Accepted Manuscript

Spectroscopic Surrogates for Real Time Monitoring of Water Quality in Wastewater

Treatment and Water Reuse

Gregory V. Korshin, Massimiliano Sgroi, Harsha Ratnaweera

PII: S2468-5844(17)30024-7
DOI: 10.1016/j.coesh.2017.11.003
Reference: COESH 10

To appear in: Current Opinion in Environmental Science & Health

Received Date: 17 September 2017

Revised Date: 11 November 2017
Accepted Date: 20 November 2017

Please cite this article as: Korshin GV, Sgroi M, Ratnaweera H, Spectroscopic Surrogates for Real
Time Monitoring of Water Quality in Wastewater Treatment and Water Reuse, Current Opinion in
Environmental Science & Health (2017), doi: 10.1016/j.coesh.2017.11.003.

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 ACCEPTED MANUSCRIPT

ter Treatment Treatment Goals

iological treatment Removal of: On-line Monitorin

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Dissolved organic matter
(COD, BOD5, DOC);

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Trace-level organic compounds;
Pathogens.
GAC

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Control of:
Disinfection by-product formation;

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O3/AOPs Extracellular soluble microbial product

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Reduction in UV254 Absorbance

RO

D
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Spectroscopic measurements
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Coagulation
450 0.5

Excitation Wavelength (nm)

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400 0.4
AC

350 0.3

Disinfection 300
0.2

0.1 Reduction in Total Fluorescenc

250

220 0
300 400 500
Emission Wavelength (nm)
 ACCEPTED MANUSCRIPT

Spectroscopic Surrogates for Real Time

Monitoring of Water Quality in Wastewater

Treatment and Water Reuse

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Gregory V. Korshin1,*, Massimiliano Sgroi2 and Harsha Ratnaweera3

1
Department of Civil and Environmental Engineering, Box 352700 University of

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Washington, Seattle, WA 98195-2700 United States
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2
Department of Civil Engineering and Architecture, University of Catania, Viale A. Doria 6,
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95125, Catania, Italy

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3
Faculty of Science and Technology, Norwegian University of Life Sciences, PO Box 5003,
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1432 Aas, Norway

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*
Corresponding author. Phone: +1-206-543-2394; fax: +1-206-685-9185; e-mail address:
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korshin@uw.edu
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ABSTRACT
 ACCEPTED MANUSCRIPT
This review examines the potential of spectroscopic methods in online and real time water

quality monitoring. Extensive research has shown that measurements of changes of

absorbance and fluorescence of wastewater and drinking water during its treatment are

predictive of the reduction of levels of trace-level organic contaminants (TrOC) or pathogens.

Changes of water fluorescence and absorbance are also correlated with the formation of

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bromate, biodegradable dissolved organic carbon BDOC and products of the oxidation of

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TrOC or dissolved organic matter (DOM). The review concludes that the current level of the

development and implementation of spectroscopic methods for online/real time water quality

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monitoring is far from its real potential.

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KEYWORDS: absorbance; fluorescence; monitoring; surrogate parameter; trace organic
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contaminants; water quality; wastewater, water reuse
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Abbreviations
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A254 UV absorbance at 254 nm;

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AOPs Advanced oxidation processes;

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ASI Absorbance slope index;

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BDOC Biodegradable DOC;

BOD Biochemical oxygen demand;

COD Chemical oxygen demand;

DBPs Disinfection by-products

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DOC Dissolved organic carbon;

DOM Dissolved organic matter;

EEM Excitation-emission matrix;

EfOM Effluent organic matter;

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GAC Granular activated carbon;

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PAC Powdered activated carbon;

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PARAFAC Parallel factor analysis;

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SMP Soluble microbial products; AN
SUVA Specific UV absorbance;

TF Total Fluorescence;
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TrOC Trace-level organic Contaminants;

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WWTPs Wastewater treatment plants.

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1. Introduction
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The rapid growth of the global economy and population has stressed water resources and
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caused their quality to deteriorate due to increasing loads of domestic wastewater, industrial

effluents and agricultural runoff. This has been compounded by climatic changes that have

resulted in extreme weather events and deficits between the amount of water needed for

consumption and that provided via natural water cycles. These trends have resulted in water

reuse practices that necessitate more attention to the occurrence and effects of water

pollutants [1-3]. Given that water reuse implies the intentional introduction of treated (or,
 ACCEPTED MANUSCRIPT
frequently, unintentional use of untreated) wastewater to augment conventional water sources

[4], continuous control of water treatment processes and monitoring of parameters of

wastewater that are pertinent to its health effects and environmental impacts becomes of

evident importance [5,6].

