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Article
Characteristics and Biodegradability of Wastewater
Organic Matter in Municipal Wastewater Treatment
Plants Collecting Domestic Wastewater and
Industrial Discharge
Yun-Young Choi 1 , Seung-Ryong Baek 1 , Jae-In Kim 1 , Jeong-Woo Choi 1 , Jin Hur 2 , Tae-U Lee 3 ,
Cheol-Joon Park 3 and Byung Joon Lee 1, *
1 Department of Construction and Environmental Engineering, Kyungpook National University, 2559
Gyeongsang-daero, Sangju, Gyeongbuk 742-711, Korea; yunchoi@knu.ac.kr (Y.-Y.C.);
ps5788@naver.com (S.-R.B.); jaein1224@naver.com (J.-I.K.); chjw51@knu.ac.kr (J.-W.C.)
2 Department of Environment & Energy, Sejong University, Seoul 143-747, Korea; jinhur@sejong.ac.kr
3 Daegu Environmental Corporation, Daegu 42720, Korea; ion094@hanmail.net (T.-U.L.);
goldberg0419@hanmail.net (C.-J.P.)
* Correspondence: bjlee@knu.ac.kr; Tel.: +82-54-530-1444

Academic Editor: Giuseppe Olivieri


Received: 7 April 2017; Accepted: 2 June 2017; Published: 8 June 2017

Abstract: Municipal wastewater treatment plants (WWTPs) in Korea collect and treat not only
domestic wastewater, but also discharge from industrial complexes. However, some industrial
discharges contain a large amount of non-biodegradable organic matter, which cannot be treated
properly in a conventional biological WWTP. This study aimed to investigate the characteristics
and biodegradability of the wastewater organic matter contained in the industrial discharges and to
examine the fate of the industrial discharges in a biological WWTP. In contrast to most previous studies
targeting a specific group of organic compounds or traditional water quality indices, such as biological
oxygen demand (BOD) and chemical oxygen demand (COD), this study was purposed to quantify
and characterize the biodegradable and nonbiodegradable fractions of the wastewater organic matter.
Chemical oxygen demand (COD) fractionation tests and fluorescence spectroscopy revealed that the
industrial discharge from dyeing or pulp mill factories contained more non-biodegradable soluble
organic matter than did the domestic wastewater. Statistical analysis on the WWTPs’ monitoring
data indicated that the industrial discharge containing non-biodegradable soluble organic matter
was not treated effectively in a biological WWTP, but was escaping from the system. Thus, industrial
discharge that contained non-biodegradable soluble organic matter was a major factor in the decrease
in biodegradability of the discharge, affecting the ultimate fate of wastewater organic matter in
a biological WWTP. Further application of COD fractionation and fluorescence spectroscopy to
wastewaters, with various industrial discharges, will help scientists and engineers to better design
and operate a biological WWTP, by understanding the fate of wastewater organic matter.

Keywords: wastewater; industrial discharge; organic matter; COD fraction; fluorescence

1. Introduction
Municipal wastewater treatment plants (WWTPs) in Korea collect and treat not only domestic
wastewater, but also discharge from industrial complexes. Industrial factories have their own facilities
for treating industrial wastewater and then discharge the treated water into the sewer system [1,2].
However, the treatment facilities target easily biodegradable organic matter, rather than refractory
non-biodegradable organic matter, as long as the facilities can comply with traditional regulations for

Water 2017, 9, 409; doi:10.3390/w9060409 www.mdpi.com/journal/water


Water 2017, 9, 409 2 of 12
Water 2017, 9, 409 2 of 11

for biodegradable
biodegradable organic
organic matter,
matter, suchsuch as for
as for biological
biological oxygen
oxygen demand
demand (BOD)[3].
(BOD) [3].Thus,
Thus,some
someindustrial
industrial
discharges are likely to contain
discharges contain aa large
largeamount
amountofofrefractory
refractorynon-biodegradable
non-biodegradableorganic organic matter.
matter.A
Aconventional
conventionalbiological
biologicalWWTP
WWTP(i.e.,
(i.e.,activated
activatedsludge
sludgesystem)
system) may
may not treat suchsuch non-biodegradable
non-biodegradable
organicmatter
organic matterproperly,
properly,andandthere
thereisisaarisk
riskofofititescaping
escapingfromfromthetheWWTP
WWTPtotoaariver riverororlake
lake[4,5].
[4,5].
Organic matter
Organic matter inin wastewater
wastewater has has been
been estimated
estimated as as an
an equivalent
equivalent quantity,
quantity, suchsuch asas chemical
chemical
oxygen demand
oxygen demand(COD)
(COD)oror biological oxygen
biological demand
oxygen (BOD).
demand However,
(BOD). the adoption
However, of tertiaryoftreatment
the adoption tertiary
processes to
treatment remove nutrients
processes to remove and refractory
nutrients and organic matter
refractory requires
organic a classification
matter requires aofclassification
the subordinate of
fractions of wastewater organic matter. For instance, the total COD of wastewater
the subordinate fractions of wastewater organic matter. For instance, the total COD of wastewater organic matter can
be classified
organic matterinto
canthe four fractions
be classified into theof readily biodegradable
four fractions of readilyCOD (RBCOD),COD
biodegradable slowly biodegradable
(RBCOD), slowly
COD (SBCOD),
biodegradable COD non-biodegradable soluble CODsoluble
(SBCOD), non-biodegradable (NBDSCOD), and non-biodegradable
COD (NBDSCOD), particulate
and non-biodegradable
COD (NBDPCOD)
particulate (Figure 1)(Figure
COD (NBDPCOD) [6,7]. 1)RBCOD, such assuch
[6,7]. RBCOD, volatile fatty fatty
as volatile acids,acids,
is readily degraded
is readily degraded by
microbial
by microbialmetabolism.
metabolism. SBCOD,
SBCOD, composed
composed of of particulate
particulate organic matter,
organic matter,is isdegraded
degradedslowlyslowlybybya
aseries
seriesofofmicrobial
microbialactions,
actions,such
such asas adsorption,
adsorption, hydrolysis, and metabolism.
metabolism. NBDSCOD, which which is is
refractory in
refractory in biodegradation, is is contained
containedin inindustrial
industrialdischarges.
discharges.Aromatic
Aromaticcompounds
compounds are used
are usedin
various
in various industries
industries and
andare
aretypical
typicalexamples
examplesof ofNBDSCOD.
NBDSCOD. NBDPCODNBDPCOD is is also non-biodegradable,
but is
but is removed
removedeasily
easilyby bysedimentation
sedimentationin inaaconventional
conventionalWWTP. WWTP.

Figure
Figure 1. Schematic diagram
1. Schematic diagram of
of the
the chemical
chemical oxygen
oxygendemand
demand(COD)
(COD)fractions
fractionsand
andtheir
theirfates
fatesinina
abiological
biologicalwastewater
wastewatertreatment
treatmentplant.
plant.

