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

net/publication/348936093

Fluorescent whitening agents in commercial detergent: A potential marker of

emerging anthropogenic pollution in freshwater of Bangladesh

Article · January 2021

CITATIONS READS

3 612

3 authors, including:

Nahin Mostofa Shafi Mohammad Tareq

Jahangirnagar University Jahangirnagar University
14 PUBLICATIONS   97 CITATIONS    118 PUBLICATIONS   1,760 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Water Quality Monitoring and Assessment View project

Microplastic pollution and health risk View project

All content following this page was uploaded by Shafi Mohammad Tareq on 02 March 2021.

The user has requested enhancement of the downloaded file.

 Environmental Nanotechnology, Monitoring & Management 15 (2021) 100419

Contents lists available at ScienceDirect

Environmental Nanotechnology, Monitoring & Management

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

Fluorescent whitening agents in commercial detergent: A potential marker

of emerging anthropogenic pollution in freshwater of Bangladesh
Nahin Mostofa Niloy, Md. Morshedul Haque, Shafi M. Tareq *
Hydrobiogeochemistry and Pollution Control Laboratory, Department of Environmental Sciences, Jahangirnagar University, Dhaka, 1342, Bangladesh

A R T I C L E I N F O A B S T R A C T

Keywords: Fluorescence whitening agents (FWAs), popular optical brighteners, are extensively used in commercial de­
FWA tergents to increase brightening of washed products. This study characterizes FWA in commercial detergents and
3DEEM quantifies its residue in sewerage linked lakes and the Ganges River water using three dimensional excitation
PARAFAC
emission matrix (3DEEM) fluorescence and Parallel Factor (PARAFAC) analysis. Concentrations of FWA in
Health risk
Water pollution
commercial detergents were varied between 0.57–12.84 mg/g, which was 0.23–5.14 times higher than the usage
guideline of FWA in commercial and household detergents. Most of the detergents used DSBP, but some low
priced detergents might not be used any FWA. Photodecay method was used for FWA analysis to circumvent the
interferences of natural organic matter (NOM) and it showed about 12–23 times and 2–8 times higher values
than the detection limit in lakes and the Ganges River water, respectively. DSBP (4,4’-bis(2-sulfostyryl) biphenyl
disodium salt) concentration was ranged between 4.7–10.42 μg/L and 0.4995–2.59 μg/L in lakes and the Ganges
River water, respectively and DAS1 (Disodium 4,4’-bis[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)amino]stil­
bene-2,2’-disulfonate) concentration was insufficient to detect due to its rapid signal reduction under photo-
irradiation and also interferences of NOM during fluorescence measurement. FWA concentration in the
Ganges River was higher in the monsoon than pre monsoon and post monsoon. Seasonal variability of FWAs in
the Ganges River might be related to high terrestrial derived input of organic matter into the river channel during
monsoon. This study confirmed the potential ability of 3DEEM–PARAFAC to monitor FWA in freshwater as an
anthropogenic molecular marker.

1. Introduction in detergent products. Firstly, in contrast to other detergent compo­

Detergent is a water soluble surfactant or a mixture of surfactants
and other minor chemicals which behaves as a cleaning agent in dilute
condition. Laundry detergents have become the most popular product
now a days in the forms of liquid, powder and spray at industries,
households and other sectors in all over the world. According to esti­
mation done by China Cleaning Industry Association (CCIA) (2011),
detergent consumption per person-year in the world was 11.9 kg and the
gross volume was approximately 78.5 million tons. In Bangladesh,
detergent is also used as a popular and commonly used cleaning product
(Afreen, 2011). Among the all constitutional components of detergent,
surfactants and phosphorous were considered as two harmful substances
previously (Qv and Jiang, 2013; Jagessar and Sooknanan, 2011). Be­
sides these two chemicals, another component named Fluorescent
Whitening Agent (FWA) could also be considered as harmful as it has
more negative impacts on environment nevertheless of minor usage of it
nents, FWAs are known to be very poorly degradable (Salas et al., 2019).
Secondly, FWAs are not carcinogenic itself, but when they occur
together with ultraviolet radiation at certain wavelengths, a pronounced
carcinogenic effect may result due to photochemical transformation
(Falk and Bingham, 1973).
Optical brighteners (Coumarin derivative and Diaminostilbene
disulfonate derivatives in dimethyl sulfoxide) together with strong
irradiation (70 μW/cm2) with ultraviolet light (60 % of energy at 254
nm) can increase the incidence of tumors, mostly squamous cell carci­
nomas, in skin painting studies in mice (Falk and Bingham, 1973). With
the presence of UV radiation, structure of FWA changes and turns into a
format to cause possible carcinogenic effects in human body as well as
other living species. Aquatic species (fishes, bacteria, yeasts) could be
the sufferer due to toxicity mainly caused by large scale of detergent
usage and poor degradation and persistent nature of FWA in surface
water. Possible other health problems could be eczema, allergies, skin

* Corresponding author.
E-mail addresses: smtareq@yahoo.com, smtareq@juniv.edu (S.M. Tareq).