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In this review, the use of spectroscopic measurements to monitor water quality in wastewater

treatments and water reuse is discussed. Spectroscopic surrogates have been proposed to

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monitor a wide range of water quality parameters, including conventional parameters (e.g.,

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COD, BOD5), pathogens, disinfection by-products (DBPs) and trace organic contaminants

(TrOCs) [6]. Extensive recent research in this area has been specifically focused on DBPs

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and TrOCs monitoring due to the increasing environmental and health concerns associated
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with these contaminants, and difficulties related to their analytical determination that must be

done using techniques that are highly precise yet laborious, time-consuming and expensive
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[7,8].
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2. General aspects of absorbance and fluorescence-based

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approaches for water quality monitoring

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Use of optical surrogate parameters, notably those based on absorbance and fluorescence, has

been particularly important for water quality monitoring [6,9-11]. Contributions of dissolved
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organic matter (DOM) or effluent organic matter (EfOM) to the absorbance of wastewater or
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surface water, and changes of these spectra associated with water treatment or with

transformation of DOM/EfOM in natural systems are indicative of the concurrent effects on

trace organic contaminants (TrOCs). Absorbance-based monitoring of these processes can be

done using a number of parameters which were recently discussed in Li and Hur [12]. That

review compares the use of single-wavelength indicators (e.g., A254), combinations of

absorbance measurements at up to four wavelength, ratios of absorbance at indicative

 ACCEPTED MANUSCRIPT
wavelengths (e.g., A254/A202) [13,14], the interpretation of absorbance data using the

differential absorbance approach and processing multi-wavelength absorbance spectra in

logA coordinate [15-18]. These and related options are compared in some detail in Table 1.

One difficulty in using absorbance spectroscopy for water quality monitoring is that the

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absorbance spectra of DOM/EfOM comprise contributions of multiple chromophores and

inter-chromophores interactions [19,20]. As a result, these spectra are featureless although

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DOM/EfOM properties such as its aromaticity, apparent molecular weight can be estimated

based on single-wavelength parameters (e.g., absorption coefficient at 280 nm - ε280, specific

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UV254 absorbance - SUVA254), absorbance ratios (e.g., A254/A202, absorbance slope index -

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ASI) and slopes of the log-transformed absorbance spectra.
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Excitation-emission matrixes (EEM) of natural waters and wastewater tend to have distinct

features with maxima located at characteristic combinations of excitation and emission

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wavelengths. Different methods have been developed to interpret the information in EEMs,
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from simple peak-picking, in which different fluorescence peaks are selected from several
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defined wavelength ranges of EEM to the more complex Parallel Factor Analysis

(PARAFAC), which can decompose the complex fluorescence spectra into a finite number of
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potentially overlapping independent components characterized by their distinct spectroscopic

features [21]. The presence of various EEMs features allows tracking contributions of the
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indicative fluorophores groups as a function of water treatment or the presence of wastewater

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in an affected body of water [22-25]. Table 2 presents an abridged list of fluorescence-based

parameters whose utility in water quality monitoring has been examined in recent research.

Nevertheless, the use of fluorescence spectroscopy for water quality monitoring has some

limitations. Issues affecting the precision of fluorescence measurements and ensuing

mathematical processing of EEM data include temperature fluctuations, interferences caused

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by turbidity and inner filter effect, and the potential presence of quenching of fluorescence

caused by some metal ions or organic contaminants [6]. Correction procedures have been

proposed for some of these issues but they tend to be more efficient for surface water samples

and their performance in the case of wastewater monitoring needs to be examined further [26-

28].

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3. Differential spectroscopy for quantitation of water quality in

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treatment operations

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One approach to using absorbance- and fluorescence-based surrogates to ascertain the

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behaviour of TrOC in water treatment operations utilizes the concept of differential
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spectroscopy. The latter concept quantifies either the absolute changes of the intensity of

absorbance (∆A=A0-Atreated) or fluorescence (∆F=F0-Ftreated) at any particular wavelength or

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their normalized (relative) intensity changes (∆A/A0 or ∆F/F0) vs. an a priori selected

reference state for which the respective absorbance or fluorescence signal intensities (A0, F0)
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are determined. Extensive research has demonstrated that strong correlations exist between
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changes of TrOC levels and, on the other hand ∆A/A0, ∆F/F0 and related parameters [29-36].
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Due to the traditional use of the wavelength of 254 nm for water quality monitoring, a

considerable portion of this research has utilized relative changes of absorbance at 254 nm
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(∆A254/A0,254) but other observation wavelengths, or their combinations can be equally

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successfully employed. For instance, data obtained by Nanaboina and Korshin [29]

demonstrate that relative changes of absorbance of ozonated wastewater are more prominent

and do not significantly depend vs. wavelength in the range of λ>350 nm.

A recent study by Stapf et al. [37] showed that online ∆A254 measurements can be used for

closed-loop process control of wastewater ozonation and TrOC elimination. Practical aspects
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of such measurements, notably the compensation for variability of dissolved organic carbon

(DOC) or nitrite levels and needs to maintain the quality of absorbance measurements were

also discussed. The use of differential absorbance spectroscopy to quantify EfOM

transformations and control operations in full scale ozonation and UV/H2O2 treatment was

discussed by Audenauert et al. [38]. That study utilized both online ∆A254 and absorbance

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slope index (ASI) measurements which were applied to quantify contribution of molecular

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ozone and hydroxyl radical.

