc.
Total organic carbon (TOC) Organic carbon bound to particles o 100 μm (TOC ¼ TC –TIC)
Dissolved organic carbon (DOC) Organic carbon in water bound to particles o45 μm
Non-purgeable organic carbon OC present after sample scrubbing to eliminate inorg.
(NPOC) C and VOCsa Table IV.
Volatile organic carbon (VOC) TOC fraction removed from the sample by gas stripping Carbon fractions
Note: aMost commercial TOC analyzers actually measure NPOC measured by organic
Source: Modified from AWWA (2002) carbon analyzers
MEQ 10,000
R 2 = 0.99
5,000
27,5 9,000
8,000 4,000
2
BOD R = 0.93
7,000
COD s::can
BOD s::can
6,000 3,000
COD
5,000
514
4,000 2,000
3,000
Figure 2. 2,000 1,000

Correlation between 1,000
BOD5 and COD 0 0
laboratory results 0 2,000 4,000 6,000 8,000 10,000
and the results COD, BOD Laboratory
measured with a
spectrometric probe Note: Reproduced with permission
Source: S::can (2015)
other parameters can be inferred by correlation to UV full spectrum absorption (Figure 4);
several organic compounds have absorption spectra that make their identification quite
easy with appropriate instrumentation (Figure 5).
Usually, cumulative parameters such as COD, CODfiltered, BOD or spectral
absorption coefficient are used to quantify organic water contamination, due to a
multitude of substances. Online spectrometric probes can continuously measure
organic parameters, as well as suspended solids, allowing detailed characterization of
water at a specific point, allowing intervention, facility process control, or other
responses. This type of monitoring is essential both in streams and in treatment
facilities, as load peaks can lead to process upsets, or even breakdown of processes.
Standard deviation of COD values from spectral measurements shows substantially
less dispersion than that measured in laboratory. Uncertainties pertaining to COD
determination (above all, at lower concentration) are well known, and can be intensified
by application of traditional standardized batch tests. Due to lower dispersion of
UV/VIS spectrometry measurements, lower detection limits can be achieved. In terms
of methodical approach, online spectrometry features the advantage of measuring
directly the concentration of oxidizable, organically bound carbon.
A patent issued recently for a chip-based TOC measurement apparatus
(Shinsuke, 2013) involves micromachining techniques to integrate devices onto
a miniaturized support, thereby reducing samples and reagents consumption.
It includes an oxidative decomposition unit oxidizing organic matter by ultraviolet
irradiation, a CO2 separation unit moving carbon dioxide into deionized water
through a permeable membrane, and a detection unit measuring conductivity to
obtain CO2 concentration. It is not known of available industrial products supported
by this technology.
In addition to organic matter, hydrocarbons are probably the main class of
contaminants found in surface and groundwater. Methods for online detection include:
fluorometry, reflectivity, light scattering and turbidity measurement, ultrasonic
methods, electrical conductivity, spectroscopy, gas-phase detection (after
volatilization), resistance-based sensors; some methods, however, give merely an
indication of the presence/absence of oil.
(a) (b)
1.2E+07 1.4E+06
1.0E+07 1.2E+06
1.0E+06
8.0E+06
8.0E+05 R 2 = 0.9992
2
6.0E+06 R = 0.9989
6.0E+05
GC-MS (counts)
GC-MS (counts)
4.0E+05
4.0E+05
2.0E+05
2.0E+05
0.0E+00 0.0E+00
0 20 40 60 80 100 0 2 4 6 8 10 12
spectrometric measurement (mg/l) spectrometric measurement (mg/l)
Notes: (a) Distilled water; (b) groundwater. Reproduced with permission

dangerous
GC-MC laboratory
pollutants
methods
Correlation of online
benzene against
priority and
Monitoring of
measurements for
Figure 3.
515
UV-VIS spectrometer
MEQ 500
UV radiation Visible radiation (Vis)
120
27,5 450
100
400
350
80
300
COD_total
250 60
516
NO2 BOD Non-compensated spectrum; represents the

NO3 TOC dissolved and non-dissolved substances
200
Benzene 40
150 Toluene
Xylene Turbidity, TSS (total dissolved solids), etc.
100 Phenol... 20
50 color Turbidity-compensated spectrum;
COD_dissolved
represents the dissolved components only
Figure 4. 0
DOC
0
Correspondence 200 250 300 350 400 450 500 550 600 650 700 750
between spectral (Nanometer)
absorption areas and
quality parameters
Note: Reproduced with permission
VOCs, including aromatic compounds, halogenates and trihalomethanes, evaporate

when exposed to air, and can be of health concern (trihalomethanes are disinfection
by-products – DBPs-possible precursors to formation of suspected carcinogens).
Current monitoring technologies for VOCs include purge-and-trap gas
chromatography (GC) with flame ionization (FID), electron capture (ECD) or
photoionization detectors or mass spectrometry (MS). Most of these methods require
skilled operators, purification and pre-concentration, sample injection and results
analysis. Detection limits for different substances vary. Pesticides, insecticides,
fungicides and herbicides comprise triazines and phenylurea compounds; they are
monitored in surface waters in order to detect accidental pollution and check
effectiveness of specific treatments.
Online monitoring of pesticides can be carried out using composite techniques, such as:
• High pressure liquid chromatography (HPLC)/diode array (DA) detection. Consists
of: extraction, enrichment, chromatographic separation, and DA detection.
• GC. Consists of extraction and enrichment, GC separation and MS detection.
• Liquid chromatography/MS. Consists of extraction and enrichment, LC
separation and MS, thermospray, electrospray or particle beam detection.
Each technique is capable to optimally detect a group of compounds, for example,
HPLC/DA is used for atrazine, chlortoluron, cyanazine, desethylkatrazine, diuron,
hexazinone, isoproturon, linuron, metazachlor, methabenzthiazuron, metobromuron,
metolachlor, metoxuron, monolinuron, sebutylazine, simazine and terbutylazine.
In theory, any analytical method can be adapted for online use, provided that
requirements for consumables and manual intervention are minimized: current online
systems are often “robotized” adaptations of offline procedures, however, not always
this solution is the most efficient. Novel technologies, such as optochemical sensors,
biosensors, and microbiological sensors are being tested for organics and hydrocarbon
analysis. Advances already in use include differential UV spectroscopy for DBPs
detection, and microphase solid-phase extraction (SPE) for analysis of semivolatile
organics (Yongtao et al., 2000).
9 UV/VIS Spectra of Benzene Contaminated Groundwater

30
8 Diesel oil 10 mL/L
Gasoline 2 mL/L 25
7
Lubricating Oil 10 mL/L
6 Motor Oil 10 m 20
SAC 254
5
15
4
3 10
Absorbance (Abs/m)
Absorbance (Abs/m)
2
5
1
0 0
240 250 260 270 280 290 300 310 320 330 340 350 220 240 260 280 300 320 340 360 380 400
Wavelength (nm) Wavelength (nm)
Note: Reproduced with permission