Depending
Depending on the the type
typeofofindustry,
industry,some some industrial
industrial discharges
discharges areare abundant
abundant in NBDSCOD,
in NBDSCOD, and
and
thus,thus,
moremore refractory
refractory in a biological
in a biological treatment
treatment process.
process. For example,
For example, it hasreported
it has been been reported that
that dyeing
dyeing
factoriesfactories
discharge discharge a large amount
a large amount of NBDSCOD of NBDSCOD [4,8,9]. many
[4,8,9]. Because Because many chemical
chemical dyes are
dyes are based on
based on aromatic or heterocyclic ring structures, which are considered non-biodegradable,
aromatic or heterocyclic ring structures, which are considered non-biodegradable, industrial discharge industrial
discharge
from dyeing from dyeing likely
factories factories likelysubstantial
contains contains substantial
amounts of amounts
NBDSCOD. of NBDSCOD.
In addition, In industrial
addition,
industrial
discharge fromdischarge fromfactories
paper mill paper wasmillreported
factoriestowas reported
contain a large to contain
amount a large
of lignin andamount of lignin
lignin derivatives,
and
whichlignin
are derivatives,
also known to which are also known to be
be non-biodegradable, andnon-biodegradable,
hence, increase theand hence,ofincrease
amount NBDSCOD the amount
[10,11].
of
AnNBDSCOD
advanced [10,11].
oxidation Anprocess
advanced oxidation
might process
be required to might
degradebe required
NBDSCOD to degrade
containing NBDSCOD
aromatic
compoundsaromatic
containing from dyeing and paper
compounds frommill factories
dyeing [9,12]. mill factories [9,12].
and paper
This study
This study aimed
aimed to to investigate
investigate howhow industrial
industrial discharges
discharges fromfrom dyeing
dyeing andand paper
paper mill
mill factories
factories
affectthe
affect thecharacteristics
characteristics andand biodegradability
biodegradability of wastewater
of wastewater organic organic
matter matter
and their and
fatetheir fate in a
in a biological
biologicalprocess.
treatment treatment In process.
contrast toIn most
contrast to most
previous previous
studies studies
targeting targeting
a specific a specific
group group
of organic of organic
compounds
compounds
or traditionalor traditional
water qualitywater
indices quality indices
(e.g., BOD and(e.g.,
COD) BOD and COD)
[4,5,13], [4,5,13],
this study this study
adopted adopted
sophisticated
sophisticated
analytical analytical
techniques techniques
to quantify andtocharacterize
quantify and thecharacterize
organic matter the composition
organic matter composition
of the wastewater of
the wastewater
containing containing
industrial dischargesindustrial
from dyeingdischarges
and pulp from
milldyeing and
factories. pulp fractionation
A COD mill factories. A based
test, COD
fractionation
on a respirometer test,technique
based on[14],a respirometer
was appliedtechnique
to quantify[14], was applied
the fractions to quantify
of RBCOD, SBCOD, the NBDSCOD,
fractions of
RBCOD,
and NBDPCOD,SBCOD, andNBDSCOD,
fluorescenceand NBDPCOD,
spectroscopy [15]and
was fluorescence spectroscopy
used to characterize [15] was
the chemical used to
composition
characterize
of wastewaterthe chemical
organic composition
matter of wastewater
qualitatively. Informationorganic
about thematter
COD qualitatively.
fractions, and Information about
the fluorescence
the COD fractions,
spectroscopic and the fluorescence
characteristics of wastewater spectroscopic
organic matter, characteristics of wastewater
will help predict the fate oforganic matter,
waste organic
will help
matter in a predict
WWTP and the provide
fate of waste
the bestorganic
availablematter in a WWTP
technologies and provide
for treating wastewater the organic
best available
matter.
technologies
Such for treating
quantitative wastewater
and qualitative organic
data about matter. Such
wastewater quantitative
organic matter willand bequalitative
used to overcomedata about
the
wastewater organic matter will be used to overcome the design and operational difficulties of a
WWTP receiving a large amount of industrial discharge from dyeing and paper mill factories.
Water 2017, 9, 409 3 of 12

design and operational difficulties of a WWTP receiving a large amount of industrial discharge from
dyeing and paper mill factories.

2. Materials and Methods

2.1. Study Site and Sampling


The Jisan (JS) WWTP is located in a commercial and residential area, and the facility collects
and treats mostly domestic wastewater. Thus, the JS WWTP was selected as a control system in
this research. In contrast, the Dalseocheon (DS) and Hyunpoong (HP) WWTPs were selected as
experimental systems, because they collect and treat large amounts of industrial discharge from dyeing
and paper mill factories, respectively. The proportion of industrial discharge in influent wastewater
was approximately 25% for the DS WWTP and 75% for the HP WWTP. Given that there are plans for
residential complexes in the HP WWTP’s catchment area, the proportion of the industrial discharge is
very high for the HP WWTP.
Two sets of sampling campaigns were conducted from October to November 2015. Each sampling
campaign was carried out in a WWTP, collecting 20 L of a wastewater sample and 2 L of an activated
sludge sample. The wastewater sample was collected in the distribution channel between the primary
sedimentation process and the biological treatment process. Thus, the wastewater sample was settled
wastewater, but not raw wastewater. The activated sludge sample was collected at the end of the
aeration tank of the biological treatment process, when presumably all of the soluble biodegradable
organic matter would have been degraded completely. The wastewater samples were stored at 4 ◦ C to
minimize biodegradation while being transported to the laboratory. Before starting the respirometer
(biodegradation) test, we warmed up the wastewater samples to 20 ◦ C and washed the sludge sample
with distilled deionized water to remove any other impurities.

2.2. Experimental Methods


For the respirometer test, we used a 4 L cylindrical reactor, equipped with a plastic impeller to stir
the mixed liquor and an air diffuser to supply oxygen. At the beginning of the test, the wastewater and
activated sludge samples were mixed rapidly in the reactor. The mixed liquor was then stirred slowly
at 40 rpm to minimize surface aeration. A Styrofoam plate was placed on the surface of the mixed
liquor to minimize surface aeration. The air diffuser was the only source of dissolved oxygen (DO) in
the reactor. The air diffuser was powered on at DO = 2.0 mg/L, and off at DO = 5.0 mg/L, so that the
DO of the mixed liquor was maintained between 2 and 5 mg/L. An LDO101 DO probe and an HQ30d
DO meter (HACH Inc., Loveland, CO, USA) were used to record the DO of the mixed liquor every 10 s.
Oxygen utilization rates (OUR) were calculated with the downward slopes of a DO curve (Figure 2).
As shown in Equation (1) and Figure 2, RBCOD can be estimated based on the area of the plateau
of the OUR graph [6,7,14,16]. The integral part of Equation (1) indicates the total amount of oxygen
consumption by RBCOD degradation. Because only a part (i.e., 33%) of RBCOD is assumed to use
oxygen via microbial catabolism, RBCOD is calculated by multiplying the integral part by 1/(1 − YZH ).
The integral part of Equation (1) is equivalent to the area between the OURTotal and OURSBCOD plots
in Figure 2b.