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Gerrity and al. [32] discussed the performance of ∆A254 and total fluorescence (∆TF)

indicators to quantify the degradation of TrOCs during ozonation. The reported laboratory

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measurements were done in nine wastewaters while pilot- and full-scale data were generated
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for eight wastewaters. Reasonably strong linear correlations were observed for most of the

examined contaminants as well as for the inactivation of three microbial surrogates

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(Escherichia coli, MS2, and Bacillus subtilis spores) (R2 from 0.46 to 0.78). Another study of
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the performance of absorbance (∆A254) and integrated total fluorescence (TF) surrogates in
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ozonation is presented by Park et al. [39]. The latter study utilized a kinetic approach to

calculate the comparative kinetics of TOrC attenuation by molecular ozone and hydroxyl
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radical and relate them to the changes of absorbance at 254 nm and total fluorescence (TF) of

filtered and unfiltered wastewater effluents. This study provides a set of guidelines for the
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implementation of surrogate models for real-time monitoring of TrOC degradation in ozone-

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based processes for water reuse.

The formation of ozonation by-products such as bromate, aldehydes, carboxylic acids,

biodegradable DOC (BDOC) and degradation products of typical TrOCs such as

fluoroquinolone antibiotics was examined by a number of researchers [40-42]. These studies

demonstrate that strong correlations exist between changes of the absorbance and
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fluorescence of treated water and the generation of bromate. Similarly strong correlations

exist for BDOC and products of DOC/EfOM degradation, notably oxalate, formate, acetate

and formaldehyde. Correlations between changes of the absorbance of ozonated wastewater

and yields of intermediates formed upon the degradation of ciprofloxacin, norfloxacin and

lomefloxacin were non-monotonic reflecting the formation of these intermediates are low

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ozone doses and/or treatment times and their breakdown at higher oxidant doses. These data

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showed that the kinetic aspects of the generation of these products and concentrations of

ozonation by-products and intermediates formed upon the oxidation of TrOCs can be

SC
determined based on the behavior of spectroscopic parameters of wastewater during its AOP

treatment.

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AN
Other recent studies have discussed the performance of ∆A254 and ∆TF indicators to predict

TrOC adsorption onto activated carbons in both powered activated carbon (PAC) processes
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[33,35,43,44] and granular activated carbon (GAC) filters [31]. The developed models

provide excellent predictions of TrOC removal in secondary or tertiary wastewater effluents

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and these models resulted independent of the wastewater quality [31,33,35,43,44] . However,
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during GAC filtration, empirical linear correlations for TrOC removal obtained using ∆TF
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showed higher R2 than models obtained using ∆A254, probably due to a slower breakthrough

of fluorescence signal than A254 signal [31]. Accordingly, a recent research has hypothesized
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fluorescence DOM to be lower in molecular weight than UV-absorbing DOM to explain its
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preferential adsorption [45].

The use of surrogate parameters to monitor changes of properties of extracellular soluble

microbial products (SMP) in a batch bioreactor under starvation conditions was discussed in

Maqbool et al. [46]. The study used measurements of A254, spectral slope, absorbance slope

index (ASI) together with the biological and humification indexes, and the ratio of
 ACCEPTED MANUSCRIPT
tryptophan-like to humic-like components (peak T1/peak M) to describe the dynamic changes

in SMP properties. ASI was determined to be strongly correlated with specific oxygen uptake

rate while the peak T1/peak M ratio was suggested as the preferable indicator of the relative

abundance of proteins to humic-like substances in SMPs.

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Fluorescence spectroscopy and components discrimination by PARAFAC or peak-picking

methods has been used for water and wastewater quality monitoring in treatment works

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[6,22,47-50]. The concentration of the proteinaceous tryptophan-like fluorescent components

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was found to be sensitive to the biological treatment, and the observed correlations with

water quality parameters typically used to evaluate effluents compliance with regulatory

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standards, such as COD, TOC, BOD5, has suggested the use of this fluorescence component
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as a tool for water treatment efficacy monitoring in conventional wastewater treatment plants

(WWTPs) [6,22,47]. Recently, correlations between tryptophan-like fluorescence and water

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quality parameters have been validated in constructed wetland systems as well [51]. The

differential spectroscopy approach allowed to found important correlations between various

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fluorescence components and TOrCs in 10 conventional WWTPs characterized by different

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secondary treatments (e.g., presence or absence of nitrification and denitrification processes,

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use of activated sludge unit or rotating biological contactors). Notably, the behaviour of

TOrCs that had very high removals (i.e., triclosan, caffeine and ibuprofen) was correlated
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with that of the fluorescence indexes associated with aromatic proteins and tyrosine-like
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components while the behaviour of moderately removed atenolol, naproxen, gemfibrozil and

trimethoprim was better correlated with the fluorescence index assigned to humic-like

substances [52]. A summary of the major aspects of the discussed regression models

developed for representative water quality parameters and based on absorbance and

fluorescence measurements is presented in Table 3 and Table 4, respectively.