https://doi.org/10.1016/j.enmm.2020.100419
Received 17 September 2020; Received in revised form 25 November 2020; Accepted 17 December 2020
Available online 28 December 2020
2215-1532/© 2020 Elsevier B.V. All rights reserved.
N.M. Niloy et al.
infections and in some cases, cancer as detergent may contain carcino­
gens (Yuan et al., 2014).
Recently, some stilbene-type FWAs have been used as persistent
water soluble molecular markers (Yamaji et al., 2010). Most anthropo­
genic markers are hydrophobic and are useful for tracking sewage par­
ticles and pollutants. Hydrophilic markers (e.g. linear
alkylbenzenesulfonates, urobilin) are not persistent and are difficult to
exploit them in aquatic environment studies (Hayashi et al., 2002). But,
despite of being hydrophilic, FWAs are persistent in nature and couldn’t
completely be removed from aquatic environments (Salas et al., 2019).
Less effective removal during sewage treatment and poor biodegrada­
tion character of FWAs suggested that they could be used as molecular
markers to detect sewage inputs in aquatic zones and to trace dilution
and movement of sewage effluents in aquatic environments such as lakes
and rivers. The freshwater monitoring of FWAs described that both
DAS1 (Disodium 4,4′ -bis[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)
amino]stilbene-2,2′ -disulfonate) and DSBP(4,4′ -bis(2-sulfostyryl)
biphenyl disodium salt) are widely distributed in the riverine environ­
ments (Hayashi et al., 2002). The contribution of photo-degradation to
change the DSBP/DAS1 ratio in the aquatic environment is minimal
because both DSBP and DAS1 are thought to be persistent (Hayashi
et al., 2002). These less photo and microbial degradation favor the
application of FWAs as anthropogenic molecular markers.
Detergents production was comparatively low in Bangladesh, but
recently their production rate increased quickly due to rapid industrial
development and urbanization. Average soap and detergent production
were about 3996.67, 3975.42, 4680.67 and 5604.08 metric ton in the
years of 1995, 2000, 2005 and 2010 respectively in Bangladesh (BBS,
1994-2019). But, from the year 2015, soap and detergent production
started to increase rapidly and was in the amount of 16036.58 metric
tons in the year of 2019 in Bangladesh (BBS, 1994-2019). 3DEEM and
PARAFAC models could detect FWA in surface water from the fluores­
cence analysis even in the very low concentration ranges. Moreover,
these techniques are easy and less expensive and could exploit effec­
tively in the FWA identification and quantification. FWAs have already
been identified in freshwater ecosystem of Japan, for example, con­
centrations of DSBP and DAS1 were between of 30.5–314 ng l− 1 and
10.6–243 ng l− 1 respectively from the year of 2001–2005 in the Yasu
River (Hayakawa et al., 2007).
Low degradation of FWA mainly allows it to sustain in freshwater for
a long time and may act as potential indicator of anthropogenic pollu­
tion. Recently 3DEEM fluorescence techniques can be successfully used
for monitoring anthropogenic pollution in groundwater (Tareq et al.,
2013; Nowicki et al., 2019) and freshwater including lake and river
(Hayakawa et al., 2007; Zhi et al., 2015). Fluorescence techniques can
analyze water samples directly without any pre-concentration and pre­
treatment and much faster, economical and easier method. Dickerson
et al. (2007) already demonstrated the successful application of the
fluorescence techniques for identifying human origin pollution in nat­
ural water. 3DEEM in combination with PARAFAC analysis could easily
decompose FWA spectrum and could even also exploit in the observa­
tion of degradation of FWA in the environment. Typical conventional
methods such as high performance liquid chromatography (HPLC) could
determine FWAs with great sensitivity but it time consuming and need
pre-processing of the sample and expensive technical supports. From
this point of view, 3DEEM and PARAFAC could be a potential technol­
ogy for determining FWAs in the freshwater.
Since FWAs have persistent nature in water and sediments, they can
carry the evidence of traces of detergent residue in environment for a
long time. Detergent residues along with other anthropogenic pollutants
are directly discharged into lakes and rivers without any treatment
especially in developing countries like Bangladesh. Therefore, detergent
residues could act as potential marker or tracer of anthropogenic
pollution and required to detect. In addition, the amount of FWA mixed
in individual commercial detergent of Bangladesh was still unknown, so
it is also important to quantify. Hence, the aim of this study is to
2
Environmental Nanotechnology, Monitoring & Management 15 (2021) 100419
determine the concentration of FWAs in commercial detergent of
Bangladesh and to assess and uses of fluorometric measurement of FWAs
as a potential tool for investigating anthropogenic molecular marker in
the lake and river water of Bangladesh. We also estimated the seasonal
variability of the FWAs in the Ganges River as an indicator of the impact
of human origin pollution in large river.
2. Materials and methods
2.1. Sampling
Nine different household laundry powder detergents available in
local markets of Bangladesh were collected for analysis. Collected
detergent samples were labeled as Detergent 1, Detergent 2, Detergent 3,
Detergent 4, Detergent 5, Detergent 6, Detergent 7, Detergent 8 and
Detergent 9 for the study. Later, stock solutions of the collected powder
detergents were prepared using ultrapure Milli-Q water at concentration
1 mg/L for the fluorescence measurement. Lake water samples were
collected from four different lakes (23◦ 52′ 48.72′ ’ N, 90◦ 15′ 53.6328′ ’
E) linked to the sewerage line of four different student dormitories in
Jahangirnagar University, Dhaka. Laundry washed water along with
grey water from student dormitory come into the sewerage line regu­
larly and mixed into the connected lake. Lakes are surrounded by
vegetation and used as a dumping center of household wastewater. River
water samples were collected at monthly interval throughout a year
from the Ganges River (Hardinge Bridge point, Kushtia, Bangladesh, 24◦
03′ 57.04′′ N, 89◦ 01′ 42.85′′ E). Residential households, agricultural
lands and power plants were mainly located nearby the sampling loca­
tion. Surrounded households and industries could be the potential
sources of detergent residue in the Ganges River. Moreover, rainfall and
water discharge facilitate sewage, lakes and terrestrial runoff into the
river water. The Ganges River water is also directly used for bathing of
human as well as domestic animals and washing clothes and utensils
throughout the entire basin, where detergent products are commonly