dangerous
pollutants
hydrocarbons and
Spectral absorption
priority and
Monitoring of
(b) of benzene
of different (a)
Figure 5.
517
MEQ 2.1.4 Biological monitors. Biosensors offer some advantages, compared to conventional
27,5 methods, since they are cheap and simple to use, and frequently able to evaluate complex
matrices with minimal sample preparation. Advantages offered by biosensors over
analytical techniques are miniaturization and portability possibilities, permitting use as
on-site devices. A biosensor is defined as device incorporating a biological, biologically
derived, or bio-mimicking material, integrated within a physicochemical transducer or
518 transducing microsystem. In addition to specific chemicals identification, some biosensors
offer the possibility of measuring their biological effects, such as toxicity, cytotoxicity,
genotoxicity or endocrine disrupting effects. This information could sometimes be more
relevant than a specific chemical composition. There are two basic types of biological
monitors in use: those that use biological species as indicators of contaminants presence
(e.g. toxic chemicals), and those that screen for biological species (e.g. nuisance algae,
pathogens) presence. In US terminology, the term biomonitor usually indicates the former,
in fact is used as synonymous with toxicity monitor. In EU terminology, biomonitor
refers generally to all types of biologically based systems. Biosensors are distinguished
from bioassays or bioanalytical systems, which require additional sample processing
(e.g. reagent addition).
Online biological monitors are an active area of R&D due to increasing demand. At this
time, many biological monitors are relatively new and can be considered experimental/
unique lab-based applications, although commercial tests have started in BOD, nitrate
and pesticide assessment (Bahadır and Sezgintürk, 2015). Table V shows an overview of
common types of online biological monitors. Table VI summarizes the comparative
features of biosensors vs online LC-MS methods (Rodriguez-Mozaz et al., 2007).
Sensitivity of test organisms to individual compounds must be determined initially.
At the moment bacterial-based systems (Kim and Gu, 2005) show poor sensitivity and
low ease of operation. Developments could derive from improved fingerprinting of
organisms, and costs reduction. Significant advances can be expected from protozoan
monitor technology, with UV absorption/scattering techniques that may soon allow
automated detection of Cryptosporidium and Giardia. Molecular techniques initially
applied to the recognition of genomic sequences in clinical applications (Bej, 2003) have
shown potential for detection of pathogens in water, and are producing results that
could soon lead to widespread online use.
Molecular methods for detection of microbial pathogens have been established,
however, most have important limitations, associated with the time necessary to isolate
and/or identify pathogens, and detection accuracy. Research toward their improvement
relies on selective media culture methods, immunological approaches, nucleic
acid-based assays and DNA microarrays (Lemarchand et al., 2004). Molecular
fingerprinting was demonstrated an effective monitoring tool for detection of
cyanobacteria in surface waters (Loza et al., 2013).
2.1.5 Indirect monitoring: “fingerprinting”. Chemical fingerprinting describes the
use of a unique chemical signature, isotopic ratio, mineral species or pattern analysis to
identify different chemicals. Optical fingerprinting by UV, VIS and NIR absorption
spectroscopy can be effectively achieved by low-cost compact devices, linked to an
online diagnostic system, to directly identify compounds (e.g. benzene, Figure 5(b))
present in the water, or to indicate the possibility of their presence.
In optical fingerprinting, a wide portion of the UV, VIS and NIR spectrum is monitored
simultaneously at high measurement frequencies (minutes or fractions); Figure 6 shows
spectral fingerprinting of a municipal wastewater, with three spectral readings, in the
Technology Measurement Comments
Monitoring of
priority and
Fish tests Swimming pattern Low sensitivity dangerous
Ventilation rate Sophisticated requirements
Biolelectric field Requires exotic “electric fish” species pollutants
Avoidance patterns Interpretation complex
Daphnid tests Swimming activity Good performance, no determination of causes
519
Behavior
Mussel tests Shell positions/opening Can concentrate pollutants to levels many times
greater than found in the water. Long
organisms life span. Similar results over
different species
Algae tests Fluorescence (photosynthesis) Commercial monitors available
Bacteria tests Luminescence Commercially available, toxicity data for
Respiration of nitrifiers over 1,000 compounds
Chlorophyll-a Fluorometry Interference with pigments, diss. organics,
sensitive to environmental variables
Chlorophyll-a Reflectance radiometry Commercial systems available
and algal
absorption
Protozoan Measurement requires preliminary By filtration on membrane cartridge
monitors concentration/centrifugation of W/modified blood cell separators, minimal
sample operation time
Laser scanning cytometry Analysis possible within 3 min, particles must
Particle characterization be confirmed by trained operator
UV spectroscopy Measure particle size/distribution, high number
Multiangle light scattering of false positive and negative results
Nucleic acid molecules and Online system, unlabeled parasites,
magnetized microbeads differentiation problems
Successfully tested in lab Table V.
Oocysts detected within 20 min, not fully Online biological
automated monitors
wavelength range 230-730 nm, recorded from the same source within short intervals.
Individual spectra show clearly different features, indicating a water quality change
occurring in the 18 min elapsed since the first reading. Although this indication alone, in
general, will not individuate responsible compound(s), it can nevertheless trigger an alert,
indicating deviation from routine conditions. Fingerprinting can be used, in conjunction
with sophisticated algorithms and statistical software, in contaminant warning or event
detection systems (CWSs or EDSs, Section 4).
3. State-of-the-art technologies: photometric water quality monitoring

Spectral photometric methods are probably the most interesting, available mature
technology covering most online monitoring needs. They are recommended by the
US-EPA (EPA, 2013) for online monitoring over traditional techniques. Other promising
methods are discussed in Section 6. Most online instrumentation uses photometric
methods with individual or multiple wavelengths, the former having been state-of-the-art
technique for some years. UV254 analyzers operate by measuring absorption at the
single 254 nm wavelength emitted by a mercury-based UV source lamp. Most recent
developments in this field relate to the measurement of not only one or two wavelengths,
but of a continuous optical spectrum from low ultraviolet to visible light. Instruments
MEQ Online SPE-LC-MS Biosensors
27,5
Comparatively higher sample volumes of water Small sample volumes are sufficient to obtain
are necessary enough sensitivity
Matrix effect; ionic suppression or enhancementMatrix effects. Variable depending on
in MS spectrometry biorecognition principle and transduction element
Pre-concentration of the sample necessary (SPE)Direct analysis of the sample. Minimal sample
520
preparation
Multi-residue analysis Limited multi-analyte determination
Automatization and minimal sampling handling Possible automatization of the system
Direct and fast elution of the sample after pre- Direct analysis after sampling is possible. Minimal
concentration. Minimal degradation degradation
No biological stability restrictions Low biological material stability
Determination of chemical composition Determination of biological effect and of
bioavailable pollutant content
Compound selectivity by using specific sorbents Compound selectivity by using specific biological
(MIPs and immunosorbents) recognition element
Minimal consumption of organic solvents Consumption of organic solvents avoided. Direct
(elution with the LC mobile phase) analysis of contaminant in water
Generation of organic solvents waste Minimal and non-contaminating waste
Short analysis time and high throughput Faster analysis. Real-time detection and high
Table VI. throughput
Comparative features Limited portability. Laboratory confined Availability of portable biosensor systems
of online SPE-LC-MS Applicability to early warning and on-site Applicability to early warning and on-site
methods vs monitoring monitoring
biosensors for Qualified personnel required Non-qualified personnel required. User friendly
environmental Expensive equipment Cost-effective equipment
analysis Source: From Rodriguez-Mozaz et al. (2007)
600
500 13.08.02 06:44