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4. Conclusions and Future Directions

Recent studies provide ample evidence of the potential of spectroscopic methods for water

quality monitoring. Changes of absorbance and fluorescence of wastewater during its

oxidative treatment have been found to be predictive of the reduction of TrOC/pathogen

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levels. Similar results have been obtained for adsorption onto activated carbon. In addition,

predictive models have been developed for the removal of conventional and emerging

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contaminants by conventional WWTPs. The formation of bromate, BDOC, aldehydes,

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carboxylic acids, and intermediates formed upon the degradation of selected TrOCs can also

be tracked based on the use of absorbance or fluorescence surrogates.

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Notwithstanding these achievements, the current level of the development and
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implementation of spectroscopic methods for water quality monitoring remains far from their

full potential. Fundamentally, it is important to understand the functional form of ∆C/C vs.
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∆F/F or ∆A/A correlations and relate them explicitly to the kinetic rates of degradation of any
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particular trace contaminant or pathogen and those of the dominant DOM or EfOM matrix.
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Further efforts will ascertain such correlations for the generation and breakdown of

intermediates and end products TrOC degradation and their applicability to monitor the
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removal of TrOCs or pathogens by a wider range of processes including UV/Cl2 and

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persulfate-based treatment methods.

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The existing data support the notion that changes of wastewater absorbance and fluorescence,

whether induced in engineered systems or in exposed streams, may be indicative of the

concurrent changes of the toxicity, mutagenicity and endocrine activity of treated wastewater.

Further experiments will establish whether this hypothesis is correct and if so how it can be

applied to monitor and predict ecological effects in real time.

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Consistent approaches to design and operate an inherently robust sensor network for any

wastewater treatment plant or reuse system needs to be pursued further, together with the

development of novel sensitive and stable sensors that provide multi-wavelength absorbance

and fluorescence, and other relevant data. Methods to process such data to generate real-time

PAPAFAC and differential spectroscopic data, and import them into advanced models

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relating the behavior the surrogate parameters and actual water quality data are necessary.

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ACKNOWLEDGMENTS

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G.V.Korshin and H.Ratnaweera would like to thank the Norwegian Research Council

(MEMPREX project) for its partial support of this research.

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Table 1 Abridged list of absorbance-based surrogate water parameters for quality monitoring.
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Parameter Previous Interpretation Reference

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A254 Standard UV absorbance parameter

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Ratio of absorbance at 254 and 202 nm; a [53]

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measure of activation of NOM (can be affected

by the presence of nitrate)

Relative treatment-induced change of water [29]

absorbance at wavelength λ.
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Differential change of water absorbance at [54,55]

wavelength λ determined vs. the absorbance

prior to treatment.

Slope of log-transformed absorbance spectra the [18]

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range of wavelength λ1 to λ2

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Logarithm of relative change of absorbance [17,18]

or

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Absorbance slope index; deemed to be a [14]

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measure of the molecular weight of NOM and
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its activity
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Table 2 Abridged list of fluorescence-based surrogate water parameters for quality

monitoring.
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Parameter Previous Interpretation Reference

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Fluorescence Index, interpreted as an [56]

indicator of aromaticity

Humification Index, interpreted as an [57]

extent of natural organic matter

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humification

Biological index, deemed a measure of [58]

DOM endogenous contribution

Peak B (λex/em= ~225 Proteins and tyrosine-like fluorescing [59]

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(~280)/~305 nm) substances

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Peak T1 (λex/em= ~225/~350 Proteins, microbial products and [59]

nm) tryptophan-like fluorescing substances

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Peak T2 (λex/em= ~280/~350 Proteins, microbial products and [59]

nm)
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tryptophan-like fluorescing substances
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Peak A (λex/em= ~225/400-500 Microbial products, fulvic and humic-like [59]
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nm) fluorescing substances

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Peak C (λex/em= 300-350/400- Terrestrial humic-like fluorescing [59]

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500 nm) substances

Autochthonous production, marine and [59]

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Peak M (λex/em= 310-320/

terrestrial humic-like fluorescing
380-420 nm)
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substances
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Indicator of the relative abundance of [22]

proteins to humic-like substances

TF is calculated integrating the volume [60]

Total Fluorescence (TF)
under the entire EEM surface, and

normalized to the projected excitation-

 ACCEPTED MANUSCRIPT
emission area

Fluorescence components discriminated by [21]

parallel factor analysis. Components are

PARAFAC components classified according to the position of the

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excitation and emission peaks and DOM

source

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M
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Table 3. Summary of absorbance-based predictive models developed for online monitoring of

representative water quality parameters

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Spectroscopic Target Wastewater Note Reference

parameter compound treatment/system
∆A254/ A0,254 TrOcs Ozonation Linear regression [29,32,37]
(removal) models; non-
applicable for
TrCOs with
kO3>10-5 M-1s-1
∆A254/ A0,254 microbial Ozonation Linear regression [32]
surrogates models
(deactivation)
∆A254/ A0,254 TrOcs Ozonation Model based on [39]
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(removal) kinetic approach
∆A254/ A0,254 Degradation Ozonation Non-monotonic [40]
products of correlation
fluoroquinolone models
antibiotics
(formation)
∆A254/ A0,254 Bromate, Ozonation Non-linear [42]
∆A280/ A0,280 BDOC correlation
(formation) models