Z t=d Z t=d
1 1
RBCOD = (OURtotal − OURSBCOD )·dt = (OURRBCOD )·dt (1)
1 − YZH t =0 1 − YZH t =0
Water 2017, 9, 409 4 of 12
Water 2017, 9, 409 4 of 11

(a) Dissolved Oxygen (b) Oxygen Utilization Rate


6.0 1.1

Oxygen Utilization Rate (mgDO/s/L)


1.0
Dissolved Oxygen (mgDO/L)

OURTotal
5.0
0.9 OURSBCOD

0.8
4.0
0.7 Area = RBCOD
3.0 0.6
OUR drops
at the DO bending point 0.5
2.0
0.4

1.0 0.3
0 2000 4000 6000 8000 0 2000 4000 6000 8000
Time (s) Time (s)

Figure2.2. Results
Figure Results from
from aa respirometer
respirometer test,
test, measuring
measuring the the readily
readily biodegradable
biodegradable COD
COD (RBCOD)
(RBCOD)
concentration in wastewater organic matter. (a,b) illustrate dissolved oxygen (DO) concentrations
concentration in wastewater organic matter. (a,b) illustrate dissolved oxygen (DO) concentrations and and
oxygen utilization rate, respectively, with increasing
oxygen utilization rate, respectively, with increasing time.time.

A BOD test was used to measure the biodegradable COD (i.e., BDCOD = RBCOD + SBCOD) of
A BOD test was used to measure the biodegradable COD (i.e., BDCOD = RBCOD + SBCOD)
the wastewater organic matter, because the BDCOD was assumed to be equal to the ultimate BOD
of the wastewater organic matter, because the BDCOD was assumed to be equal to the ultimate
(BODU) [17]. A measurement of 0.3 mL of the 40 g/L allyl thiourea (ATU) stock solution was added
BOD (BODU ) [17]. A measurement of 0.3 mL of the 40 g/L allyl thiourea (ATU) stock solution was
to each BOD bottle to prevent oxygen utilization by nitrification. For each wastewater sample, a series
added to each BOD bottle to prevent oxygen utilization by nitrification. For each wastewater sample,
of BOD concentrations was measured on 3, 5, 8, 12, 15, and 20 days. Subsequently, the ultimate
a series of BOD concentrations was measured on 3, 5, 8, 12, 15, and 20 days. Subsequently, the
BOD (BODU) was estimated with a curve-fitting analysis, adopting the first-order decaying model
ultimate BOD (BODU ) was estimated with a curve-fitting analysis, adopting the first-order decaying
(Equation (2)). The curve-fitting analysis was performed with a scientific graphing program
model (Equation (2)). The curve-fitting analysis was performed with a scientific graphing program
(SigmaPlotTM, Systat Inc., San Jose, CA, USA). Finally, the SBCOD of a wastewater sample was
(SigmaPlotTM, Systat Inc., San Jose, CA, USA). Finally, the SBCOD of a wastewater sample was
estimated by subtracting RBCOD from BDCOD.
estimated by subtracting RBCOD from BDCOD.
BOD ≈ BDCOD = RBCOD + SBCOD = BOD / 1 −e  (2)
−kt
BOD ≈ BDCOD = RBCOD + SBCOD = BOD / 1 − e
The NBDSCOD of Ua wastewater sample was measured witht consecutive biodegradation and (2)
coagulation
The NBDSCODtests [18,19]. After 24-h biodegradation
of a wastewater sample was measured and 1-h withsedimentation,
consecutive a sample was collected
biodegradation and
from the reactor. Then 5 mL of the 1 M ZnSO 4 stock solution and 5 mL of the 1 M NaOH solution
coagulation tests [18,19]. After 24-h biodegradation and 1-h sedimentation, a sample was collected
werethe
from added to theThen
reactor. collected
5 mL500 mL1sample,
of the M ZnSO andstock
the mixture
solutionwas andcoagulated
5 mL of the by1stirring
M NaOH rapidly at 80
solution
4
rpm for 1 min, and slowly at 20 rpm for 5 min. ZnSO 4 as a coagulant is supposed to aggregate and
were added to the collected 500 mL sample, and the mixture was coagulated by stirring rapidly at
remove
80 rpm for all1the
min, colloidal
and slowlyand particulate
at 20 rpm for organic
5 min.matter.
ZnSO4Thus, the remaining
as a coagulant organic to
is supposed matter in the
aggregate
solution
and remove phase is assumed
all the colloidal to andbeparticulate
soluble [19,20].
organic After 1-h Thus,
matter. sedimentation, a supernatant
the remaining sample
organic matter in was
the
taken and filtered through 0.45 µm pore size membrane filter paper
solution phase is assumed to be soluble [19,20]. After 1-h sedimentation, a supernatant sample was (Hyundai Micro Inc., Seoul,
Korea).
taken andAssuming
filtered through that 0.45
all the soluble
µm pore biodegradable
size membrane filter organic matter Micro
paper (Hyundai was degraded
Inc., Seoul,by 24-h
Korea).
biodegradation,
Assuming that allandtheall the particulate
soluble organic
biodegradable mattermatter
organic was removed by coagulation
was degraded by 24-hand filtration, the
biodegradation,
and all the particulate organic matter was removed by coagulation and filtration, the CODestimated
COD of the final filtrate would be equal to the NBDSCOD. Finally, the NBDPCOD was by
of the final
subtracting the RBCOD, the SBCOD, and the NBDSCOD from the
filtrate would be equal to the NBDSCOD. Finally, the NBDPCOD was estimated by subtracting the total COD.
RBCOD, Thethe
fluorescence
SBCOD, and emission–excitation
the NBDSCOD from matrices and
the total parallel factor analysis (FEEM-PARAFAC)
COD.
wasTheapplied
fluorescence emission–excitation matrices and parallelcomposition
to characterize the dissolved organic matter (DOM) factor analysisof a (FEEM-PARAFAC)
wastewater sample.
Theapplied
was wastewater samples, filtered
to characterize through
the dissolved a 0.45 matter
organic µm pore size membrane
(DOM) composition filter
of a(Hyundai
wastewater Micro Inc.,
sample.
The wastewater samples, filtered through a 0.45 µm pore size membrane filter (Hyundai Micro Inc.,3
Seoul, Korea) were kept in a freezer prior to the FEEM analysis. The samples were adjusted to pH
by adding
Seoul, Korea) 1M wereHCl prior
kept in atofreezer
absorbance
prior and
to the fluorescence
FEEM analysis. measurements
The samples to were
minimize the potential
adjusted to pH 3
interference of pH variability and metal bindings. Ultraviolet
by adding 1 M HCl prior to absorbance and fluorescence measurements to minimize the potential(UV) absorbance at 254 nm was
measured with a Hach DR5000 UV-visible spectrophotometer (Hach,
interference of pH variability and metal bindings. Ultraviolet (UV) absorbance at 254 nm was measuredLoveland, CO, USA), with
Milli-Q water as the blank. The FEEMs of the samples, diluted until
with a Hach DR5000 UV-visible spectrophotometer (Hach, Loveland, CO, USA), with Milli-Q water UV254 < 0.05 cm −1, were scanned