used for bathing and washing purpose. Detergent residue can also come
into the river from the local inland navigations. Lake and river water
samples were collected in 1 L prewashed polypropylene bottles and
filtered in-situ using pre-combusted (450 ◦ C for 4 h) 0.7 μm glassfiber
filters (Whatman GF/F) immediately after sampling and preserved in
cooler box at 4 ◦ C during transport to laboratory at Department of
Environmental Sciences, Jahangirnagar University and until further
analysis.
2.2. Optical characteristics and FWA analysis
Fluorescence properties of samples were measured in Hitachi F-4600
fluorescence spectrophotometer using a 1 cm quartz cell. For three
dimensional fluorescence spectrum, excitation (Ex) and emission (Em)
scans were carried out between 225− 400 nm (5 nm interval) and
250− 500 nm (1 nm interval) wavelengths respectively. Excitation and
emission bandpass width silts were 5 nm, PMT voltage was 700 V,
response was auto and scanning speed was set at 1200 nm min− 1 in
Fluorescence Spectrophotometer during measurement. The Raman peak
of ultra-purified Milli-Q water was used as reference value to express
fluorescence intensities in Raman units.
DAS1 and DSBP (Tinopal CBS-X), two FWAs commonly used in
laundry detergents, were used as a reference for calibration curve to
quantify FWA concentration in commercial detergents and surface water
(lake and river). FWA standards and standard Suwannee River Natural
Organic Matter (NOM) from the International Humic Substances Society
(IHSS) were also used to determine detection limits of FWA and in­
terferences during fluorescence measurement in water samples (Dubber
and Gill, 2017).
N.M. Niloy et al.
2.3. PARAFAC modeling
PARAFAC (Parallel Factor) analysis was carried out to decompose
EEM spectra and prepare individual fluorescent component model in
MATLAB (v.2016a) using ‘DOMFluor v1.7’ toolbox (Stedmon and Bro,
2008). Blank data (Milli-Q water) was subtracted from the original
dataset, Raman and Rayleigh scattering were completely removed to
count exact component numbers and arbitrary unit was converted into
Raman normalized fluorescence unit (RU) to measure fluorescence in­
tensity (i.e. Fmax) of FWA in RU before using fluorescence dataset for
EEM and PARAFAC model (Stedmon and Bro, 2008; Goletz et al., 2011;
Mostofa et al., 2009). Data validation and calibration techniques such as
split-half and residual analysis were also followed to choose the optimal
number of components.
2.4. NOM interferences and detection limit of FWA
Detection limit of FWA was quantified using the built-up equation
from NOM concentration-FWA detection limit plot according to Dubber
and Gill (2017). Different NOM concentration spiked with different
amounts of FWA standards were taken under UV radiation to record
intensity reduction and form the ratio dividing % signal decrease after 1
min by % signal decrease after 10 min (ratio>0.25 were considered to
present FWA in samples). The resultant photo-decay FWA ratio was
plotted against the corresponded standard NOM concentration and an
acceptable equation was built to quantify expected FWA concentration
subject to any NOM concentration in environmental samples.
3. Results and discussions
3.1. Fluorescence characteristics
Maximum two fluorescence peak positions were identified in stan­
dard DSBP at peak A (Ex/Em = 240/434 nm) and peak W (Ex/Em =
350/430 nm) in three dimensional excitation emission matrix (3DEEM)
(Fig. 1a). But in commercial detergent brands, apart from these two peak
positions (Peak A and W), another additional peak Wuv at Ex/Em =
230/286 nm was identified in 3DEEM analysis indicating the usage of
another type of whitening agents besides DSBP (Fig. 1b). 3DEEM also
identified similar detergent like fluorescence peak positions at peak A
Fig. 1. Three dimensional Excitation Emission Matrix (3DEEM) model of (a) DSBP (b) Commercial detergents (c) Jahangirnagar University lake and (d) the Ganges
River water; intensity express in Raman Unit (RU).
3
Environmental Nanotechnology, Monitoring & Management 15 (2021) 100419
(Ex/Em = 250–255/424–430 nm) and peak W (325–335/414–426 nm)
and peak Wuv (230/292− 294 nm) in lake water samples and most of the
months in the Ganges River water indicating the presence of detergent
traces in surface water (Fig. 1c and 1d). Peak labels (A, W and Wuv) of
specific wavelength regions were named following Mostofa et al. (2010).
A comparison among emission spectra at excitation 350 nm of
standard DSBP and DAS1, standard humic acid, standard fulvic acid,
standard NOM from IHSS and commercial local detergents showed that,
DSBP and DAS1 not only have different fluorescence intensity but also
show different emission maxima at specific wavelengths and locally
available detergent mostly contain DSBP as FWA (Fig. 2). DSBP shows
emission maxima sharp at 430 nm while emission spectra in DAS1 has
maximum peak at 441 nm containing higher fluorescence intensity than
DSBP at same concentration (Fig. 2a). Standard NOM and fulvic acid
have closely similar patterned emission spectra presenting slightly flat
area between 422− 450 nm and maximum peak value at 452− 465 nm
(Fig. 2a). Spectrum of standard NOM and fulvic acid showed close as­
sociation with standard DSBP and DAS1 between 390− 440 nm indi­
cating possibility of interference during FWA measurements in natural
environmental samples. Whereas, humic acid, has comparatively lower
fluorescence intensity than NOM and fulvic acid and represent flat
emission areas between 415− 487 nm. Standard humic acid also showed
possibility of interferences in FWA estimation because of its well asso­
ciation of emission spectra with DSBP and DAS1 both (Fig. 2a). Among
commercial detergents, Detergent 1, Detergent 2, Detergent 5, Detergent
6 and Detergent 9 showed emission maximum sharp at 430 nm and had
similar fluorescence spectra with standard DSBP describing the usage of
DSBP standards as optical brighteners in these commercial detergents
(Fig. 2b). Other analyzed detergents such as Detergent 3, Detergent 4,
Detergent 7 and Detergent 8 had peak maxima at 408 nm and a wide flat
area between 421− 500 nm (Fig. 2b). Peak maxima of these four com­
mercial detergents were completely different from standard DSBP and
DAS1, which implied that, these low priced detergents don’t use luxu­
rious and costly DSBP and DAS1 brighteners in their products.
3.2. FWA concentration in commercial detergent
Since most of the commercial detergents contain DSBP, fluorescence
intensity-concentration linear calibration curves was prepared for DSBP
(slope 16.538, R2 ≥ 0.9727) to estimate concentration of FWA in
N.M. Niloy et al. Environmental Nanotechnology, Monitoring & Management 15 (2021) 100419