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∆A254/ A0,254 TrOcs Powdered Linear and non- [33,35,43,44]
(removal) activated carbon linear correlation
(PAC) models

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∆A254/ A0,254 TrOcs Granular activated Linear regression [31]
(removal) carbon (GAC) models
∆A254/ A0,254 TrOcs UV/H2O2 Linear regression [30]

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(removal) models

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Table 4. Summary of fluorescence-based predictive models developed for online monitoring

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of representative water quality parameters

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Spectroscopic Target Wastewater Note Reference

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parameter compound treatment/system

∆TF/TF0 TrOcs Ozonation Linear regression [32]
(removal) models
∆TF/TF0 microbial Ozonation Linear regression [32]
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surrogates models
(deactivation)
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∆TF/TF0 TrOcs Ozonation Model based on [39]

(removal) kinetic approach
∆TF/TF0 Aldehydes and Ozonation Linear regression [41]
carboxylic models.
acids
(formation)
∆F/F0 Bromate, Ozonation non-linear correlation [42]
(Humic-like BDOC models
fluorescence (formation)
intensity
measured by
 ACCEPTED MANUSCRIPT
LED sensor)
∆TF/TF0 TrOcs Powdered Linear and non-linear [43]
(removal) activated carbon correlation models
(PAC)
∆TF/TF0 TrOcs Granular activated Linear regression [31]
(removal) carbon (GAC) models
∆TF/TF0 TrOcs UV/H2O2 Linear regression [30]
(removal) models
∆F/F0 COD, BOD5, Conventional Linear correlation [47]

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(tryptophan- total carbon WWTPs
like (removal)
PARAFAC

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component)
∆F/F0 COD, BOD5 Constructed Linear correlation [51]
(tryptophan- (removal) wetlands

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like
PARAFAC
component)
∆F/F0 (peak highly Conventional Linear regression [52]

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B) removed WWTPs models
TrOCs (e.g.,
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ibuprofen,
caffeine,
triclosan)
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∆F/F0 (peak Moderately Conventional Linear regression [52]

C, humic-like removed WWTPs models
PARAFAC TrOCs (e.g.,
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components) trimethoprim,
atenolol,
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gemfibrozil,
naproxen)
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REFERENCES

1 Focazio MJ, Kolpin DW, Barnes KK, Furlong ET, Meyer MT, Zaugg SD, Barber LB, Thurman

ME: A national reconnaissance for pharmaceuticals and other organic wastewater

contaminants in the United States—II) Untreated drinking water sources. Sci Total

Environ 2008, 402: 201-216.

 ACCEPTED MANUSCRIPT
2 Al-Rifai JH, Gabelish CL, Schäfer AI: Occurrence of pharmaceutically active and non-

steroidal estrogenic compounds in three different wastewater recycling schemes in

Australia. Chemosphere 2007, 69:803-815.

3 Dickenson ER, Snyder SA, Sedlak DL, Drewes JE: Indicator compounds for assessment

of wastewater effluent contributions to flow and water quality. Water Res 2011, 45:1199-

PT
1212.

4 Amoueyan E, Ahmad S, Eisenberg JN, Pecson B, Gerrity D: Quantifying pathogen risks

RI
associated with potable reuse: A risk assessment case study for Cryptosporidium.

SC
Water Res 2017, 119:252-266.

5 Altenburger R, Ait-Aissa S, Antczak P, Backhaus T, Barceló D, Seiler TB, Brion F., Busch W,

U
Chipman K, López de Alda M et al: Future water quality monitoring—adapting tools to
AN
deal with mixtures of pollutants in water resource management. Sci Total Environ 2015,

512:540-551.
M

6 *Carstea EM, Bridgeman J, Baker A, Reynolds DM: Fluorescence spectroscopy for

wastewater monitoring: A review. Water Res 2016, 95:205-219. This study provides a
D

detailed review of the results of extensive research concerned with the elucidation of water
TE

quality based on its fluoresnce spectra and formal parameters that characterize them.
EP

7 Richardson SD, Ternes TA: Water analysis: Emerging contaminants and current issues.

Anal Chem 2017, 10.1021/acs.analchem.7b04577

C

8 Anumol T, Merel S, Clarke B, Snyder SA: Ultra high performance liquid chromatography
AC

tandem mass spectrometry for rapid analysis of trace organic contaminants in water.

Chem. Cent. J. 2013, 7:104

9 Storey MV, Van der Gaag B, Burns BP: Advances in on-line drinking water quality

monitoring and early warning systems. Water Res 2011, 45:741-747.