using
as the ablank.
Perkin-Elmer
The FEEMs LS-55ofluminescence
the samples,spectrometer
diluted until(Perkin-Elmer
UV254 < 0.05 Inc.,
cmWaltham, MA, USA)
−1 , were scanned over
using
Ex/Em wavelengths of 250–500 and 280–550 nm, with increments of
a Perkin-Elmer LS-55 luminescence spectrometer (Perkin-Elmer Inc., Waltham, MA, USA) over Ex/Em 5 nm and 0.5 nm, respectively.
The FEEM of each sample was subject to blank subtraction and normalized by the Raman peak of
Milli-Q water excited at 350 nm. The detailed procedures of fluorescence EEMs are described
Water 2017, 9, 409 5 of 12

wavelengths of 250–500 and 280–550 nm, with increments of 5 nm and 0.5 nm, respectively. The FEEM
of each sample was subject to blank subtraction and normalized by the Raman peak of Milli-Q water
excited at 350 nm. The detailed procedures of fluorescence EEMs are described elsewhere [15,21]. All of
the FEEM results for the 20 collected samples were statistically analyzed by PARAFAC modeling, using
MATLAB version 8.5 software (MathWorks Inc., Natick, MA, USA) with the DOMFluor toolbox [22].
The number of components was determined based on split-half analysis.

3. Results and Discussion

3.1. COD Fractionation


Results from the COD fractionation tests for the wastewater samples are summarized in Table 1.
The total COD (TCOD) concentrations of the JS, DS, and HP WWTPs were relatively low at 156, 111,
and 112 mg/L for the first sampling campaign, and 150, 105, and 129 mg/L for the second sampling
campaign. Wastewaters in Korea usually have a low COD concentration, compared to wastewaters in
other developed countries, because the wastewaters are collected in a combined sewer system [7,23].
The TCOD of the control system (i.e., the JS WWTP), collecting mostly domestic wastewater, was
higher than that of the experimental systems (i.e., DS and HP WWTPs). The RBCOD for both the
control and experimental systems was relatively low, less than 10 mg/L. The RBCOD of the DS and
HP WWTPs, in particular, was in some cases very low, less than 1 mg/L. The combined sewer system,
which often has an open channel, might reduce the fermentation from wastewater organic matter to
volatile fatty acids (i.e., RBCOD) [24]. Above all, it is important to note that the DS and HP WWTP
had values for NBDSCOD that were two to three times higher than those for the JS WWTP, but those
values were two to three times lower than the BODU (i.e., BDCOD). This observation indicates that the
industrial discharge from the DS and HP WWTPs changed the COD fractions of wastewater organic
matter substantially.

Table 1. Summarized results of the COD fractionation tests carried out for the two sampling campaigns
from October to November 2015.

First Sampling Campaign Second Sampling Campaign


ITEM
JS WWTP DS WWTP HP WWTP JS WWTP DS WWTP HP WWTP
Total COD 155.5 ± 0.5 110.7 ± 3.3 112 ± 3.2 150 ± 3.7 105 ± 3.7 129 ± 4.0
CODZn24 (a) 28.5 ± 0.5 43.7 ± 2.1 67 ± 1.2 21 ± 1.0 45.5 ± 1.5 71 ± 1.7
BODu (b) 124 52.4 38.8 123.2 52.6 43.8
RBCOD 9.2 4.7 0.7 7.7 0.3 8
SBCOD 114.8 47.7 38.1 115.5 52.3 35.8
NBDSCOD 28.5 43.7 67.0 21.0 45.5 71.0
NBDPCOD 3.0 14.6 6.2 5.8 6.9 14.2
Notes: Total COD and CODZn24 show the mean value and standard deviation of the triplicated measurements.
(a)
CODZn24 = Measured COD after 24-h biodegradation and flocculation (Unit: mgCOD/L); (b) BODU = Ultimate
BOD estimated by the data-fitting analysis;

The COD fractions of the JS, DS, and HP wastewaters are shown graphically in the pie charts
(Figure 3). Wastewater organic matter of the JS WWTP, collecting mostly domestic wastewater, had
a large BDCOD (=RBCOD + SBCOD) fraction at 81% of the TCOD. A typical BDCOD fraction was
reported to be about 80% to 90% for raw and primary effluent wastewaters [7,25]. This observation,
and the earlier reports, indicate that domestic wastewater consisted mostly of biodegradable organic
matter. In contrast, wastewater organic matter of the DS and HP WWTPs had a small BDCOD fraction,
but a large NBDSCOD fraction. The NBDSCOD of the HP WWTP was especially high at 57% of the
TCOD. Because a large amount of the industrial discharge from dyeing and paper mill factories flowed
to the DS and HP WWTPs, it was inevitable that the NBDSCOD fraction increased.
Water 2017, 9, 409 6 of 12

The COD fractionation test was also applied to the sample collected directly from the paper mill
factories in the HP WWTP’s catchment area. The NBDSCOD fraction of the direct industrial discharge
was 80% of the TCOD, but the BDCOD fraction was only 6%. Thus, it appears that the treatment
facilities in the paper mill factories were able to treat the BDCOD easily, but dumped the refractory
NBDSCOD
Water into the sewer system. Unfortunately, the current standards for industrial discharges 6focus
2017, 9, 409 of 11
on an integrated parameter, such as BOD5 or CODMn , which do not indicate the subordinate COD
fractions
COD properly.
fractions The operators
properly. of the treatment
The operators facilities might
of the treatment be satisfied
facilities might bewith their performance,
satisfied with their
performance,
but nonetheless butappear
nonetheless appear to be with
to be unconcerned unconcerned with the
the refractory refractory NBDSCOD.
NBDSCOD.

100
Wastewater COD Fractions (%)

80 RBCOD
SBCOD
NBDSCOD
60 NBDPCOD

40

20

0
JS DS HP HP ( Industrial)
WWTPs

EstimatedCOD
Figure 3. Estimated CODfractions
fractionsofofthe
theinfluent
influent wastewaters
wastewaters in in Jisan
Jisan wastewater
wastewater treatment
treatment plant
plant (JS
(JS WWTP), Dalseocheon wastewater treatment plant (DS WWTP), Hyunpoong
WWTP), Dalseocheon wastewater treatment plant (DS WWTP), Hyunpoong wastewater wastewater treatment
plant (HP WWTP), and the industrial discharge from pulp mill factories in the HP WWTP’s WWTP’s catchment
catchment
area. The fractions in the figures represent the average
average values
values of
of the
the two
two measurement
measurement campaigns.
campaigns.