Fig. 2. Emission spectrum at 350 nm excitation of (a) standard DSBP (5 μg/L), standard DAS1 (0.5 μg/L), IHSS NOM (3 mg/L), standard humic acid (3 mg/L) and
standard fulvic acid (3 mg/L). (b) Standard DSBP (5 μg/L), Standard DAS1 (0.5 μg/L), Detergent 2 (300 μg/L), Detergent 8 (990 μg/L).

commercial detergents. But this calibration curve was applied only for
those five commercial detergents which used DSBP as whitening agent.
As rest four commercial detergents don’t use either DSBP or DAS1 as
FWA, so their FWA concentration couldn’t be quantified. Fig. 3 shows
that, five DSBP using commercial detergents have concentrations in the
range between 0.57–12.84 mg/g and maximum in Detergent 9 and
minimum in Detergent 1 (Fig. 3). Fluorescence intensity of standard
DSBP and DAS1 were 0.457 and 0.91 RU at concentration 5 μg/L and 0.5
μg/L respectively. Among commercial detergents, intensity was in the
range between 0.74–4.38 RU and was maximum in Detergent 9 and
minimum in Detergent 3 (Fig. 3). Standard DSBP had higher fluores­
cence intensity at peak W (Ex/Em = 350/430) (76 %) region and didn’t
show Wuv fluorophore in 3DEEM spectra (Fig. 4). Detergent 2 and
Detergent 6 had higher fluorescence intensity at peak W (Ex/Em = 350/
430) region quantifying 66 % and 59 % respectively (Fig. 4). But,
remainder detergents, Detergent 1, Detergent 3, Detergent 4, Detergent
5, Detergent 7, Detergent 8 and Detergent 9 had their higher fluores­
cence intensity at peak Wuv (Ex/Em = 225/287− 294 nm) showing in­
tensity percentage about 71 %, 94 %, 96 %, 81 %, 97 %, 99 % and 80 % Fig. 4. Fluorescence intensity of various fluorophores (A, W, Wuv) of standar
(Fig. 4). DSBP and commercial detergents.
Kramer et al. (1996) and Blanco et al. (2001) described the usage
quantity of FWA in detergents at an average concentration of about 0.15 in conventional detergent powder (0.05− 0.25 %), compact Detergent
% by weight. Home Care and Formulation Technologies (2011) powder (0.1− 0.4 %), unstructured liquid detergent (0.05− 0.4 %),
described some technical information on Tinopal CBS-X (chemical na­ structured liquid detergent (0.05− 0.15 %), anhydrous liquid detergent
ture DSBP type) on which they suggested guidelines about usage (0.1− 0.4 %), detergent bars (0.05− 0.15 %), soap bars (0.02− 0.05 %),
quantity (percentage of weight) of Tinopal CBS-X at different areas of rinse softeners (0.02− 0.05 %), boosters (0.02–1.00 %), creams
application. This suggested guideline described the use of Tinopal CBS-X (0.05− 0.15 %) and industrial detergents (0.2–1.00 %).
FWA concentration in DSBP containing five commercial detergents
described that, usage quantity of FWA varied among detergents and
were in the quantity by percentage in Detergent 1 (0.57 mg/g), Deter­
gent 2 (4.42 mg/g), Detergent 5 (3.06 mg/g), Detergent 6 (1.34 mg/g)
and Detergent 9 (12.84 mg/g) (Fig. 3). From this usage quantity, it could
be stated that, DSBP was used in these five detergents at excessively high
amounts. According to standard guidelines, if average usable amount of
FWA in detergent is considered as 0.25 % by weight, then usage FWA
quantity in Detergent 1, Detergent 2, Detergent 5, Detergent 6 and
Detergent 9 were respectively about 0.23 times, 1.77 times, 1.22 times,
0.54 times and 5.14 times higher than the maximum permissible limit.
Among the five DSBP containing detergents, Detergent 5, Detergent 6
and Detergent 9 are popular and commonly used among a wide range of
population in Bangladesh than the four low priced commercial de­
tergents without FWA. Reasons behind using more DSBP in detergents
could be to attract people at their products making more whitening
appearance in washed apparels. Popularly used detergents also
demonstrated their brightening purposes in commercial advertisements
Fig. 3. Concentration and fluorescence intensity of DSBP-like FWA in com­ and posters to compete in detergent markets despite of health risk of
mercial detergents. Red line- Flu Intensity (RU) and bar- Conc of FWA.