13.08.02 06:52
absorbance (abs/m)
400 13.08.02 07:02
300
200
Figure 6.
Optical 100
fingerprinting in
a pipe (at different
0
times) indicating 230 280 330 380 430 480 530 580 630 680 730
rapid water wavelength (nm)
quality changes
Source: Created by authors
that analyze a broad spectrum from 200 to 720 nm are referred to as spectral
analyzers and utilize a xenon lamp as a light source. These were tested and explicitly
recommended by the US-EPA for online drinking water quality monitoring, instead
of traditional reagent-based analyzers (EPA, 2009). Absorbance measurement at
254 discrete wavelengths across that range allows construction of an absorbance
(spectral) curve (Figure 4). Absorbance, reported as a percent of the uninhibited lamp Monitoring of
intensity (0-100 percent) has shown to be strongly correlated to TOC content. Due to priority and
substantially greater information provided, the broadband spectrum enables TOC
measurement based on all the associated UV/visible light wavelength. Turbidity is
dangerous
calculated based on a similar analysis. Subtraction of the turbidity component enables pollutants
derived measurement of nitrate and DOC. Other parameters, not typically included in this
analysis, also may be inferred from broad spectral absorbance. 521
The result of such measurements is the so-called “fingerprint” (Figure 5). This
contains more information about water quality than a single wavelength instrument
can provide, allowing more accurate and comprehensive assessments. Continuous
spectrum readings feature two substantial advantages: nitrate, turbidity and organic
substances are measured simultaneously; a qualitative assessment of wastewater
composition is possible. Spectral nitrate measurement is extremely robust, unlike
single or dual wavelength photometry, works under most conditions, and is much less
cross-sensitive to organic carbon and turbidity (Figure 7).
The main features that have contributed to the wide acceptance of spectrometric
methods, are:
• Cost efficiency: continuous UV/VIS spectrum enables simultaneous measurement
of organic carbon, nitrate and turbidity, for which only one spectrometer is
required, instead of three photometers (Figure 8).
• Lower cross-sensitivity on turbidity, coloration, surface growth, etc.: potential
interferences, not detectable by single/dual wavelength measurement, are nearly
always compensated using spectral information.
• Greater precision, higher selectivity and reproducibility: since cross-sensitivity is
substantially reduced, heterodyning of signals due to interference/noise is
significantly less than with photometers; individual substances and/or groups can
be allocated to specific spectral features, resulting in high reproducibility.
• Qualitative evaluation: in addition to calibrated parameters, qualitative
information contained in the “fingerprint” can be directly applied for alarm
and control systems. Qualitative and quantitative differentiation of different
carbon fractions, for more detailed assessment of wastewaters (e.g. industrial
discharges) is possible.
Continuous, consistent online data can be used to extract information about the system
not available elsehow. As shown in Figure 9, nitrate profiles measured continuously are
compared to calculate travel time between monitoring sites, determine water age, and
verify the network’s hydraulic model (Thompson and Kadiyala, 2013).
4. Integrated CWSs
Following “9-11” events in the USA, after completion of risk assessments for water
systems serving populations greater than 3,300, distribution systems were identified as
the most vulnerable area of attack from terrorist groups. Although no deliberate hostile
actions on water supplies has been reported to date, in January 2002 the FBI circulated
a reserved bulletin warning water industry managers of possible al-Qaida attacks on
American water-supply systems (Ion Life, 2002). Homeland Security Presidential
Directive 9 required the US EPA to develop a program to improve protection of utilities
water distribution systems. Online quality monitoring of distribution systems has
27,5
522
MEQ
Figure 7.
in an aeration tank
Nitrate measurement
4.0
spectrometric measure
3.5
online cabinet analyzer 4.0
3.0 3.5
2.5 3.0
2.5
2.0
2.0
NO3 (mg/I)
1.5 1.5
1.0
spectral probe (mg/I)

1.0
0.5
0.5
0.0
0.0
14:24 16:48 19:12 21:36 00:00 02:24 04:48 07:12 09:36 12:00 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
time laboratory (mg/I)
Notes: (a) Online spectrometric reading vs traditional cabinet analyzer; (b) cross-calibration of nitrate readings of an online UV-VIS
spectrometer against laboratory methods. Reproduced with permission
500 10
Monitoring of
COD_eq, solids_eq, CODFilt_eq (mg/l)
9
400 8
priority and
7
dangerous
Nitrate_eq (mg/l)
300 6 pollutants
5
523
200 4
3
100 CODhom_eq (mg/l) 2
solids_eq (mg/l) Figure 8.
CODfilt_eq (mg/l) 1
Single probe
0 Nitrate_eq (mg/I) 0 continuous reading
Fr/23.03
Fr/30.03
Fr/06.04
Fr/13.04
Fr/20.04
Fr/27.04
Fr/04.05
Fr/11.05
time
of four parameters’
time series in a large
WWTP influent
Nitrate Concentration
5
4.5
Zone 4
3.5
NO3-N (mg/L)
3 Site 1
2.5
2
Figure 9.
1.5
Nitrate concentration profiles illustrate 16-hour travel time between the two sites Comparison of
continuous nitrate
1
18.01 19.01 20.01 21.01 22.01 23.01 24.01 25.01 26.01 27.01 28.01 profiles in different
Date
sections of a
distribution network
been investigated extensively for some time (CH2M HILL, 2013; Hasan et al., 2004;
Grayman et al., 2001) as such, or as CWSs, or as water quality EDSs. These consist of
integrated in-situ sensor, SCADA systems, to continuously monitor network conditions
and warn of potential contamination events. In addition to security, their benefits
may be categorized as operational enhancements, regulatory compliance and
contamination warning.
Operational enhancements include continuous indication of water quality in the
distribution system beyond that possible through routine sampling. Early indications
of water quality problems may consist of unusually low residual chlorine, impending
nitrification (elevated ammonia), turbidity excursions, and other unusual quality
changes. Monitoring is achieved through measurement of parameters familiar to
utilities (e.g. chlorine residual), and/or other relatively new parameters (e.g. TOC).
The EPA recommends monitoring four key parameters: TOC, pH, conductivity and
Chlorine (EPA, 2009), while a later study, considering all instruments and technologies
available, suggested the following: conductivity, chlorine (combined), pH, ORP,
MEQ temperature, turbidity, UV absorption (PWD, Ch2M Hill, 2013). Regulatory compliance
27,5 benefits include ability to maintain proper chlorine residuals and pH control in the
network (to avoid Pb and Cu leaching from pipes).
Warning of intentional or unintentional contamination in distribution systems is
more complex. Specialized analyzers are available, including GCs that may detect
specific contaminants and toxicity monitors providing general warnings. Due to the
524 large number of potential contaminants, it is more practical to monitor for indications
of contamination through changes in the same water quality parameters, or surrogates,

used for operational monitoring (Table VII).
Real-time monitoring strategies are the answer to detect low probability/high impact
events at an early stage, while chronic or long-term risks must be monitored with
traditional sampling. Considering safety of drinking water supplies, realistic detection
limits of available online instrumentation must be considered (Figure 10). These could
be enhanced by combining technologies, e.g. spectrometry with online toxicity
tests (Weingartner, 2013), but their sensibility will not suffice to warn about
long-term contaminants effects. The ideal EDS will react to most types of threats,
at concentrations far below the LD50 lethal dose (much higher than drinking limits),
provide distinct signals to each threat, not respond to harmless substances or
operational fluctuations (i.e. “false alarms”), and have a “fast” response. The sensoristic
component can consist of various sensing platforms, including contaminant-specific, or
quality sensors (e.g. pH, Cl, electrical conductivity, etc.) currently installed in municipal
water distribution systems to provide “surrogate” data to CWSs.
Table VIII lists in‐pipe physical/chemical parameters that can be reliably measured
along with current technologies. The most difficult issue is to distinguish actual
contamination from natural fluctuations of the water matrix. Figure 11 summarizes
capability, reliability and O&M requirements for physicochemical in-pipe sensors.
Laboratory experiments and pipe-tests proved that a majority of contaminants will
change the value of at least one surrogate parameter from normal background levels
(Byer and Carlson, 2005; Cook et al., 2005; Hall et al., 2007). Monitoring surrogate
parameters can therefore provide information on contaminants presence within a
distribution system. The challenge is to analyze surrogate signals to identify changes
Parameter Significance
TOC Total organic carbon. Elevated turbidity excursions can be associated with a
breakthrough at the water treatment plant (WTP) or scouring and release of biofilm
within the distribution system
Residual A sudden loss in residual could promote biofilm growth and potential violation of the
chlorine Total coliform rule
Conductivity Its measurement provides an easy method for identifying mixing or different water
sources, which can have a significant impact on many industrial operations
pH Controlled for disinfection and corrosion control. The formation of some disinfection
by-products is pH dependent
Turbidity Provides warning of a system disruption created by a surge or reversal in flow that
Table VII. scours the pipeline. This could be caused by a pipeline break, hydrant knock over, or
Parameters typically other problems that will impact chlorine residual and customer satisfaction
included in Notes: Utilities that use chloramines for disinfection should also measure ammonia, nitrates, and
operational water dissolved organic carbon (DOC) to provide early warning of nitrification in the distribution system.
quality monitoring The first water quality indicator of nitrification will be the increase of ammonia, which will occur
systems before nitrites and nitrates begin to increase
ppb Monitoring of
12,500 LD50 Saxitoxine priority and
dangerous
acute toxicity
pollutants
1,000 LD1, estimated
525
100 Toxicity Limit, estimated