3.2. FEEM-PARAFAC
FEEM-PARAFAC
FEEM-PARAFAC
FEEM-PARAFAC was was used to characterize the chemical composition of wastewater dissolved
organic matter (DOM) and to investigate the compositional
compositional change
change inin biodegradation.
biodegradation. FEEM-PARAFAC
FEEM-PARAFAC
revealed that a four-component model could represent represent the characteristics
characteristics of
of wastewater
wastewater DOM
DOM (Figure
(Figure 4).
4).
Components C1, C2, C2, C3,
C3, and
andC4C4were
werecharacterized
characterizedwith
withthe
theExcitation/Emission maximaatat≤≤230/345,
Excitation/Emissionmaxima 230/345,
≤220(275)/355,≤275(220)/320,
≤220(275)/355, ≤275(220)/320, andand243/430 nm,nm,
243/430 respectively.
respectively.Reviewing
Reviewingthe references (Table
the references 2), we
(Table 2),
could
we assign
could thethe
assign four components
four components of of
C1,C1,
C2,C2,
C3, and
C3, and C4C4totoprotein-like,
protein-like,tryptophan-like,
tryptophan-like,tyrosine-like,
tyrosine-like,
and humic-like
humic-likefluorescent
fluorescentDOM,DOM, respectively.
respectively. TheThe protein-like
protein-like C1 component
C1 component was reported
was reported to
to include
include extracellular
extracellular polymeric polymeric
substances substances (EPS) in sludge
(EPS) in activated activated sludge
[26–28]. The[26–28]. The protein-like
protein-like C1 component C1
component
increased inincreased in autilization
a substrate substrate utilization
phase (i.e.,phase (i.e.,phase),
growth growthbutphase), but decreased
decreased in an endogenous
in an endogenous phase
phasedeath
(i.e., (i.e., death phase).
phase). The C1 Thecomponent
C1 component waswas
thusthus considered
considered a by-productassociated
a by-product associatedwith
withmicrobial
microbial
growth. The tryptophan-like C2 component was reported to be resistant to filtration, but susceptible
to biodegradation, therefore it should be soluble and biodegradable [27,29,30]. The tyrosine-like C3
component
component was reported to be a soluble microbial product (SMP) commonly present in recycled
wastewater [27,31–33].
[27,31–33].ItItcould
couldbe
beremoved
removed by by physico-chemical
physico-chemical treatments,
treatments, such as coagulation, but not
entirely with a biological treatment system. The fulvic-like C4 component was reported to be recalcitrant
in a conventional activated
activated sludge
sludgesystem,
system,because
becauseititisisconsidered
considerednon-biodegradable
non-biodegradable[11,29,30].
[11,29,30].

(a) Component
Component 1 1
550

500

450
Em. (nm)

400

350

300

250 300 350 400 450 500


growth. The tryptophan-like C2 component was reported to be resistant to filtration, but susceptible
to biodegradation, therefore it should be soluble and biodegradable [27,29,30]. The tyrosine-like C3
component was reported to be a soluble microbial product (SMP) commonly present in recycled
wastewater [27,31–33]. It could be removed by physico-chemical treatments, such as coagulation, but not
entirely with a biological treatment system. The fulvic-like C4 component was reported to be recalcitrant
Water 2017, 9, 409 7 of 12
in a conventional activated sludge system, because it is considered non-biodegradable [11,29,30].

(a) Component
Component 1 1
550

500

450
Em. (nm)

400

350

300

250
Water 2017, 9, 409 300 350 400 450 500 7 of 11
Ex. (nm)

Figure4.4.Typical
Figure Typicalexcitation–emission
excitation–emission matrices
matrices (EEM)
(EEM) for
for the
thewastewater
wastewatersamples.
samples.(a)(a)
protein-like C1
protein-like
component;
C1 component; (b)(b)
tryptophan-like C2C2
tryptophan-like component;
component; (c)(c)
tyrosine-like C3C3
tyrosine-like component;
component; (d)(d)
fulvic-like C4
fulvic-like
component.
C4 component.

Table2.2.Characteristics
Table Characteristicsof of
thethe fluorescence
fluorescence excitation–emission
excitation–emission matrices
matrices (FEEM)
(FEEM) peakspeaks instudy,
in this this study,
and
and commonly observed FEEM peaks from previous studies. Values in brackets represent
commonly observed FEEM peaks from previous studies. Values in brackets represent secondary secondary
peaks.
peaks.
This Study Previous Study
This Study Previous Study
Comp.
Comp. /λexem/λem
λexλ λex
λex/λ/λ
em
em
Substance
Substance Reference
Reference
230/350
230/350 Protein-like
Protein-like Shen et al.et(2012)
Shen [27] [27]
al. (2012)
C1 C1 230/345
230/345 280/340
280/340 Protein-like
Protein-like Ni et al. (2009) [26]
Ni et al. (2009) [26]
250–280/<380 Protein-like Fan et al. (2014) [28]
250–280/<380 Protein-like Fan et al. (2014) [28]
220(280)/350
220(280)/350 Tryptophan-like, SMP
Tryptophan-like, SMP Yu et
Yual.et(2013) [29] [29]
al. (2013)
220(275)/355
C2 C2 220(275)/355 275(240)/346
275(240)/346 Tryptophan-like
Tryptophan-like Cohen et al. (2014)
Cohen et al. (2014)[30] [30]
220(275)/343 Tryptophan-like Shen et al. (2012) [27]
220(275)/343 Tryptophan-like Shen et al. (2012) [27]
270/300
270/300 Tyrosine-like
Tyrosine-like Murphy
Murphy et al.et(2011) [31] [31]
al. (2011)
279/315 Protein-like Shen et al. (2012) [27]
C3 275(220)/320 279/315 Protein-like Shen et al. (2012) [27]
C3 275(220)/320 280(230)/310 Tyrosine-like Li et al. (2014) [32]
280(230)/310
280/320 Tyrosine-like
Phenol-like, protein-like Lial.
Ou et et (2014)
al. (2014)
[33][32]
280/320 Phenol-like, protein-like Ou et al. (2014) [33]
230–245/425–430 Fulvic-like Yu et al. (2013) [29]
230–245/425–430 Fulvic-like Yu et al. (2013) [29]
C4 243/430 270(350)/432 Humic-like Cohen et al. (2014) [30]
C4 243/430 270(350)/432
230–275/400–520 Humic-like
Fulvic-like, Lignins Cohen et (2016)
Carstea et al. al. (2014)
[11] [30]
230–275/400–520 Fulvic-like, Lignins Carstea et al. (2016) [11]

Figure
Figure5a–c
5a–c illustrate
illustrate the relative fractions
the relative fractions ofofthe
theC1,
C1,C2,
C2,C3,C3,and
and
C4C4 components
components in the
in the JS,
JS, DS,
DS, and HP wastewaters, respectively. The blak bars indicate the relative fractions
and HP wastewaters, respectively. The blak bars indicate the relative fractions of the influent of the influent
wastewater,
wastewater,whereas
whereasthe thered
redbars
barsshow
showthe
thefractions
fractionsofofthe
thetreated
treatedwastewater
wastewaterbased
basedon onthe
the24-h
24-h
biodegradation
biodegradation test. The dominant component in the JS influent wastewater was found tobe
test. The dominant component in the JS influent wastewater was found to bethe
the
tryptophan-like C2 component, which had a relative fraction of 75% (Figure 5a).
tryptophan-like C2 component, which had a relative fraction of 75% (Figure 5a). The dominant The dominant
components
componentsininthe
theDSDSand
andHP HPinfluent
influentwastewaters
wastewaterswere werethetheprotein-like
protein-likeC1C1and
andtyrosine-like
tyrosine-likeC3 C3
components (Figure 5b,c). The HP influent wastewaters also contained the tryptophan-like C2 and
the fulvic-like C4 components, which had relative fractions of 8% and 15%, respectively (Figure 5c).
The changes from the black bars to the red bars indicate the compositional changes of the
wastewater DOM in biodegradation (Figure 5). The dominant tryptophan-like C2 component in the
JS wastewater decreased substantially from 75% to 31% in the 24-h biodegradation test, whereas the
Water 2017, 9, 409 8 of 11

[11]. Overall, the JS wastewater contained a large amount of biodegradable components (i.e., the
tryptophan-like C2 component) and exhibited an apparent compositional change of wastewater organic
Water 2017, 9, 409 8 of 12
matter during the biodegradation process, whereas the DS and HP wastewaters contained mostly non-
biodegradable components. Thus, the results from FEEM-PARAFAC also supported the findings
from the COD
components fractionation
(Figure 5b,c). Thetests, in that the
HP influent JS wastewater
wastewaters consistedthe
also contained mostly of BDCOD,C2
tryptophan-like butand
thethe
DS
and HP wastewaters
fulvic-like C4 components,consisted
whichmostly of NBDSCOD.
had relative fractions of 8% and 15%, respectively (Figure 5c).