10 Vaillant S, Pouet MF, Thomas O: Basic handling of UV spectra for urban water quality

monitoring. Urban Water 2002, 4:273-281.

 ACCEPTED MANUSCRIPT
11 Thomas O, Burgess C (Eds.): UV-visible spectrophotometry of water and wastewater (Vol.

27). Elsevier; 2004.

12 *Li P, Hur J: Utilization of UV-Vis spectroscopy and related data analyses for dissolved

organic matter (DOM) studies: A review. Crit Rev Env Sci Tec 2017, 47:131-154. This

study provided an excellent outline of the significance and relative advantages of absorbance-

PT
based parameters that can be uilitized to determine properties of dissolve organic matter.

13 Her N, Amy G, Sohn J, von Gunten U: UV absorbance ratio index with size exclusion

RI
chromatography (URI-SEC) as an NOM property indicator. J Water Supply Res T 2008,

SC
57:35-44.

14 Korshin GV, Chow CW, Fabris R, Drikas M: Absorbance spectroscopy-based examination

U
of effects of coagulation on the reactivity of fractions of natural organic matter with
AN
varying apparent molecular weights. Water Res 2009, 43:1541-1548.

15 Helms JR, Stubbins A, Ritchie JD, Minor EC, Kieber DJ, Mopper K: Absorption spectral
M

slopes and slope ratios as indicators of molecular weight, source, and photobleaching

of chromophoric dissolved organic matter. Limnol and Oceanogr 2008, 53:955-969.

D
TE

16 Fichot CG, Benner R: The spectral slope coefficient of chromophoric dissolved organic

matter (S275–295) as a tracer of terrigenous dissolved organic carbon in

EP

river‐‐influenced ocean margins. Limnol and Oceanogr 2012, 57:1453-1466.

17 Yan M, Korshin GV, Chang HS: Examination of disinfection by-product (DBP) formation
C

in source waters: a study using log-transformed differential spectra. Water Res 2014,
AC

50:179-188.

18 Roccaro P, Yan M, Korshin GV: Use of log-transformed absorbance spectra for online

monitoring of the reactivity of natural organic matter. Water Res 2015, 84:136-143.

19 Del Vecchio R, Blough NV: On the origin of the optical properties of humic substances.

Environmental Sci Technol 2004, 38:3885-3891.

 ACCEPTED MANUSCRIPT
20 Yan M, Dryer D, Korshin GV, Benedetti MF: In situ study of binding of copper by fulvic

acid: comparison of differential absorbance data and model predictions. Water Res

2013, 47:588-596.

21 Murphy KR, Stedmon CA, Graeber D, Bro R: Fluorescence spectroscopy and multi-way

techniques. PARAFAC. Anal Methods-UK 2013, 5:6557-6566.

PT
22 Henderson RK, Baker A, Murphy KR, Hambly A, Stuetz RM, Khan SJ: Fluorescence as a

potential monitoring tool for recycled water systems: a review. Water Res 2009, 43:863-

RI
881.

SC
23 Cohen E, Levy GJ, Borisover M: Fluorescent components of organic matter in

wastewater: efficacy and selectivity of the water treatment. Water Res 2014, 55:323-334.

24
U
Zhou Y, Jeppesen E, Zhang Y, Shi K, Liu X, Zhu G: Dissolved organic matter fluorescence
AN
at wavelength 275/342 nm as a key indicator for detection of point-source

contamination in a large Chinese drinking water lake. Chemosphere 2016, 144:503-509.

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25 Sgroi M, Roccaro P, Korshin GV, Vagliasindi FGA: Monitoring the behavior of emerging
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contaminants in wastewater-impacted rivers based on the use of fluorescence

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excitation emission eatrixes (EEM). Environmental Sci.Technol. 2017, 51: 4306-4316.

26 Luciani X, Mounier S, Redon R, Bois A: A simple correction method of inner filter effects
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affecting FEEM and its application to the PARAFAC decomposition. Anal. Chim. Acta

2009, 96:227–238.
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27 Kothawala DN, Murphy KR, Stedmon CA, Weyhenmeyer GA, Tranvik LJ: Inner filter
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correction of dissolved organic matter fluorescence. Limnol. Oceanogr. Methods 2013,

11:616–630. doi:10.4319/lom.2013.11.616

28 Khamis K, Sorensen JPR, Bradley C, Hannah DM, Lapworth DJ, Stevens R: In situ

tryptophan-like fluorometers: assessing turbidity and temperature effects for

freshwater applications. Environ Sci Process Impacts 2015, 17:740-752.

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29 Nanaboina V, Korshin GV: Evolution of absorbance spectra of ozonated wastewater and

its relationship with the degradation of trace-level organic species. Environmental Sci

Technol 2010, 44:6130-6137.

30 Yu HW, Anumol T, Park M, Pepper I, Scheideler J, Snyder SA: On-line sensor monitoring

for chemical contaminant attenuation during UV/H2O2 advanced oxidation process.