LOG Concentration
long-term effects
Online Sensors Detection Limit
10
0.1 No known Drinking Water Limits
safe
Figure 10.
0.01 Laboratory Detection Limit Detection limits of
online sensors
Available technology
General parameters
Pressure On-chip
Temperature On-chip PPT
pH On-chip or electrolyte
ORP On-chip or electrolyte
Conductivity On-chip
Dissolved oxygen (on-chip) On-chip
Chlorine (free, total) On-chip amperometric; use of ORP
Chloramines: calculated from total – free chlorine On-chip amperometric; use of ORP
General optical parameters
Turbidity (optical) Optical
Color Optical
UV254 – simple surrogate organics indicator Optical
Spectral TOC/DOC – broad organics detector Optical
UV spectral alarms Optical
Spectral parameters for special purpose
NH4 (chloraminating systems): ISE ISE
NO2 (chloraminating systems): spectral hi-resolution UV-VIS Optical
NO3 (groundwater under agricultural influence): spectral UV-VIS Optical Table VIII.
Hydrocarbon alarm: UV-VIS or fluorescence Optical In-pipe measurable
Other important parameters no sensors exist for physical/chemical
Arsenic none parameters with
Endocrine disruptors none current available
Pesticides/herbicides none technology
MEQ
score (current technology assessment)
10 detects water quality problem = selectivity
27,5 9
8
reliability
maintenance (x per year)

7
6
5
4
526 3
2
1
Figure 11.
0
Capability, reliability
n
m
ity
ity
P
54
e*
*
pH
l
l
and O&M
ra
ra
lo
r in
ge
re
ru
tiv
id
ur
co
V2
ct
ct
su
O
lo
y
ct
rb
t
uc
pe
pe
ox
ra
ch
pe
es
requirements for
tu
nd
pe
_s
_s
pr
S
ve
C
C
V-
co
m
existing
TO
O
ol
te
U
ss
di
physicochemical quality parameter
in-pipe sensors
that are significantly beyond the range of natural ambient variability of the background
water quality, or to establish a detection baseline. Event detection by using upper and
lower concentration thresholds is virtually impossible; complex pattern recognition
algorithms are indispensable. These are implemented in event detection software,
maintaining use of already installed sensors, resulting at the moment the most
economical and effective solution to distribution system security (Weingartner, 2013).
The CANARY EDS software (Hart et al., 2007), an open-source platform developed
by the EPA, gathers water quality inputs from SCADA systems and processes data
using event detection algorithms and statistics to determine the probability of
anomalous events occurring within distribution networks (McKenna and Hart, 2008).
CANARY was tested along with four other EDS software tools under real-life conditions
by the US-EPA (EPA, 2013). The results of this evaluation were encouraging, as
conclusions regarding EDS performance showed that event detection is possible. Ability
to detect anomalous conditions strongly depends on EDS configuration, baseline
variability of the monitoring location, and the nature of the change.
5. State-of-the-art application examples

5.1 Early warning system for Bratislava’s water supply
Bratislava Water Company (BVS) is responsible for the operation of water and
wastewater systems of the capital of Slovakia, supplying a population of over 600,000.
Drinking water is produced in seven treatment facilities from 176 groundwater sources
with capacity of over 6,300 l/s.
Given the high quality of raw water the only treatment is chlorination, to prevent
microbiological growth during distribution. To ensure that contamination of a source
would not compromise overall high quality, BVS implemented a monitoring system
that oversees all sources, coupled with a EDS sending an alarm in case of unexpected
event. Measured parameters include TSS, turbidity, NO3-N, COD, BOD, TOC, DOC,
UV254, color, BTX, O3, H2S, AOC, temperature and pressure. Monitoring occurs by
means of submersible online spectrometric probes combined with a centralized system,
continuously analyzing four spectral alarm parameters from each site. On-site
evaluation of the EDS showed that the spectral alarm system is able to detect
contaminations events down to 100 μg/L TOC, 25 μg/L carbendazim, 100 μg/L benzene
and 50 μg/L Saxitoxin (Figure 12) (BVS, 2013).
4.5 distilled water Monitoring of
Carbendazim 20 g/L priority and
4 Carbendazim 50 g/L
Carbendazim 100 g/L
dangerous
3.5 drinking water pollutants
Absorption (Abs/m)
527
2.5
1.5
1
Figure 12.
0.5 Absorbance spectra
for Carbendazim
0
220 240 260 280 300 320 340 360 380 measured with an
Wavelength (nm) online spectrometer
during spike tests
5.2 Effluent of an electroplating factory with varying process agents

The detection of changes in wastewater composition in complex, multi-process facilities
can be useful to operators of local treatment. Even though exact determination of
different polluting parameters was not achieved in this case, spectral effluent
monitoring allowed identification of varying quality conditions. Association of
variations to specific operations, and calibration to process-related compounds could
then enable rapid assessment of discharged substances, and the establishment of
internal alarms (e.g. release of toxic substances). COD itself, in these cases, may have a
very restricted indicative potential as overall parameter. Figure 13(a)-(c) illustrate sets
of daily contours of the UV/VIS spectra (taken at 1-hour intervals) of an industrial
WWTP effluent. A pronounced time-dynamic behavior can be identified, and
individual groups can be clearly distinguished based on spectral properties: these are
comprised of organic carbons of Group A (250-290 nm: low molecular compounds,
aromatics, proteins, short-chain aliphatics, organic solvents, etc.), Group B (290-350
nm), organic and humic acids, biological degradation products, etc.) and Group C
(350-380 nm) not identified, but not just simple colorants.
5.3 Thames water nutrient and organics monitoring

Thames Water Utilities Ltd is the largest UK water company providing supply,
collection and treatment to over 13 million people in the Thames region. In 2007, the
company established an innovative approach to water monitoring, ensuring that all
facilities are operated at maximum efficiency, and in compliance with tight
requirements of discharge. This approach was extremely innovative and unique,
remaining unparalleled until today.
In total, 143 online water monitoring stations are located at both ends of many
WWTPs, to monitor parameters like COD, BOD, NO3, NH4 and TSS in real-time.
Spectrophotometric sensors in each station provide results at proven accuracy, and
send them to a central database, without “wet chemistry” systems, at negligible
consumables’ costs and maintenance. In a three-year review of this operational
experience, Thames Water, underlined the following operations statistics: about two
MEQ (a) 25 08 (b)
100 25 08
27,5 90
5
5
80
4
Extinction (Abs/m)
70
Extinction (Abs/m)
4
60
3
50 3
528
40 2
30 2
20 1
10 1
0 0
230 260 290 320 350 380 230 260 290 320 350 380
Wavelength (nm) Wavelength (nm)
(c) 07 09
100
90
80
Extinction (Abs/m)
70
60
50
40
30
20
10
0
230 260 290 320 350 380
Wavelength (nm)
Figure 13. Notes: (a) Relatively steady behavior, movement only in the organic carbon area
Daily contours of (250-290 nm), turbidity relatively constant; (b) same day, different vertical scale: peak in the
UV/VIS spectra carbon area (350-380 nm) is perceptible; (c) extremely high turbidity high values in organic
(at 1-hour intervals) carbon area for a short time; short peak in the area (350-380 nm) indicates pure water for a
in an industrial
WWTP effluent short time (perhaps rinsing). Reproduced with permission
million system-operating hours, with maximum failure rate of 1 in 153,500 operating

hours, concluding that online optical monitoring was in fact more economical than
traditional “wet chemistry” monitoring (S::can, 2015).
5.4 CWS/EDS implementation