(a) JS WWTP (b) DS WWTP


1.0 1.0
Raw Wastewater Raw Wastewater
After 24hrs Degradation After 24hrs Degradation
0.8 0.8
Relative Proportion

Relative Proportion
0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
C1 C2 C3 C4 C1 C2 C3 C4

(c) HP WWTP
1.0
Raw Wastewater
After 24hrs Degradation
0.8
Relative Proportion

0.6

0.4

0.2

0.0
C1 C2 C3 C4

Figure5.5. Relative
Figure Relative fractions
fractions of
of the
the protein-like
protein-like (C1),
(C1),tryptophan-like
tryptophan-like (C2),
(C2), tyrosine-like
tyrosine-like (C3),
(C3),and
and
fulvic-like (C4) components of the wastewater dissolved organic matter in (a) JS; (b) DS; and
fulvic-like (C4) components of the wastewater dissolved organic matter in (a) JS; (b) DS; and (c) HP (c) HP
WWTPs.
WWTPs.The Theblack and and
black red bars
redindicate the relative
bars indicate thefractions
relativebefore and after
fractions the 24-h
before and biodegradation
after the 24-h
test, respectively.
biodegradation test, respectively.

3.3. Fate
The of Wastewater
changes fromOrganic Matter
the black in to
bars a Biological WWTP
the red bars indicate the compositional changes of the
wastewater DOM in biodegradation (Figure 5). The dominant tryptophan-like C2 component in the JS
The box plots in Figure 6a illustrate the statistical analysis of the effluent COD concentrations,
wastewater decreased substantially from 75% to 31% in the 24-h biodegradation test, whereas the C1,
which had been monitored from the discharge of the WWTPs’ biological treatment process over the
C3, and C4 components increased (Figure 5a). These results indicate that only the C2 component is
last three years (from 2013 to 2015). The average effluent COD concentrations of the DS and HP
biodegradable, but that the other components are non-biodegradable, and are produced by microbial
WWTPs were 21.0 and 25.5 mg/L, respectively, which is much higher than the values for the JS
metabolism (i.e., biodegradation). The dominant protein-like C1 and tyrosine-like C3 components
WWTP (7.5 mg/L). In addition, the difference in the effluent COD concentrations between the control
in the DS and HP wastewater exhibited little change in biodegradation, and were thus characterized
(i.e., the JS WWTP) and experimental systems (i.e., the DS and HP WWTP) was statistically
as non-biodegradable (Figure 5b,c). In the authors’ opinion, aromatic compounds discharged from
significant. Indeed, industrial discharge with a substantial amount of NBDSCOD increased the
dyeing and paper mill factories might be the major source of the C1 and C3 components [11,28].
effluent COD concentrations of the biological treatment process. The box plots of the normalized
The fulvic-like C4 component, which was evident in the HP wastewater at a relative fraction of
COD removal efficiency (Figure 6b) also illustrate the apparent differences between the control and
15% (Figure 5c), might be caused by lignins and lignin derivatives discharged from the paper mill
experimental systems. The averages of the normalized COD removal efficiencies were 0.85, 0.69, and
factories [11]. Overall, the JS wastewater contained a large amount of biodegradable components
0.64 for the JS, DS, and HP WWTPs, respectively, indicating that industrial discharge with a
(i.e., the tryptophan-like C2 component) and exhibited an apparent compositional change of wastewater
substantial amount of NBDSCOD decreased the COD removal efficiency of the biological treatment
organic matter during the biodegradation process, whereas the DS and HP wastewaters contained
mostly non-biodegradable components. Thus, the results from FEEM-PARAFAC also supported the
Water 2017, 9, 409 9 of 12

findings from the COD fractionation tests, in that the JS wastewater consisted mostly of BDCOD,
but the DS and HP wastewaters consisted mostly of NBDSCOD.

3.3. Fate of Wastewater Organic Matter in a Biological WWTP


The box plots in Figure 6a illustrate the statistical analysis of the effluent COD concentrations,
which had been monitored from the discharge of the WWTPs’ biological treatment process over the
last three years (from 2013 to 2015). The average effluent COD concentrations of the DS and HP
WWTPs were 21.0 and 25.5 mg/L, respectively, which is much higher than the values for the JS
WWTP (7.5 mg/L). In addition, the difference in the effluent COD concentrations between the control
(i.e., the JS WWTP) and experimental systems (i.e., the DS and HP WWTP) was statistically significant.
Indeed, industrial discharge with a substantial amount of NBDSCOD increased the effluent COD
concentrations of the biological treatment process. The box plots of the normalized COD removal
efficiency (Figure 6b) also illustrate the apparent differences between the control and experimental
systems.
Water 2017,The averages of the normalized COD removal efficiencies were 0.85, 0.69, and 0.64 for9 the
9, 409 of 11
JS, DS, and HP WWTPs, respectively, indicating that industrial discharge with a substantial amount
of NBDSCOD
process. We thus decreased the that,
concluded CODbased
removal efficiency
on our of the biological
determination treatment
of the effluent COD process. We thus
concentration and
concluded that, based
the COD removal on our determination
efficiency, of the effluent
industrial discharge COD concentration
with a substantial amount and the COD removal
of NBDSCOD affected
efficiency,
the fate ofindustrial
wastewaterdischarge
organicwith a substantial
matter in a WWTP.amount of NBDSCOD affected the fate of wastewater
organic matter in a WWTP.

(a) Effluent COD Concentration (b) COD Removal Efficiency


1.0

30 0.9
(CODinf - CODeff ) / CODinf

0.8
CODeff (mg/L)

20
0.7

0.6
10

0.5

0 0.4
JS WWTP DS WWTP HP WWTP JS WWTP DS WWTP HP WWTP

Figure 6. Box plots of (a) the effluent COD concentrations and (b) the normalized COD removal
Figure 6. Box plots of (a) the effluent COD concentrations and (b) the normalized COD removal
efficiency of the biological treatment processes of the JS, DS, and HP WWTPs. The WWTPs’ monitoring
efficiency of the biological treatment processes of the JS, DS, and HP WWTPs. The WWTPs’
data from recent years (2013–2015) were used for the statistical analysis.
monitoring data from recent years (2013–2015) were used for the statistical analysis.