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Water Res 2015, 81:250-260.

31 **Anumol T, Sgroi M, Park M, Roccaro P, Snyder SA: Predicting trace organic compound

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breakthrough in granular activated carbon using fluorescence and UV absorbance as

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surrogates. Water Res 2015, 76:76-87. This study investigated the applicability of UV

absorbance at 254 nm (UV254), and total fluorescence (TF) to act as surrogates in predicting

trace organic compound (TOrC) removal by granular activated carbon at scaled-test.

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Application of the empirical linear correlation models to full-scale samples provided good
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results for six of seven TOrCs tested when comparing predicted TOrC removal by UV254 and

TF with actual removals for GAC.

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32 Gerrity D, Gamage S, Jones D, Korshin GV, Lee Y, Pisarenko A, Trenholm RA, von Gunten
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U, Wert EC, Snyder SA: Development of surrogate correlation models to predict trace
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organic contaminant oxidation and microbial inactivation during ozonation. Water Res

2012, 46:6257-6272.
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33 Zietzschmann F, Altmann J, Ruhl AS, Dunnbier U, Dommisch I, Sperlich A, Meinel F, Jekel

M: Estimating organic micro-pollutant removal potential of activated carbons using UV

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absorption and carbon characteristics. Water Res 2014, 56:48-55.

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34 Li W, Majewsky M, Abbt-braun G, Horn H, Jin J, Li Q, Zhou Q, Li A-M: Application of

portable online LED UV fluorescence sensor to predict the degradation of dissolved

organic matter and trace organic contaminants during ozonation. Water Res 2016,

101:262–271.

35 *Zietzschmann F, Aschermann G, Jekel M: Comparing and modeling organic micro-

pollutant adsorption onto powdered activated carbon in different drinking waters and
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WWTP effluents. Water Res 2016, 102:190-201. The adsorption of organic micro-pollutants

(OMP) onto powdered activated carbon (PAC) was compared between regionally different

waters within two groups, namely five drinking waters and seven wastewater treatment plant

(WWTP) effluents. Correlations between OMP removals and UV254 removals were

independent of the water (within the respective group).

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36 Li W, Nanaboina V, Chen F, Korshin GV: Removal of polycyclic synthetic musks and

antineoplastic drugs in ozonated wastewater: quantitation based on the data of

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differential spectroscopy. J Hazard Mater 2016, 304:242-250.

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37 **Stapf M, Miehe U, Jekel M: Application of online UV absorption measurements for

ozone process control in secondary effluent with variable nitrite concentration. Water

Res 2016, 104:111-118. In this study, a closed-loop process control based online UVA254

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measurements for elimination of trace organic compounds was successfully implemented and
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tested under realistic conditions at a pilot scale to adapt the ozone dose to a varying water

quality.
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38 Audenaert WTM, Vandierendonck D, Van Hulle SWH, Nopens I: Comparison of ozone and
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HO induced conversion of effluent organic matter (EfOM) using ozonation and UV/H2O2
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treatment. Water Res 2013, 47:2387-2398.

39 Park M, Anumol T, Daniels KD, Wu S, Ziska AD, Snyder SA: Predicting trace organic
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compound attenuation by ozone oxidation: Development of indicator and surrogate

models. Water Res 2017, 119:21-32.

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40 Liu C, Nanaboina V, Korshin GV: Formation of degradation products of fluoroquinolone

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antibiotics in ozonated water and their modeling based on in situ absorbance

monitoring data. Water Res 2012, 46:5235-5246.

41 Liu C, Tang X, Kim J, Korshin GV: Formation of aldehydes and carboxylic acids in

ozonated surface water and wastewater: a clear relationship with fluorescence

changes. Chemosphere 2015, 125:182-190.

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42 **Li WT, Cao MJ, Young T, Ruffino B, Dodd M, Li AM, Korshin GV: Application of UV

absorbance and fluorescence indicators to assess the formation of biodegradable

dissolved organic carbon and bromate during ozonation. Water Res 2017, 111:154-162.

The study examined the significance of changes of UV absorbance and fluorescence of

dissolved organic matter (DOM), using miniature LED UV/fluorescence sensor, as surrogate

indicators for assessing the formation of bromate and biodegradable dissolved organic carbon

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(BDOC) during the ozonation of surface water and wastewater effluent.

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43 Ziska AD, Park M, Anumol T, Snyder SA: Predicting trace organic compound attenuation

with spectroscopic parameters in powdered activated carbon processes. Chemosphere

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2016, 156:163-171.

44 Altmann J, Massa L, Sperlich A, Gnirss R, Jekel M: UV254 absorbance as real-time

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monitoring and control parameter for micropollutant removal in advanced wastewater
AN
treatment with powdered activated carbon. Water Res 2016, 94:240-245.
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45 Shimabuku, KK, Kennedy AM, Mulhern RE, Summers RS: Evaluating Activated Carbon

Adsorption of Dissolved Organic Matter and Micropollutants Using Fluorescence

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Spectroscopy. Environ Sci Technolol 2017, 51:2676-2684.