The US‐EPA runs the water security initiative (WSI), a nationwide project to support
investigation and deployment of water security systems, based on distributed spectral
(and other) sensors, centralized data collecting, and on event detection software. The
first implementation of a working Water Security system was in Glendale (Arizona)
with about ten monitoring stations fully integrated into a central database (Thompson,
2008). In New York City, all existing sampling stations are being converted into
monitoring stations with the use of online spectral monitors: over 30 have been
installed to date, and proprietary software Moni::Tool was selected as detection
software (EPA, 2013). Philadelphia’s water utility developed a CWS for its drinking
water system under a EPA-WSI grant, where instrumentation selection was made by
field comparing products from different manufacturers (PWD, Ch2M Hill, 2013). Dallas
(Texas) developed a CWS consisting of four spectral UV-VIS monitors based at water Monitoring of
treatment facilities, giving a “fingerprint” of the water leaving each plant, and priority and
32 monitors providing continuous water analysis at sixteen checkpoints in the system.
Monitoring is supported by an EDS constantly checking for anomalies in the
dangerous
background. Reported benefits of expanded monitoring capabilities are: a 24/7 view of pollutants
water quality available to staff, including parameters such as nitrate, total chlorine
turbidity, TOC, conductivity, UV spectral absorbance, DOC, pH, free ammonia. All are 529
web-accessible to water operators and constitute valuable information for the detection
of water quality changes from intentional or unintentional actions, natural phenomena
and/or problems at treatment plants (Sanchez and Brashear, 2011).
6. New developing technologies

Several emerging sensor technologies could find future applications in the water
industry. Emerging biological sensors based on the detection of specific biomolecules,
enzymes and other proteins, as well as immunoassay and polymerase chain reaction
techniques (Hawkins et al., 2005) are being studied. Major biological systems current
limitations lie in their sensitivity to detect low microorganisms concentrations.
Other biosensors under development, based on evaporative light scattering
detection, refractive index measurement, fluorescence detection, and Raman
spectroscopy, exploit optical properties of water and analytes. Fluorescence uses
emitted light to measure excitation spectra of compounds such as chlorophyll, aromatic
compounds, pesticides and humic acids. Application of fluorescence for the detection of
cross-connections in drinking water systems has been recently studied (Henderson
et al., 2009). Raman spectroscopy developed into different technologies for microbial
detection, surface enhanced Raman spectroscopy (SERS) and laser tweezer Raman
spectroscopy (LTRS). SERS consists of identification of microorganisms from spectra
produced at their surface after reaction with antibodies. LTRS uses an “optical tweezer”
to pinpoint a microorganism, and laser light to produce a unique Raman spectrum that
can distinguish between strains of bacteria or spores.
Other sensor technologies based on water and contaminants’ optical properties
include infra-red (IR) spectroscopy, relying on the ability of organic functional groups
(proteins, carbohydrates, lipids, nucleic acids) to absorb IR light at specific wavelengths.
Surface acoustic wave (SAW) devices include electronic “noses,” “tongues,” and
μChemLab. SAW devices generate an acoustic wave producing, in turn, a mechanical
wave that travels through the surface of the device. Surface and frequency changes
due to bound analytes provide information about compounds concentration (Groves
et al., 2006). An electronic “nose” or “tongue” contains non-specific biological/chemical
sensors which outputs are analyzed by pattern recognition algorithms or artificial neural
networks (Krantz-Rückler et al., 2001). While electronic noses have found relatively
diffuse application in air pollution/odor recognition problems, their application in the
water field is not reported. μChemLab are gas- and/or liquid-phase monitors able to detect
biotoxins and other inorganic, high-molecular weight chemicals. The gas-phase type
consists of GC channels and SAW sensors, while the liquid type combines chip-based
techniques with fluorescence detectors. The μChemLab is commercially available
as a system for detection and analysis of bacteria, viruses and protozoa (VanderNoot
et al., 2010; Fruetel et al., 2001).
Organic thin-film transistors (OTFTs) have been investigated (Mabeck and Malliaras,
2006), as they seem ideal for inexpensive, single-use chemical or biological sensors due to
compatibility with flexible, large-area substrates, simple processing, and highly tunable
MEQ active layer materials (Roberts et al., 2008). OTFT sensors were demonstrated in aqueous
27,5 solutions with ppb-level concentrations of trinitrobenzene, methylphosphonic acid,
cysteine, showing reliable operation (Roberts et al., 2009). Given their progress, commercial
production of OTFTs could be expected in the near future (Elkington et al., 2014).
Amperometric sensors are used to detect free chlorine and consist of a flow-through
cell and an electrode layer capable of amperometric measurements due to changes in
530 analytes concentrations. They can be used for online measurements and their
integration onto chip optics is under development.
6.1 Gas and liquid chromatography screening for new contaminants

Analysis of organic micro-contaminants has been performed for many years by high
performance liquid chromatography coupled to ultraviolet detection (HPLC-UV) and
GC coupled to flame ionization detection (GC-FID), electron capture detection (GC-ECD)
and mass spectrometry (GC-MS). With the introduction of atmospheric pressure
ionization, liquid chromatography coupled to mass spectrometry (LC-MS) has largely
replaced GC methods. LC-MS presents various advantages, such as reduced sample
pretreatment and the capability to determine very polar compounds and
transformation products without derivatization. In the case of emerging pollutants,
LC-MS and especially LC-tandem mass spectrometry (LC-MS/MS), providing better
selectivity and sensitivity, has become the technique of choice. The use of MS,
and particularly MS-MS, while allowing increasing sensitivity, requires analyte
pre-concentration (SPE) to reach ultra-trace level limits of detection at which these
contaminants are present (ng/L or low μg/L).
Online configuration used for analytical determination of emerging contaminants
has been SPE coupled to LC-MS and LC-MS/MS using quadrupole instruments, joining
the inherent advantages of online SPE and LC-MS in a single methodology. Most
methods, including online methodologies, are usually restricted to few preselected
compounds and are not sufficient to assess water quality, since many more unknown
micro-contaminants may be present (Rodriguez-Mozaz et al., 2007).
Growing interest in identification of new emerging contaminants not covered by
existing water quality regulations has identified new time-of-flight (TOF) MS and
hybrid quadrupole-TOF (qTOF)-MS/MS techniques, allowing accurate determination
of the mass of precursor and product ions, respectively (Ibáñez et al., 2005). So far,
applicability of TOF and qTOF in environmental monitoring has been limited by low
sensitivity, which often is insufficient to detect low concentrations (ng/L); however,
these have been applied to pesticides, usually present at higher concentrations.
A new generation of qTOF instruments, and use of efficient separation systems, such
as ultra-performance liquid chromatography, enabling high peak resolution, high
analysis sensitivity and speed, and higher sample throughput (75 percent time reduction
compared with HPLC), could improve sensitivity of qTOF methods, facilitating
their field application. Methods were developed for rapid, automated screening of almost
400 organic micro-contaminants, and positive quantification in samples, using
liquid chromatography-electrospray quadrupole-time-of-flight mass spectrometry
(LC-qTOFMS) based on the use of accurate-mass databases (Gómez et al., 2010). These
methods are currently applicable only in laboratory settings.
6.2 Two-dimensional GC
In comprehensive two-dimensional GC, also referred to as GC × GC, all eluted
compounds from a first column are submitted to a new separation in a second column
with different selectivity. Contrary to GC employing only one column, GC × GC uses Monitoring of
two chromatographic columns in series, with a modulator. Effluent from the first priority and
column is trapped in the modulator for a known period of time (modulation time),
before being injected into the second column. The chromatograms, obtained
dangerous
through repeated trapping and injection, are rendered in two dimensions using pollutants
specialized software. Comprehensive chromatography is the last technological
development reached by separation science. While multidimensional 531
chromatography transfers only selected portions of eluate from the first to the
second dimension, in comprehensive chromatography every portion of the eluate
coming from the primary (1D) column undergoes a further 2D separation, resulting in
a greater resolution and accuracy.
Thanks to the enhanced sensitivity of GC × GC (threefold to fivefold higher than GC)
some compounds can be detected at the ng/L level. Semard et al. (2008) applied this
technique to the screening of wastewater and effluents samples. A method for target
analysis of over 100 pesticides and contaminants in a complex feed matrix was
demonstrated, based on extraction with ethyl acetate, cleanup by gel permeation
chromatography and dispersive SPE with primary secondary amine phase, followed by
analysis with full-scan TOF mass spectrometric detection (GC × GC-TOF-MS). At levels
of 50 µg/kg and higher, all targeted compounds could be identified in fully automatic
mode, based on their mass spectra. At lower levels, the hit rate decreased with
concentration. Quantification limits were in the 1-20 µg/kg range for most compounds.
The method was validated for 106 compounds at the 10 and 100 µg/kg level (van der
Lee et al., 2008). A wide range of drugs (antidepressors, antibiotics, anticoagulants),
personal care products (sunscreens, antiseptics, cosmetics) and carcinogen compounds
were similarly found in raw wastewater (Gómez et al., 2011).
In addition to the mentioned micropollutants, a wide variety of nitrogen aliphatic
and aromatic structures, possible DBP precursors, were uncovered. Figure 14 shows
results from a GC × GC-quadMS chromatogram for high-molecular weight pesticides,
in which identification was achieved using a dedicated MS pesticide library.
sec
4.749
3.582
2.376
1.187
Figure 14.
GC × GC-quadMS
0.000
chromatogram of a
0.680 17.519 23.359 29.199 35.039 min 40 pesticide standard
solution at the
Note: Reproduced with permission 10 ppb level
Source: Purcaro et al. (2011)
MEQ Non-polar halogenated micropollutants have been identified by comprehensive
27,5 two-dimensional gas chromatography (GC × GC) coupled to microelectron capture
detector (μECD) in wastewater treatment plant influent, effluent, primary and
secondary sludge matrices (including liquid and particulate phases). The target
analytes included toxaphenes, polychlorinated naphthalenes, organochlorine
pesticides, polychlorinated biphenyls, polybrominated diphenyl ethers, emerging
532 persistent and bioaccumulative chemicals. The method demonstrated robustness for a
wide range of non-polar halogenated micropollutants in all matrices (Dimitriou-