Wastewater
Wastewaterfromfromdyeing
dyeingand andpaper
paper mill factories
mill has
factories been
has beenreported
reportedto contain a large
to contain amount
a large amountof
non-biodegradable
of non-biodegradable organic
organiccompounds.
compounds.OrganicOrganicdyes
dyes with aromatic ring
with aromatic ringstructures,
structures,lignin
ligninand
and its
its derivatives,
derivatives, andand chlorinated
chlorinated organic
organic compounds,
compounds, are typical
are typical refractory
refractory organic organic compounds,
compounds, resistant
resistant to biodegradation
to biodegradation [4,5,13]. However,
[4,5,13]. However, quantification
quantification and characterization
and characterization of all
of all of the of the
individual
individual organic compounds
organic compounds are practicallyareimpossible
practicallywith
impossible withanalytical
any present any present analytical
techniques. techniques.
Most previous
Most previous studies only measured a specific group of organic compounds
studies only measured a specific group of organic compounds and monitored the ratio of BOD/COD and monitored the
ratio of BOD/COD as a relative index of biodegradability [34,35]. Thus, the COD
as a relative index of biodegradability [34,35]. Thus, the COD fractionation test was applied in this fractionation test
was
studyapplied in this NBDSCOD,
to quantify study to quantify
as an NBDSCOD,
actual amountas anof actual amount of nonbiodegradable
nonbiodegradable organic compounds. organic
The
compounds. The FEEM-PARAFAC technique was applied to classify nonbiodegradable
FEEM-PARAFAC technique was applied to classify nonbiodegradable organic compounds, based on organic
compounds,
the fluorescentbased on the fluorescent
characteristics characteristics
of the compounds. of thefractionation
The COD compounds.test Theand
CODthefractionation
FEEM-PARAFAC test
and the FEEM-PARAFAC
analysis analysis
could generate reliable couldsupporting
results, generate reliable results,
the system supporting
responses of a the systemWWTP
biological responses(see
of a biological WWTP (see Figure 6), so they have been proven straightforward
Figure 6), so they have been proven straightforward and reliable for quantifying and characterizing and reliable for
quantifying
wastewaterand characterizing
organic matter. wastewater organic matter.

4. Conclusions
This study elucidated how industrial discharge with a substantial amount of NBDSCOD affected
the characteristics and biodegradability of wastewater organic matter and their fate in a biological
WWTP, applying COD fractionation testing, fluorescence spectroscopy, and statistical analysis of the
WWTPs’ monitoring data. The findings are summarized below.
Water 2017, 9, 409 10 of 12

4. Conclusions
This study elucidated how industrial discharge with a substantial amount of NBDSCOD affected
the characteristics and biodegradability of wastewater organic matter and their fate in a biological
WWTP, applying COD fractionation testing, fluorescence spectroscopy, and statistical analysis of the
WWTPs’ monitoring data. The findings are summarized below.

(1) The COD fractionation tests could quantify an integrated index of the non-biodegradable soluble
organic matter (i.e., NBDSCOD), which is abundant in industrial discharges.
(2) FEEM-PARAFAC revealed that domestic wastewater contained biodegradable tryptophan-like
components, whereas the industrial discharge contained larger amounts of the non-biodegradable
protein-, tyrosine-, and fulvic-like components.
(3) NBDSCOD contained in industrial discharge cannot be treated effectively in a conventional
biological treatment process, and hence, escaped treatment.

In short, industrial discharge with a substantial amount of NBDSCOD was found to decrease
biodegradability, affecting the fate of wastewater organic matter in a biological WWTP. Amendments to
water quality standards, especially with regard to refractory NBDSCOD, might be required to enforce
appropriate treatment methods for industrial discharge containing substantial amounts of NBDSCOD.
Further application of COD fractionation and fluorescence spectroscopy to various wastewaters will
help scientists and engineers to better design and operate a biological WWTP, by understanding the
fate of the wastewater organic matter.

Acknowledgments: This work was supported by the 2015 DEGEC Research Funding Program and the Basic
Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of
Education (No. 2014R1A1A2055622).
Author Contributions: Byung Joon Lee, Jin Hur and Tae-U Lee conceived and designed the experiments;
Jae-In Kim, Seung-Ryong Baek and Cheol-Joon Park performed the experiments; Jeong-Woo Choi, Yun-Young Choi
and Byung Joon Lee analyzed the results and wrote the paper.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Yu, S.J.; Park, S.M.; Kwon, O.S.; Park, S.J.; Yeom, I.T. Improvement on Sewerage Effluent Standard of Public
Sewerage Treatment Plants. J. Korean Soc. Water Environ. 2013, 29, 276–287. (In Korean)
2. NIER. Study on Appropriate Treatment & Management of the Public Sewage Treatment Works Entering the Industrial
Wastewater; Ministry of Environment: Seoul, Korea, 2011. (In Korean)
3. NARS. Improvement Plans for the Current Industrial Effluent Guidlines; National Assembly Research Service:
Seoul, Korea, 2015. (In Korean)
4. Carmen, Z.; Daniela, S. Textile organic dyes—Characteristics, polluting effects and separation/elimination
procedures from industrial effluents—A critical overview. In Organic Pollutants Ten Years after the Stockholm
Convention—Environmental and Analytical Update; InTech Euro: Rijeka, Croatia, 2012; pp. 55–85.
5. Hubbe, M.A.; Metts, J.R.; Hermosilla, D.; Blanco, A.; Yerushalmi, L.; Haghighat, F.; Lindholm-Lehto, P.;
Khodaparast, Z.; Kamali, M.; Elliott, A. Pulp and paper effluent. Bioresouces 2016, 11, 1–139.
6. Wentzel, M.C.; Mbewe, A.; Lakay, M.T.; Ekama, G.A. Batch test for characterisation of the carbonaceous
materials in municipal wastewaters. Water SA 1999, 25, 327–336.
7. Henze, M.; van Loosdrecht, M.C.; Ekama, G.A.; Brdjandnovic, D. Biological Wastewater Treatment—Principles,
Modeling and Design; IWA Publishing: London, UK, 2008.
8. Takahashi, N.; Kumagai, T. Removal of dissolved organic carbon and color from dyeing wastewater by
pre-ozonation and subsequent biological treatment. Ozone Sci. Eng. 2006, 28, 199–205. [CrossRef]
9. Bae, W.; Won, H.; Hwang, B.; Toledo, R.A.; Chung, J.W.; Kwon, K.; Shim, H. Characterization of refractory
matters in dyeing wastewater during a full-scale Fenton process following pure-oxygen activated sludge
treatment. J. Hazard. Mater. 2015, 287, 421–428. [CrossRef] [PubMed]
Water 2017, 9, 409 11 of 12