4
N.M. Niloy et al. Environmental Nanotechnology, Monitoring & Management 15 (2021) 100419

high FWA. Anthropogenic originated other organic and inorganic components can
also cause disturbance during FWA analysis (Hartel et al., 2007). High
3.3. PARAFAC analysis performance liquid chromatography (HPLC) faced difficulties to identify
FWA in freshwater due to unexpected organic matter interferences
PARAFAC model also identified two fluorescent components in (Hartel et al., 2007). To solve interference problem in analysis, UV
commercial detergents as like standard DSBP at peak A (Ex/Em = 245/ exposure method was exploited to distinguish between FWA and NOM
430 nm) and peak W (Ex/Em = 345/434 nm) wavelength regions substances. FWA standards have higher sensitivity and decay rapidly
(Fig. 5a, c). In addition, it also showed another fluorophore at peak Wuv than other interfering organic compounds under UV (Hartel et al., 2007;
(Ex/Em = 230/290 nm) region (Fig. 5b). Unlike commercial detergents, Cao et al., 2009). Changes in FWA concentration before and after
single fluorescent component was identified by PARAFAC model in lake photo-decay can be used as a confirmation test to describe the presence
and the Ganges river water samples. This only identified fluorescent or absence of FWA in water as fluorescing and photo-decay rate of FWA
component showed fluorophore at peak A (Ex/Em = 265/470 nm) and and NOM components are not similar under UV radiation (Hartel et al.,
peak W (Ex/Em = 355/470 nm) regions indicating the presence of 2007).
detergent FWA in lakes and river (Fig. 5d). Absence of fluorophore Wuv Expected and estimated FWA concentrations in the lake water are
in lakes and river indicated its higher sensitivity to photo-irradiation and showed in Table 1. Estimated FWA concentration ≥ detection limit can
having higher photo-decay rates. Red shifts of wavelengths of fluores­ be considered for the presence of FWA in sample with ≥97.5 % confi­
cent components in lakes and river also indicated the effects of irradi­ dence level (Dubber and Gill, 2017). Expected FWA concentration was
ation on fluorescence intensity. estimated based on the simplifying assumption that residents and/or
cleaning industries in the sampling sites either use DAS1 or DSBP con­
taining laundry detergents. Though concentration of DAS1 failed to
3.4. NOM interferences and detection limit of FWA cross the detection threshold line, but DSBP concentration was above the
detection limit in all four lakes of Jahangirnagar University and proved
PARAFAC model identified three more fluorescent dissolved organic theoretically possible for DSBP detection in surface water. Estimated
components besides detergent like component both in the studied lakes DSBP concentrations were about 12–23 times higher than the detection
and the Ganges River water. The three other identified fluorescent limit in the lake samples (Table 1). Similar DSBP and DAS1 detection
components in lakes were allochthonous fulvic acid like component (Ex/
Em = 245/390 nm and 305/386 nm) (Fig. S1a), protein like component
(Ex/Em = 230/342 nm and 375/338 nm) (Fig. S1b) and humic acid like Table 1
component (Ex/Em = 230/426 nm (Fig. S1c) (Holbrook et al., 2006; Fluorescence intensity, estimated concentrations and detection limits of FWA in
lake water. Higher estimated FWA concentrations than detection limit are
Mostofa et al., 2005a, 2010). At the Ganges River water, identified three
highlighted in bold.
fluorescent components except detergent like component were biolog­
ical or microbial originated recently produced humic acid like compo­ Sample Fluorescence intensity (RU) Estimated FWA FWA detection
concentration (μg/ limit (μg/L)
nent (Ex/Em = 255 (310)/395 nm) (Fig. S2a), terrestrial derived fulvic
L)
acid like component (Ex/Em = 275 (325)/410 (414) nm and 325/414
nm) (Fig. S2b) and tryptophan like component (Ex/Em = 280/342 nm) DSBP DAS1 DSBP DAS1
Lake 1 0.527 5.76 0.24 0.370 0.873
(Fig. S2c) (Salve et al., 2012; Yamashita and Jaffe, 2008; Murphy et al., Lake 2 0.629 6.88 0.29 0.401 0.858
2008). Natural organic materials (both humic and fulvic acid) can Lake 3 0.953 10.42 0.44 0.452 0.863
interfere during fluorescence analysis of FWA showing closest emission Lake 4 0.430 4.70 0.20 0.396 0.860
maxima with DSBP and DAS1 in surface water (Dubber and Gill, 2017).

Fig. 5. Fluorescent components of DSBP (a), commercial detergents (b and c), lakes and the Ganges River water (d) identified by PARAFAC model.