Christidis et al., 2015). Although powerful, this technology does not have potential for
direct online application, yet.
7. Discussion and conclusions

An overview of existing instrumentation for water and wastewater online monitoring
and forthcoming developments were given, and few state-of-the-art application
examples examined. It is clear that technological development in this field is very rapid,
and that astonishing advances are anticipated (fingerprinting, optochemical sensors,
biosensors, molecular techniques). Some of the technologies mentioned are not at
commercial or online, standalone application stage. Software, together with new
generation sensors, is also contributing to the identification of otherwise difficultly
identifiable parameters. Presence of contaminants not directly observable can be
inferred by water properties (e.g. absorbance) changes or indirect indicators, hence the
possibility of water quality “alerts,” pending more detailed analysis. Examples of
CWSs applications, have been illustrated. CWS is perhaps the sector in which more
rapid development is expected in coming years, possibly creating a drive for further
technological breakthroughs.
In spite of high technology instrumentation being developed, monitoring costs are
bound to become a lesser and lesser part of water utilities budgets due to automation
and technological simplification abatement of human cost factors and significant
reduction of procedural complexity (sample preparation, etc.).
Proper interpretation of the mass of water quality data that will become available
through new monitoring and information technologies will allow better management of
water resources, and of water/wastewater treatment facilities.
References
APHA, AWWA, WEF (2012), Standard Methods for the Examination of Water and Wastewater,
22nd ed., APHA, AWWA, WEF, Alexandria, VA.
AWWA (2002), “Rationale for online monitoring”, in Hargesheimer, E., Conio, O. and
Popovicova, J. (Eds), Online Monitoring for Drinking Water Utilities. Cooperative Research
Report, Chapter 2, AWWA Research Foundation, Denver, CO, pp. 9-30.
Bahadır, E.B. and Sezgintürk, M.K. (2015), “Applications of commercial biosensors in clinical,
food, environmental, and biothreat/biowarfare analyses”, Analytical Biochemistry, Vol. 1
No. 478, pp. 107-120.
Bej, A.K. (2003), “Molecular based methods for the detection of microbial pathogens in the
environment”, Journal of Microbiological Methods, Vol. 53 No. 2, pp. 139-140.
BVS (2013), “Early warning system for monitoring of Bratislava’s water supply”, internal report,
BVS, Bratislava.
Byer, D. and Carlson, K.H. (2005), “Real-time detection of intentional chemical contamination in the
distribution system”, American Water Works Association Journal, Vol. 97 No. 7, pp. 130-133.
Capodaglio, A.G. and Callegari, A. (2009), “Online monitoring technologies for drinking water Monitoring of
systems security”, in Havlinek, P., Popovska, C., Marsalek, J. and Mahrikova, I. (Eds),
Risk Management of Water Supply and Sanitation Systems, NATO Science for Peace and
priority and
Security Series, Springer, Dordrecht, pp. 153-179. dangerous
Capodaglio, A.G., Callegari, A. and Weingartner, A. (2002), “Application of innovative tools to pollutants
meet impending water resources monitoring requirements according to WFD 2000/60”,
Proceedings, EUROCONFERENCE Science for Water Policy: The Implications of the Water 533
Framework Directive, University of East Anglia, Norwich, September 2-4.