10. Lindholm-Lehto, P.C.; Knuutinen, J.S.; Ahkola, H.S.J.; Herve, S.H. Refractory organic pollutants and toxicity
in pulp and paper mill wastewaters. Environ. Sci. Pollut. Res. 2015, 22, 6473–6499. [CrossRef] [PubMed]
11. Carstea, F.M.; Bridgeman, J.; Baker, A.; Reynolds, D.M. Fluorescence spectroscopy for wastewater monitoring:
A review. Water Res. 2016, 95, 205–219. [CrossRef] [PubMed]
12. Plosz, B.G.; Vogelsang, C.; Macrae, K.; Heiaas, H.; Lopez, A.; Liltved, H.; Langford, K. The BIOZO process—A
biofilm system combined with ozonation: Occurrence of xenobiotic organic micro-pollutants in and removal
of polycyclic aromatic hydrocarbons and nitrogen from landfill leachate. Water Sci. Technol. 2010, 61,
3188–3197. [CrossRef] [PubMed]
13. Ince, B.K.; Cetecioglu, Z.; Ince, O. Pollution prevention in the pulp and paper industries. In Environmental
Management in Practice; InTech: Rijeka, Croatia, 2011.
14. Wentzel, M.C.; Mbewe, A.; Ekama, G.A. Batch test for measurement of readily biodegradable COD and
active organism concentrations in municipal waste waters. Water SA 1995, 21, 118–124.
15. Yang, L.; Han, D.H.; Lee, B.M.; Hur, J. Characterizing treated wastewaters of different industries using
clustered fluorescence EEM–PARAFAC and FT-IR spectroscopy: Implications for downstream impact and
source identification. Chemosphere 2015, 127, 222–228. [CrossRef] [PubMed]
16. Ekama, G.A.; Dold, P.A.; Marais, G.v.R. Procedures for determining influent COD fractions and the maximum
specific growth rate of heterotrophs in activated sludge. Water Sci. Technol. 1986, 18, 91–114.
17. Grady, C.P.L.; Daigger, G.T.; Love, N.G.; Filipe, C.D.M. Biological Wastewater Treatment, 3rd ed.; CRC Press:
Boca Raton, FL, USA, 2011.
18. Orhon, D.; Cokgor, U.E. COD Fractionation in Wastewater Characterization—The State of the Art. J. Chem.
Technol. Biotechnol. 1997, 68, 283–293. [CrossRef]
19. Hu, Z.; Chanadran, K.; Smets, B.F.; Grasso, D. Evaluation of a rapid physical-chemical method for the
determination of extant soluble COD. Water Res. 2002, 36, 617–624. [CrossRef]
20. Mamais, D.; Jenkins, D.; Pitt, P. A rapid physical-chemical method for the determination of readily
biodegradable soluble COD in municipal wastewater. Water Res. 1993, 27, 195–197. [CrossRef]
21. Hur, J.; Cho, J. Prediction of BOD, COD, and total nitrogen concentrations in a typical urban river using
a fluorescence excitation–emission matrix with PARAFAC and UV absorption indices. Sensors 2012, 12,
972–986. [CrossRef] [PubMed]
22. Stedmon, C.A.; Bro, R. Characterizing dissolved organic matter fluorescence with parallel factor analysis:
A tutorial. Limnol. Oceanogr. Methods 2008, 6, 572–579. [CrossRef]
23. Choi, E.; Rhu, D.; Yun, Z.; Lee, E. Temperature effects on biological nutrient removal system with weak
municipal wastewater. Water Sci. Technol. 1998, 37, 219–226. [CrossRef]
24. Mikola, A.M.K.; Vahala, R.; Rautiainen, J.A. Factors affecting the quality of the plant influent and its
suitability for prefermentation and the biological nutrient removal process. J. Environ. Eng. 2011, 137,
1185–1192. [CrossRef]
25. EnviroSim Associates. General Activated Dludge-Digestion Model (General ASDM); EnviroSim Associates:
Hamilton, ON, Canada, 2007.
26. Ni, B.J.; Fang, F.; Xie, W.M.; Sun, M.; Sheng, G.P.; Li, W.H.; Yu, H.Q. Characterization of extracellular
polymeric substances produced by mixed microorganisms in activated sludge with gel-permeating
chromatography, excitation–emission matrix fluorescence spectroscopy measurement and kinetic modeling.
Water Res. 2009, 43, 1350–1358. [CrossRef] [PubMed]
27. Shen, Y.X.; Xiao, K.; Liang, P.; Sun, J.Y.; Sai, S.J.; Huang, X. Characterization of soluble microbial products in
10 large-scale membrane bioreactors for municipal wastewater treatment in China. J. Membr. Sci. 2012, 415,
336–345. [CrossRef]
28. Fan, J.; Li, H.; Shuang, C.; Li, W.; Li, A. Dissolved organic matter removal using magnetic anion exchange
resin treatment on biological effluent of textile dyeing wastewater. J. Environ. Sci. 2014, 26, 1567–1574.
[CrossRef] [PubMed]
29. Yu, H.B.; Song, Y.H.; Tu, X.; Du, E.D.; Liu, R.X.; Peng, J.F. Assessing removal efficiency of dissolved organic
matter in wastewater treatment using fluorescence excitation emission matrices with parallel factor analysis
and second derivative synchronous fluorescence. Bioresour. Technol. 2013, 144, 595–601. [CrossRef] [PubMed]
30. Cohen, E.; Levy, G.J.; Borisover, M. Fluorescent components of organic matter in wastewater: Efficacy and
selectivity of the water treatment. Water Res. 2014, 55, 323–334. [CrossRef] [PubMed]
Water 2017, 9, 409 12 of 12

31. Murphy, K.R.; Hambly, A.; Singh, S.; Henderson, R.K.; Baker, A.; Stueyz, R.; Khan, S.J. Organic matter
fluorescence in municipal water recycling schemes: Toward a unified PARAFAC model. Environ. Sci. Technol.
2011, 45, 2909–2916. [CrossRef] [PubMed]
32. Li, W.T.; Chen, S.Y.; Xu, Z.X.; Li, Y.; Shuang, C.D.; Li, A.M. Characterization of dissolved
organic matter in municipal wastewater using fluorescence PARAFAC analysis and chromatography
multi-excitation/emission scan: A comparative study. Environ. Sci. Technol. 2014, 48, 2603–2609. [CrossRef]
[PubMed]
33. Ou, H.S.; Wei, C.H.; Mo, C.H.; Wu, H.Z.; Ren, Y.; Feng, C.H. Novel insights into anoxic/aerobic1/aerobic2
biological fluidized-bed system for coke wastewater treatment by fluorescence excitation–emission matrix
spectra coupled with parallel factor analysis. Chemosphere 2014, 113, 158–164. [CrossRef] [PubMed]
34. Kreetachat, T.; Damrongsri, M.; Punsuwon, V.; Vaithanomsat, P.; Chiemchaisri, C. Effects of ozonation
process on lignin-derived compounds in pulp and paper mill effluents. J. Hazard. Mater. 2007, 142, 250–257.
[CrossRef] [PubMed]
35. Ghaly, M.Y.; Jamil, T.S.; EL-Seesy, I.E.; Souaya, E.R.; Nasr, R.A. Treatment of highly polluted paper mill
wastewater by lolar photocatalytic oxidation with synthesized nano TiO2 . Chem. Eng. J. 2011, 168, 446–454.
[CrossRef]

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