5
N.M. Niloy et al.
patterns were observed in the Ganges River water. Estimated DSBP was
also 2–8 times higher than the detection limit in most of the months in
the Ganges River and showed higher DSBP concentration in the
monsoon than pre monsoon and post monsoon (Fig. 6). Reasons behind
the higher DSBP concentration in the Ganges River during monsoon
were the high monsoon rainfall and river water discharge which washed
out large amounts of anthropogenic originated detergent residue from
terrestrial environment into the river. DAS1 was theoretically unable to
detect (detection limit > estimated DAS1) throughout the entire year in
the Ganges River. Higher sensitivity and photo-decay rate (>75 % for
DAS1 and 15 % for DSBP signal decrease after 1 min UV exposure) of
DAS1 than DSBP would be the reason for below detection limit con­
centrations of DAS1 in surface water. In addition, high NOM concen­
tration often makes it difficult to detect DAS1 in the surface water
(Dubber and Gill, 2017) due to closer peak position of DAS1 and NOM
(Fig. 2a).
3.5. Fate of FWA in freshwater: A potential marker of anthropogenic
pollution
Fluorescence intensity of FWA in lake waters was in the range be­
tween 0.43− 0.95 RU (mean = 0.64 RU, σ = 0.23 RU) showing maximum
intensity in Lake 3 and minimum in Lake 4 (Table 1). Even though DAS1
was not detected in studied commercial powder detergents, but it may
be present in liquid household and industrial detergents (Dubber and
Gill, 2017). Concentration of DAS1 was also estimated besides DSBP in
the lake. Concentration of DSBP and DAS1 varied between 4.7–10.42
μg/L (mean = 6.94 μg/L, σ = 2.483 μg/L) and 0.2− 0.44 μg/L (mean =
0.29 μg/L, σ = 0.11 μg/L) respectively in the lakes water (Table 1).Water
in Lake 3 is not stagnant like other three lakes and receives huge amount
of sewage water from food courts inside the university campus besides
nearby linked student dormitory. Sample from Lake 3 was collected
from non-point sewage input pathways, nonetheless higher fluorescence
intensity indicated the wide-spread strong distribution of FWA in water.
Samples from other three lakes were collected from comparatively close
to point sources of sewage inputs. But, in these three lakes, autochtho­
nous natural DOM (fulvic acid and humic acid) production and
allochthonous organic inputs were relatively high. High NOM concen­
tration in lakes water might be interfered the estimation of FWA which
ultimately also quench the FWA concentration. Moreover, high NOM
concentration in these three lakes (Lake 1, Lake 2 and Lake 4) also
increased the FWA detection limit and made it difficult to detect DAS1.
Detergent residue from student dormitories sewage system mixed to the
lake water directly without any wastewater treatment and natural
Fig. 6. Variability of DSBP-like FWA concentrations in the Ganges River and
rainfall at the sampling. High concentration of FWA in April might be related to
flash flood at early; line-Rainfall (mm) and bar-Conc. of FWA and also correct
capital O in COncentaration.
6
Environmental Nanotechnology, Monitoring & Management 15 (2021) 100419
dependable removal processes such as photo-irradiation, biodegrada­
tion and sorption not effectively worked. Sedimentation and adsorption
couldn’t completely remove FWA from aquatic body (Hayashi et al.,
2002) and remain detectable as an anthropogenic molecular marker in
natural system. Concentrations of DAS1 and DSBP were found between
0.0015− 0.0035 μg/L and 0.00026− 0.0017 μg/L respectively at lake
Biwa (Yamaji et al., 2010), 0.021− 0.127 μg/L and 0.019− 0.264 μg/L
respectively at Tokyo Bay water (Hayashi et al., 2002). Higher con­
centration of DAS1 and DSBP in the present study than Lake Biwa and
Tokyo Bay water indicated the excessive usage of FWA in detergent
products of Bangladesh.
In the Ganges River, fluorescence intensity of FWA was in the range
between 0.046− 0.24 RU (mean = 0.14 RU, standard deviation = 0.07
RU) and was high in the monsoon period. DSBP-like FWA showed
concentration ranges in the Ganges river between 0.4995–2.59 μg/L
(mean = 1.54 μg/L, σ = 0.79 μg/L) (Fig. 6). Comparatively lower
fluorescence intensity in the Ganges River than that of lake waters
caused from the dilution effects due to high water discharges in river.
Photo-degradation, biodegradation and adsorption by clay minerals
during transportations from sources to river were also reduced FWA
concentration in the river water. However, presence of FWA in the river
water in most of the months throughout the year demonstrated its
persistent nature of the anthropogenic molecular marker in the aquatic
environments. Due to monsoon climate in Bengal delta, rainfall started
to increase rapidly at the late pre-monsoon or early monsoon which
caused the swift wash out of anthropogenic derived materials including
household and industrial discharges in the low land and cannel into the
Ganges River. Monsoon derived anthropogenic materials might be car­
ried detergent residues and reflected in the higher intensity of FWA
throughout the monsoon period (Fig. 6).
DAS1 and DSBP concentration at the Yasu River was found between
10.6–243 ng/L and 30.5–314 ng/L respectively (Hayakawa et al., 2007)