CH2M HILL (2013), “Contamination warning system demonstration pilot project: implementation
and assessment”, internal report, CH2M Hill, Philadelphia, PA.
Cook, J.E., Roehl, R. and Daamen, K. (2005), “Decision support system for water distribution
system monitoring for homeland security”, Proceedings of the AWWA Water Security
Conference, Oklahoma City, OK, April 9-13.
Copetti, D., Valsecchi, L., Sanfilippo, L., Capodaglio, A.G., Moscetta, P. and Tartari, G. (2014),
“Real-time evaluation of nutrient concentrations in surface waters using a portable probe”,
Proceedings, IWA XIII Specialist Conference on Watershed and River Basin Management,
San Francisco, CA, September, pp. 9-14.
Daughton, C.G. and Ternes, T.A. (1999), “Pharmaceuticals and personal care products in
the environment: agents of subtle change?”, Environmental Health Perspectives, Vol. 107
No. 6, pp. 907-916.
Dimitriou-Christidis, P., Bonvin, A., Samanipour, S., Hollender, J., Rutler, R., Westphale, J., Gros, J.
and Arey, J.S. (2015), “GC × GC quantification of priority and emerging nonpolar
halogenated micropollutants in all types of wastewater matrices: analysis methodology,
chemical occurrence, and partitioning”, Environmental Science & Technology, Vol. 49
No. 13, pp. 7914-7925.
Elkington, D., Cooling, N., Belcher, W., Dastoor, P.C. and Zhou, X. (2014), “Organic thin-film
transistor (OTFT)-based sensors”, Electronics, Vol. 3, pp. 234-254.
EPA (2009), “Distribution system water quality monitoring: sensor technology evaluation
methodology and results. A guide for sensor manufacturers and water utilities”, EPA 600/R-
09/076, US Environmental Protection Agency Office of Research and Development, Water
Infrastructure Protection Division. National Homeland Security Research Center, Cincinnati, OH.
EPA (2013), “Water quality event detection system challenge: methodology and findings”,
EPA 817-R-13-002, Office of Water (MC-140), Cincinnati, OH.
Fruetel, J., Kottenstette, R. and Foote, R. (2001), “µChemLab™/CB Handheld Detector”, report,
Oak Ridge National Laboratories, Oak Ridge, TN.
Glasgow, H.B., Burkholder, J.M., Reed, R.E., Lewitus, A.J. and Kleinman, J.E. (2004), “Real-time
remote monitoring of water quality: a review of current applications, and advancements in
sensor, telemetry, and computing technologies”, Journal of Experimental Marine Biology
and Ecology, Vol. 300 No. 1, pp. 409-448.
Gómez, M.J., Gómez-Ramos, M.M., Malato, O., Mezcua, M. and Férnandez-Alba, A.R. (2010),
“Rapid automated screening, identification and quantification of organic micro-
contaminants and their main transformation products in wastewater and river waters
using liquid chromatography-quadrupole-time-of-flight mass spectrometry with an
accurate-mass database”, Journal Chromatography A, Vol. 1217 No. 45, pp. 7038-7054.
Gómez, M.J., Herrera, S., Solé, D., García-Calvo, E. and Fernández-Alba, A.R. (2011), “Automatic
searching and evaluation of priority and emerging contaminants in wastewater and river
water by stir bar sorptive extraction followed by comprehensive two-dimensional gas
chromatography-time-of-flight mass spectrometry”, Analytical Chemistry, Vol. 83 No. 7,
pp. 2638-2647.
MEQ Grayman, W.M., Deininger, R.A. and Males, R.M. (2001), Design of Early Warning and Predictive
Source Water Monitoring Systems, AWWA Research Foundation, Denver, CO.
27,5
Groves, W.A., Grey, A.B. and O’Shaughnessy, P.T. (2006), “Surface acoustic wave (SAW)
microsensor array for measuring VOCs in drinking water”, Journal of Environmental
Monitoring, Vol. 8 No. 9, pp. 932-941.
Hall, J., Zaffiro, A.D., Marx, R.B., Kefauver, P.C., Krishnan, E.R., Haught, R.C. and Herrmann, J.C.
534 (2007), “On-line water quality parameters as indicators of distribution system
contamination”, American Water Works Association Journal, Vol. 99 No. 1, pp. 66-72.
Hanrahan, H., Patila, D.G. and Wang, J. (2004), “Electrochemical sensors for environmental
monitoring: design, development and applications”, Journal of Environmental Monitoring,
Vol. 6 No. 8, pp. 657-664.
Hart, D.B., McKenna, S.A., Klise, K.A., Cruz, V. and Wilson, M. (2007), “CANARY: a water quality
event detection algorithm development tool”, Proceedings ASCE World Environmental and
Water Resources Congress, Tampa, FL, May 15-19.
Hasan, J., States, S. and Deininger, R. (2004), “Safeguarding the security of public water supplies
using early warning systems: a brief review”, Journal of Contemporary Water Research and
Education, No. 129, pp. 27-33.
Hawkins, P.R., Novic, S., Cox, P., Neilan, B.A., Burns, B.P., Shaw, G., Wickramasinghe, W.,
Peerapornpisal, Y., Ruangyuttikarn, W., Itayama, T., Saitou, T., Mizuochi, M. and Inamori, Y.
(2005), “A review of analytical methods for assessing the public health risk from microcystin
in the aquatic environment”, Journal of Water Supply Research & Technology, Vol. 54,
pp. 509-518.
Henderson, R.K., Baker, A., Murphy, K.R., Hambly, A., Stuetz, R.M. and Khan, S.J. (2009),
“Fluorescence as a potential monitoring tool for recycled water systems: a review”, Water
Research, Vol. 43 No. 4, pp. 863-881.
Ibáñez, M., Sancho, J.V., Pozo, O.J., Niessen, W. and Hernández, F. (2005), “Use of quadrupole
time-of-flight mass spectrometry in the elucidation of unknown compounds present in
environmental water”, Rapid Communications in Mass Spectrometry, Vol. 19 No. 2,
pp. 169-178.
Ion Life (2002), “How safe is our water? The threat of terrorism”, Ion Life, available at: www.
ionlife.org (accessed July 2008).
Jones, O.A.H., Voulvoulis, N. and Lester, J.N. (2002), “Human pharmaceuticals in the aquatic
environment”, Environmental Technology, Vol. 22 No. 12, pp. 1383-1394.
Jothimuthu, P., Wilson, R.A., Herren, J., Haynes, E.N., Heineman, W.R. and Papautsky, I. (2011),
“Lab-on-a-chip sensor for detection of highly electronegative heavy metals by anodic
stripping voltammetry”, Biomedical Microdevices, Vol. 13 No. 4, pp. 695-703.
Kim, B.C. and Gu, M.B. (2005), “A multi-channel continuous water toxicity monitoring system: its
evaluation and application to water discharged from a power plant”, Environmental
Monitoring and Assessment, Vol. 109 Nos 1-3, pp. 123-133.
Kissinger, P.T. and Heineman, W.R. (Eds) (1996), Laboratory Techniques in Electroanalytical
Chemistry, 2nd ed., Chapter 24, Marcel Dekker, New York, NY.
Kolpin, D.W., Furlong, E.T., Meyer, M.T., Thurman, E.M., Zaugg, S.D., Barber, L.B. and Buxton, H.
(2002), “Pharmaceuticals, hormones, and other organic wastewater contaminants in US
streams, 1999-2000: a national reconnaissance”, Environmental Science & Technology,
Vol. 36 No. 6, pp. 1202-1211.
Krantz-Rückler, C., Stenberg, M., Winquist, F. and Lundström, I. (2001), “Electronic tongues for
environmental monitoring based on sensor arrays and pattern recognition: a review”,
Analytica Chimica Acta, Vol. 426 No. 2, pp. 217-226.
Lemarchand, K., Masson, L. and Brousseau, R. (2004), “Molecular biology and DNA microarray Monitoring of
technology for microbial quality monitoring of water”, Critical Reviews in Microbiology,
Vol. 30 No. 2, pp. 145-172.
priority and
Loza, V., Perona, E. and Mateo, P. (2013), “Molecular fingerprinting of cyanobacteria from river
dangerous
biofilms as a water quality monitoring tool”, Applied Environmental Microbiology, Vol. 79 pollutants
No. 5, pp. 1459-1472.
McKenna, S.A. and Hart, D. (2008), “On-line identification of adverse water quality events from 535
monitoring of surrogate data: CANARY software”, Proceedings, Singapore International