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46 *Maqbool T, Cho J, Hur J: Spectroscopic descriptors for dynamic changes of soluble

microbial products from activated sludge at different biomass growth phases under
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prolonged starvation. Water Res 2017, 123:751-760. The spectroscopic indices pertinent to

the evaluation of properites of soluble microbial products (SMP) were explored using
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absorption and fluorescence spectroscopy to identify different distinctive biomass growth

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phases (i.e., exponential phase, pseudo-endogenous phase, and endogenous phase) and to

describe the microbial activity of activated sludge in a batch type bioreactor under prolonged

starvation.

47 Cohen E, Levy GJ, Borisover M: Fluorescent components of organic matter in

wastewater: efficacy and selectivity of the water treatment. Water Res 2014, 55:323-334.
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48 Sanchez NP, Skeriotis AT, Miller CM: Assessment of dissolved organic matter

fluorescence PARAFAC components before and after coagulation–filtration in a full

scale water treatment plant. Water Res 2013, 47:1679-1690.

49 Yang L, Hur J, Zhuang W: Occurrence and behaviors of fluorescence EEM-PARAFAC

components in drinking water and wastewater treatment systems and their

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applications: a review. Environ Pollut Sci Res 2015, 22:6500-6510

50 Murphy KR, Hambly A, Singh S, Henderson RK, Baker A, Stuetz R, Khan SJ: Organic

RI
matter fluorescence in municipal water recycling schemes: toward a unified PARAFAC

SC
model. Environmental Sci Technol 2011, 45:2909-2916.

51 Sgroi M, Pelissari C, Roccaro P, Sezerino PH, García J, Vagliasindi FGA, Ávila C: Removal

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of Organic Carbon, Nitrogen, Emerging Contaminants and Fluorescing Organic Matter
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in Different Constructed Wetland Configurations. Chem Eng J 2018, 332:619-627.

52 **Sgroi M, Roccaro P, Korshin G V., Greco V, Sciuto S, Anumol T, Snyder SA, Vagliasindi
M

FGA: Use of fluorescence EEM to monitor the removal of emerging contaminants in full

scale wastewater treatment plants. J Hazard Mater 2017, 323:367–376. This study
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investigated the applicability of fluorescence indexes to act as surrogates in predicting trace

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organic compounds (TOrCs) removal during conventional wastewater treatments that usually

comprise primary and secondary treatments. Particularly, the behaviour of TOrCs that had
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very high removals (i.e., triclosan, caffeine and ibuprofen) was correlated with that of the

fluorescence indexes associated with tyrosine-like components; whereas the moderate

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removal of atenolol, naproxen, gemfibrozil and trimethoprim was correlated with the
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fluorescence index assigned to humic-like substances

53 Korshin GV, Li CW, Benjamin MM: Monitoring the properties of natural organic matter

through UV spectroscopy. Evaluation of a consistent theory. Water Res 1997, 31:1787–

1795.

54 Korshin GV, Wells W, Benjamin MM, Hemingway O: Correlations between differential

absorbance and the formation of individual DBP species. Water Res 2002, 36:3273-3282
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55 Korshin GV, Benjamin MM, Li CW: Principles and applications of differential UV

spectroscopy for monitoring and predicting the formation of disinfection by-products.

J Am Water Works Assoc 1998, 90: 88-100

56 Mcknight D, Boyer EW, Westerhoff PK, Doran PT, Kulbe T, Andersen DT:

Spectrofluorometric characterization of dissolved organic matter for indication of

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precursor organic material and aromaticity. Limnol Oceanogr 2011, 46:38-48

57 Ohno T, Chorover J, Omoike A, Hunt J: Molecular weight and humification index as

RI
predictors of adsorption for plant- and manure-derived dissolved organic matter to

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goethite. Eur J Soil Sci 2007, 58:125-132

58 Huguet A, Vacher L, Relexans S, Saubusse S, Froidefond JM, Parlanti E: Properties of

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fluorescent dissolved organic matter in the Gironde Estuary. Org. Geochem. 2009,
AN
40:706–719

59 Coble PG: Characterization of marine and terrestrial DOM in seawater using excitation-
M

emission matrix spectroscopy. Mar Chem 1996, 51:325-346

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60 Chen, W., Westerhoff, P., Leenheer, J.A., Booksh, K., 2003. Fluorescence excitation-
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emission matrix regional integration to quantify spectra or dissolved organic matter.

Environ. Sci. Technol. 37, 5701-5710.

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Potential of spectroscopic methods for water quality monitoring is discussed.

Changes of absorbance and fluorescence of wastewater are predictive of the removal of trace-

level organic contaminants and pathogens.

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Formation of by-products of wastewater treatment can be tracked using spectroscopic surrogates.

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Further efforts will develop correlations between changes of surrogate parameters and ecological

endpoints.

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