and only DSBP concentration was varied between 0.28–1.84 μg/L on
average at various river waters of Saitama Prefecture in Japan (Taka­
hashi and Kawamura, 2007). DSBP concentration in our study was much
higher than the concentration found in Yasu River, but was in the closer
ranges found in various river waters at Saitama Prefecture in Japan.
River water samples in Saitama Prefecture were collected considering
population density and industrial and domestic wastewater flow sta­
tions. So, more FWA containing wastewater input from domestic and
industrial sources were mainly responsible for the presence of significant
amount DSBP in the Ganges River.
FWA is mainly used in commercial detergents to increase to whit­
ening appearance of apparels and enters into the surface water (lake and
river) after laundry washing through sewerage lines. Untreated indus­
trial wastewater may also add FWAs in freshwater of Bangladesh. This
study identified excess amount of FWA in commercial detergents, lakes
and most of the times of the year in the Ganges River. Most of the
anthropogenic markers are hydrophobic and useful for tracking sewage
particles and pollutants. But, earlier, it was difficult to exploit hydro­
philic markers (e.g. linear alkylbenzenesulfonates, urobilin) due to their
non-persistent and easily degradable nature in freshwater and estuarine
environments. But the persistent nature of FWA and trace detection
capacity of 3DEEM fluorescence techniques could be able to resolve it.
FWA could potentially be used to trace the movement of water-soluble
anthropogenic pollutants in aquatic systems. Thus, FWA could be a
potential molecular marker to identify anthropogenic pollution in the
environment.
4. Conclusion
3DEEM fluorescence spectroscopy and PARAFAC modeling identi­
fied and estimated commonly used FWA namely DSBP-like product in
the commercial detergents of Bangladesh. Concentration of DSBP in the
commercial detergents varied between 0.57–12.84 mg/g respectively,
which was 0.23–5.14 times higher than the usage guideline of FWA in
N.M. Niloy et al.
detergents. Impacts of over using of FWA can deteriorate the surface
water quality as well as natural ecosystem. DSBP concentrations were
ranged between 4.7–10.42 μg/L and 0.4995–2.59 μg/L in lake and the
Ganges River, respectively. DSBP could also be identified by photo-
decay method, but it looked difficult to detect DAS1 in the Ganges
River because of its lower concentration and rapid signal reduction.
FWA concentration was higher in the monsoon than other seasons in the
Ganges River. The large size and length of the Ganges River and the
inevitable precipitation during the monsoon, may account for the vari­
ation in FWA concentrations.
From the present study, we conclude that FWAs are potential marker
in tracing sewerage and wastewater effluents and/or terrestrial derived
organic pollutants in aquatic environments. Small volume of water
sample (> 50 mL) without any pretreatment and pre-concentration is
required for 3DEEM fluorescence analysis which simplifies clear
reflection of this molecular marker and assist to track the anthropogenic
pollutants seasonal variability in the Ganges river. FWAs may supple­
ment a new tool to investigate the behavior of emerging organic
micropollutants in the aquatic environments.
Author statement
Nahin Mostofa Niloy: sampling, data collection and analysis, draft
preparation. Md. Morshedul Haque: sampling and data collection.
Shafi M Tareq: Conceptualization, methodology, software, validation,
reviewing and editing manuscript, providing necessary laboratory sup­
ports including chemicals and instruments and supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was supported by University Grants Commission of
Bangladesh. We thank to Bangladesh Police, Hardinge Bridge Camp,
Khulna Range for providing security during monthly field monitoring.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.enmm.2020.100419.
References
Afreen, S., 2011. Developing a new combination and proportion of chemicals for the
production of laundry detergent at low cost in context of Bangladesh. J. Chem. Eng.,
IEB ChE 26, 50–53.
BBS, Bangladesh Bureau of Statistics, 1994-2019. https://www.ceicdata.com/en/bangla
desh/production-by-commodity/production-soap–detergent.
Blanco, M., Jiménez, L., Valverde, I., 2001. Degradation of a stilbene-type fluorescent
whitening agent with hypochlorite: identification of the degradation products by
capillary electrophoresis. Environ. Toxicol. Chem. 20, 2193–2197.
Cao, Y., Griffith, J.F., Weisberg, S.B., 2009. Evaluation of optical brightener photodecay
characteristics for detection of human fecal contamination. Water Res. 43,
2273–2279.
China Cleaning Industry Association (CCIA), 2011. The Market Analysis of Laundry
Powder Detergent and Additives -2-. Green Chemical.
Dickerson, J.W.J., Hagedorn, C., Hassall, A., 2007. Detection and remediation of human-
origin pollution at two public beaches in Virginia using multiple source tracking
methods. Water Res. 41, 3758–3770.
View publication stats
Environmental Nanotechnology, Monitoring & Management 15 (2021) 100419
Dubber, D., Gill, L.W., 2017. Suitability of Fluorescent Whitening Compounds (FWCs) as