Water Week Conference, Singapore, June.
Mabeck, J.T. and Malliaras, G.G. (2006), “Chemical and biological sensors based on
organic thin-film transistors”, Analytical and Bioanalytical Chemistry, Vol. 384 No. 2,
pp. 343-353.
Modern Water (2015), available at: www.modernwater.com/monitoring/trace-metals/online-ova
(accessed January-February 2015).
Nunes, C.N., Pauluk, L.E., dos Anjos, V.E., Chierici Lopes, M. and Quináia, S.P. (2015), “New
approach to the determination of contaminants of emerging concern in natural water:
study of alprazolam employing adsorptive cathodic stripping voltammetry”, Analytical and
Bioanalytical Chemistry, Vol. 5, pp. 1-9.
O’Halloran, R., Fogelman, S. and Zhao, H. (2009), “Current online water quality monitoring methods
and their suitability for the western corridor purified recycled water scheme”, Urban Water
Security Research Alliance Technical Report No. 10, UWSRA, City East, Queensland.
Öllers, S., Singer, H.P., Fässler, P. and Müller, S.R. (2001), “Simultaneous quantification of neutral
and acidic pharmaceuticals and pesticides at the low-ng/l level in surface waters”,
Journal Chromatography A, Vol. 911 No. 2, pp. 225-231.
Purcaro, G., Quinto Tranchida, P., Conte, L., Obiedzinska, A., Dugo, P., Dugo, G. and Mondello, L.
(2011), “Performance evaluation of a rapid-scanning quadrupole mass spectrometer in the
comprehensive two-dimensional gas chromatography analysis of pesticides in water”,
Journal of Separation Science, Vol. 34, pp. 2411-2417.
PWD, Ch2M Hill (2013), “Philadelphia water department contamination warning system
demonstration pilot project: selection of online water quality monitoring technologies and
station design”, white paper submitted to EPA as part of the Water Security Initiative
Grant Awarded to Philadelphia Water Department, Philadelphia, PA.
Roberts, M.E., Mannsfeld, S.C.B., Stoltenberg, R.M. and Bao, Z. (2009), “Flexible, plastic transistor-
based chemical sensors”, Organic Electronics, Vol. 10 No. 3, pp. 377-383.
Roberts, M.E., Mannsfeld, S.C.B., Queraltó, N., Reese, C., Locklin, J., Knoll, W. and Bao, Z. (2008),
“Water-stable organic transistors and their application in chemical and biological sensors”,
Proceedings National Academy of Sciences USA, Vol. 105 No. 34, pp. 12134-12139.
Rodriguez-Mozaz, S., Lopez de Alda, M.J. and Barcelo, D. (2007), “Advantages and limitations of
on-line solid phase extraction coupled to liquid chromatography – mass spectrometry
technologies versus biosensors for monitoring of emerging contaminants in water”, Journal
Chromatography A, Vol. 1152, pp. 97-115.
Sanchez, C. and Brashear, K. (2011), “City of Dallas water utilities contamination warning system”,
City of Dallas Department of Public Works, Dallas, available at: http://dallascounty.org/
department/pubworks/media/InfrastructureForum_2011 (accessed June 2015).
S::can (2015), available at: www.s-can.at (accessed May-July 2015).
Semard, G., Do-Quang, Z. and Bruchet, A. (2008), “Screening of emerging contaminants in
wastewaters using advanced GC × GC-TOFMS”, Proceedings, Singapore International
Water Week Conference, Singapore, June.
MEQ Shao, Y., Wang, J., Wu, H., Liu, J., Aksay, I.A. and Lina, Y. (2010), “Graphene based
electrochemical sensors and biosensors: a review”, Electroanalysis, Vol. 22 No. 10,
27,5 pp. 1027-1036.
Shinsuke, I. (2013), “Total organic carbon measurement apparatus”, US Patent No. 8420013 B1,
Washington, DC.
Storey, M.V., van der Gaag, B. and Burns, B.P. (2011), “Advances in on-line drinking water
536 quality monitoring and early warning systems”, Water Research, Vol. 45 No. 2, pp. 741-747.
Tengberg, A., Hovdenes, J., Andersson, H., Brocandel, O., Diaz, R., Hebert, D., Arnerich, T.,
Huber, C., Kortzinger, A., Khripounoff, A., Rey, F., Ronning, C., Schimanski, J., Sommer, S.
and Stangelmayer, A. (2006), “Evaluation of a lifetime-based optode to measure oxygen in
aquatic systems”, Limnology and Oceanography Methods, Vol. 4, pp. 7-17.
Thompson, K. and Kadiyala, R. (2013), “Protecting water quality and public health using
a smart grid”, Computational Water, Energy, and Environmental Engineering, Vol. 2,
pp. 73-80.
Thompson, K.A. (2008), “Operational enhancements resulting from the development and
implementation of a contaminant warning system for Glendale (AZ)”, Proceedings 2008
AWWA Water Security Congress, Denver, CO, August 7-11.
van der Lee, M.K., van der Weg, G., Traag, W.A. and Mol, H.G.J. (2008), “Qualitative screening
and quantitative determination of pesticides and contaminants in animal feed using
comprehensive two-dimensional gas chromatography with time-of-flight mass
spectrometry”, Journal of Chromatography A, Vol. 1186 Nos 1-2, pp. 325-339.
VanderNoot, V.A., Renzi, R.F., Mosier, B.P., Van de Vreugde, J.L., Shokair, I. and Haroldsen, B.L.
(2010), “Development of an integrated microfluidic instrument for unattended water
monitoring applications”, Electrophoresis, Vol. 31 No. 15, pp. 2632-2640.
Weingartner, A. (2013), “Real‐time technologies for early contamination warning in water
security systems”, presentation done at ERNCIP Operator’s Workshop, Brussel,
September 11-12.
Xie, X., Zhai, J. and Bakker, E. (2014), “pH independent nano-optode sensors based on exhaustive
ion-selective nanospheres”, Analytical Chemistry, Vol. 86 No. 6, pp. 2853-2856.
Yongtao, L., George, E.J., Hansen, E.M., Toma, J.J., Werner, M. and Smith, P.D. (2000), “SPE Twin-
PAL. ‘Online in situ monitoring of semivolatile organic compounds in water’”, Proceedings,
AWWA Water Quality Technology Conference, Salt Lake City, UT.
Yue, W., Bange, A., Riehl, B.L., Riehl, B.D., Johnson, J.M., Papautsky, I. and Heineman, W.R.
(2012), “Manganese detection with a metal catalyst free carbon nanotube electrode: anodic
versus cathodic stripping voltammetry”, Electroanalysis, Vol. 24 No. 10, pp. 10-18.
Corresponding author
Andrea G. Capodaglio can be contacted at: capo@unipv.it
For instructions on how to order reprints of this article, please visit our website:
www.emeraldgrouppublishing.com/licensing/reprints.htm
Or contact us for further details: permissions@emeraldinsight.com
View publication stats

Online Monitoring of Priority and Dangerous Pollutants in Natural and Urban Waters: A State-Of-The-Art Review

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Online Monitoring of Priority and Dangerous Pollutants in Natural and Urban Waters: A State-Of-The-Art Review

Uploaded by

Copyright:

Available Formats

See discussions, stats, and author profiles for this publication at: https://www.researchgate.

Online monitoring of priority and dangerous pollutants in natural and urban

Article in Management of Environmental Quality An International Journal · June 2016

Andrea G Capodaglio Arianna Callegari

SEE PROFILE SEE PROFILE

sustainability of the urban water cycle View project

The user has requested enhancement of the downloaded file.

Access to this document was granted through an Emerald subscription provided by

*Related content and download information correct at time of download.

Online monitoring of priority Monitoring of

2. Online monitoring definition and rationale

• vulnerability (type and location of possible contaminating activity),

2.1 Online monitoring instrumentation overview

raw water Modulated four-beam turbidimeter

Parameter Currently applied technology Other technologies

DO, pH Ion-selective electrodes (IESs) Fiber-optics chemical sensors (FOCS)

accumulated as an oxidized species, and is stripped by potential sweep in the negative

Carbon fraction Definition

Total carbon (TC) Sum of organically and inorganically bound carbon

Figure 2. 2,000 1,000

Notes: (a) Distilled water; (b) groundwater. Reproduced with permission

NO2 BOD Non-compensated spectrum; represents the

VOCs, including aromatic compounds, halogenates and trihalomethanes, evaporate

9 UV/VIS Spectra of Benzene Contaminated Groundwater

Note: Reproduced with permission

3. State-of-the-art technologies: photometric water quality monitoring

500 13.08.02 06:44

400 13.08.02 07:02

spectral probe (mg/I)

of contamination through changes in the same water quality parameters, or surrogates,

100 Toxicity Limit, estimated

0.1 No known Drinking Water Limits

maintenance (x per year)

5. State-of-the-art application examples

5.2 Effluent of an electroplating factory with varying process agents

5.3 Thames water nutrient and organics monitoring

million system-operating hours, with maximum failure rate of 1 in 153,500 operating

5.4 CWS/EDS implementation

6. New developing technologies

integration onto chip optics is under development.

6.1 Gas and liquid chromatography screening for new contaminants

wide range of non-polar halogenated micropollutants in all matrices (Dimitriou-

7. Discussion and conclusions

Framework Directive, University of East Anglia, Norwich, September 2-4.

monitoring of surrogate data: CANARY software”, Proceedings, Singapore International

View publication stats

You might also like