indicators of human faecal contamination from septic tanks in rural catchments.
Water Res. 127, 104–117. https://doi.org/10.1016/j.watres.2017.10.005.
Falk, H.L., Bingham, E., 1973. Interaction of fluorescent whitening agents and ultraviolet
radiation. Ambio 2, 22–25.
Goletz, C., Wagner, M., Grübel, A., Schmidt, W., Korf, N., Werner, P., 2011.
Standardization of fluorescence excitation–emission-matrices in aquatic milieu.
Talanta 85, 650–656. https://doi.org/10.1016/j.talanta.2011.04.045.
Hartel, P.G., Hagedorn, C., McDonald, J.L., Fisher, J.A., Saluta, M.A., Dickerson Jr., J.W.,
Gentit, L.C., Smith, S.L., Mantripragada, N.S., Ritter, K.J., Belcher, C.N., 2007.
Exposing water samples to ultraviolet light improves fluorometry for detecting
human fecal contamination. Water Res. 41, 3629–3642.
Hayakawa, K., Okumura, R., Yamamoto, H., Fujiwara, M., Yamaji, N., Takada, H.,
Kanematsu, M., Shimizu, Y., 2007. Distribution and fluxes of fluorescent whitening
agents discharged from domestic wastewater into small rivers with seasonal changes
of flow rates. Limnology 8, 251–259. https://doi.org/10.1007/s10201-007-0220-6.
Hayashi, Y., Managaki, S., Takada, H., 2002. Fluorescent whitening agents in Tokyo Bay
and adjacent rivers: their application as anthropogenic molecular markers in coastal
environments. Environ. Sci. Technol. 36, 3556–3563.
Holbrook, R.D., Yen, J.H., Grizzard, T.J., 2006. Characterizing natural organic material
from the Occoquan Watershed (Northern Virginia, US) using fluorescence
spectroscopy and PARAFAC. Sci. Total Environ. 361, 249–266.
Home Care & Formulation Technologies, 2011. Fluorescent Whitening Agent for Laundry
Products. Tinopal CBS-X 08_101035e-00.
Jagessar, R.C., Sooknanan, L., 2011. Spectrophotometric determination of phosphates
(PO43-) anion in waste water from selected areas of Coastal Guyana via the stannous
chloridemolybdate calorimetric method. Int. J. Acad. Res. 3, 98–107.
Kramer, J.B., Canonica, S., Hoigne, J., 1996. Degradation of fluorescent whitening agents
in sunlit natural waters. Environ. Sci. Technol. 30, 2227–2234.
Mostofa, K.M.G., Honda, Y., Sakugawa, H., 2005a. Dynamics and optical nature of
fluorescent dissolved organic matter in river waters in Hiroshima prefecture. Japan.
Geochem J 39, 257–271.
Mostofa, K.M.G., Wu, F.C., Yoshioka, T., Sakugawa, H., Tanoue, E., 2009. Dissolved
organic matter in the aquatic environments. In: Wu, F.C., Xing, B. (Eds.), Natural
Organic Matter and Its Significance in the Environment. Science Press, Beijing,
pp. 3–66.
Mostofa, K.M.G., Wu, F.C., Liu, C.Q., Fang, W.L., Yuan, J., Ying, W.L., Wen, L., Yi, M.,
2010. Characterization of Nanming River (Southwestern China) impacted by
sewerage pollution using excitation-emission matrix and PARAFAC. Limnology 11,
217–231.
Murphy, K.R., Stedmon, C.A., Waite, T.D., Ruiz, G.M., 2008. Distinguishing between
terrestrial and autochthonous organic matter sources in marine environments using
fluorescence spectroscopy. Mar. Chem. 108, 40–58.
Nowicki, S., Lapworth, D.J., Ward, J.S.T., Thomson, P., Charles, K., 2019. Tryptophan-
like fluorescence as a measure of microbial contamination risk in groundwater. Sci.
Total Environ. 646, 782–791. https://doi.org/10.1016/j.scitotenv.2018.07.274.
Qv, X.-Y., Jiang, J.-G., 2013. Toxicity evaluation of two typical surfactants to Dunaliella
bardawil, an environmentally tolerant alga. Environ. Toxicol. Chem. 32, 426–433.
Salas, H., Gutiérrez-Bouzán, C., López-Grimau, V., Vilaseca, M., 2019. Respirometric
study of optical brighteners in textile wastewater. Materials 12, 785.
Salve, P.R., Lohkare, H., Gobre, T., Bodhe, G., Krupadam, R.J., Ramteke, D.S., Wate, S.R.,
2012. Characterization of chromophoric dissolved organic matter (CDOM) in
rainwater using fluorescence spectrophotometry. Bull. Environ. Contam. Toxicol. 88
(2), 215–218.
Stedmon, C.A., Bro, R., 2008. Characterizing dissolved organic matter fluorescence with
parallel factor analysis: a tutorial. Limnol. Oceanogr. Methods 6.
Takahashi, M., Kawamura, K., 2007. Simple measurement of 4,4’-bis(2-sulfostyryl)-
biphenyl in River Water by Fluorescence Analysis and its application as an Indicator
of domestic wastewater contamination. Water Air Soil Pollut. 180, 39–49.
Tareq, S.M., Rahaman, M.S., Rikta, S.Y., Islam, S.M.N., Sultana, M.S., 2013. Seasonal
variations in water quality of the Ganges and Brahmaputra river, Bangladesh.
Jahangirnagar Univ. Environ. Bull. 2, 71–82.
Yamaji, N., Hayakawa, K., Takada, H., 2010. Role of photodegradation in the fate of
fluorescent whitening agents (FWAs) in lacustrine environments. Environ. Sci.
Technol. 44, 7796–7801.
Yamashita, Y., Jaffe, R., 2008. Characterizing the interactions between trace metals and
dissolved organic matter using excitation-emission matrix and parallel factor
analysis. Environ. Sci. Technol. 42, 7374–7379.
Yuan, C.L., Xu, Z.Z., Fan, M.X., Liu, H.Y., Xie, Y.H., Zhu, T., 2014. Study on
characteristics and harm of surfactants. J. Chem. Pharm. Res. 6 (7), 2233–2237.
Zhi, E., Yu, H., Duan, L., Han, L., Liu, L., Song, Y., 2015. Characterization of the
composition of water DOM in a surface flow constructed wetland using fluorescence
spectroscopy coupled with derivative and PARAFAC. Environ. Earth Sci. 4148.
https://doi.org/10.1007/s12665-015. -6.