Environment International 9293 (2016) 3342

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Environment International

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Occurrence and fate of emerging trace organic chemicals in wastewater

plants in Chennai, India
Tarun Anumol a,b, Arya Vijayanandan c, Minkyu Park a, Ligy Philip c, Shane A. Snyder a,
a
Department of Chemical & Environmental Engineering, University of Arizona, Tucson, AZ, USA
b
Agilent Technologies Inc., Wilmington, DE, USA
c
Environmental and Water Resources Engineering Division, Department of Civil Engineering, Indian Institute of Technology Madras, Chennai, India

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

Article history: The presence of pharmaceuticals, hormones, pesticides and industrial contaminants collectively termed as trace
Received 21 January 2016 organic compounds (TOrCs) in wastewater has been well-documented in USA, Europe, China and other regions.
Received in revised form 17 March 2016 However, data from India, the second most populous country in the world is severely lacking. This study
Accepted 17 March 2016
investigated the occurrence and concentrations of twenty-two indicator TOrCs at three wastewater treatment
Available online xxxx
plants (WWTPs) in South India serving diverse communities across three sampling campaigns. Samples were
Keywords:
collected after each WWTP treatment unit and removal efciencies for TOrCs were determined. Eleven TOrCs
Emerging contaminants were detected in every sample from every location at all sites, while only ve TOrCs were detected consistently
India in efuent samples. Caffeine was present at greatest concentration in the inuent of all three plants with average
Wastewater treatment concentrations ranging between 56 and 65 g/L. In contrast, the x-ray contrast media pharmaceutical, iohexol,
Indicator chemicals was the highest detected compound on average in the efuent at all three WWTPs (2.18.7 g/L). TOrCs were
Tracers not completely removed in the WWTPs with removal efciencies being compound specic and most of the atten-
Pharmaceuticals uation being attributed to the biological treatment processes. Caffeine and triclocarban were well removed
(N80%), while other compounds were poorly removed (acesulfame, sucralose, iohexol) or maybe even formed
(carbamazepine) within the WWTPs. The efuent composition of the 22 TOrCs were similar within the three
WWTPs but quite different to those seen in the US, indicating the importance of region-specic monitoring. Di-
urnal trends indicated that variability is compound specic but trended within certain classes of compounds (ar-
ticial sweeteners, and pharmaceuticals). The data collected on TOrCs from this study can be used as a baseline to
identify potential remediation and regulatory strategies in this understudied region of India.
2016 Elsevier Ltd. All rights reserved.

1. Introduction
Pharmaceuticals, personal-care products, hormones, and industrial
compounds, are often collectively termed as trace organic compounds
(TOrCs). These substances are generally ubiquitous in municipal waste-
water. Several thousand pharmaceuticals are currently in circulation
and their primary route into the environment is through human excre-
tion into wastewater. Similarly, hormones enter wastewater through
human excretion and concentrated animal feeding operations while in-
dustrial compounds can enter wastewater through point discharges and
surface runoff. Thus wastewater can be considered as the important
contributor of TOrCs to the aquatic environment with high potential
to enter source and potable water (Lee et al., 2015).
The primary concern associated with TOrCs is potentially adverse
effects to wildlife and aquatic systems at environmentally relevant
Corresponding author at: Department of Chemical and Environmental Engineering,
University of Arizona, 108 Harshbarger, 1133 E James E Rogers Way, Tucson, AZ 19808,
USA.
E-mail address: snyders2@email.arizona.edu (S.A. Snyder).
concentrations (vom Saal and Hughes, 2005; Kidd et al., 2007; la Farre
et al., 2008). Further, potential chronic effects associated with low
dose, long-term human exposures and mixture toxicity through potable
water contamination has not yet been characterized (Daughton and
Ternes, 1999; Snyder, 2014). Many of these TOrCs are not completely
removed by conventional water treatment processes, which were not
designed for their attenuation (Westerhoff et al., 2005; Kosma et al.,
2014). Consequently, TOrCs have been detected in wastewater efuents
and receiving water bodies in many regions. Numerous studies have
characterized the presence of TOrCs in wastewaters across North
America, Europe, Asia, and Australia. A summary of concentrations
reported in the literature across the world has been provided in Table 1.
However, concentrations of TOrCs are known to vary among regions
due to sales and usage patterns, water consumption and water treat-
ment methods employed (Verlicchi et al., 2012; Alidina et al., 2014).
Thus no generalized conclusions can be drawn from one region to
another without empirical data.
India is the second most populous country in the world with an es-
timated average water demand of 710 billion cubic meters. The study
area, Chennai is the fourth most populous city in India with a population

http://dx.doi.org/10.1016/j.envint.2016.03.022
0160-4120/ 2016 Elsevier Ltd. All rights reserved.
34 T. Anumol et al. / Environment International 9293 (2016) 3342

Table 1
TOrCs reported in studies around the world.

Contaminants Country Concentration range (g/L)^ Samples* Matrix References

Pharmaceuticals USA nd-5.2 50 Wastewater Efuent Batt et al. (2008), Sui et al. (2011), Bijlsma et al. (2012), Alidina
nd-2.95 7 Wastewater Efuent et al. (2014), Kosma et al. (2014), Kostich et al. (2014), Kwon
0.0663.91 3 Wastewater Inuent and Rodriguez (2014)
nd-1.32 3 Wastewater Efuent
nd-96.6 32 Wastewater Inuent
Greece
nd-1.07 32 Wastewater Efuent
Saudi Arabia nd-3.2 4 Wastewater Efuent
nd-0.8 4 Wastewater Inuent
China
nd-0.2 4 Wastewater Efuent
nd-3.70 5 Wastewater inuent
Netherlands
nd-0.994 5 Wastewater efuent
Hormones Spain nd-0.004 1 Wastewater Inuent Carballa et al. (2004), Chang et al. (2011), Sapozhnikova et al.
0.0270.179 2 Wastewater Inuent (2011)
USA
nd-0.024 2 Wastewater Efuent
nd-3.7 7 Wastewater Inuent
China
nd-0.012 7 Wastewater Efuent
Pesticides Spain nd-1.94 5 Wastewater Efuent Barco-Bonilla et al. (2010), Singer et al., (2010)
Switzerland nd-1.01 Wastewater Efuent
Peruorinated compounds Japan/Thailand nd-0.574 13 Wastewater Efuent Sinclair and Kannan (2006), Shivakoti et al. (2010), Llorca et al.
USA nd-1.05 6 Wastewater Efuent (2012)
Germany/Spain nd-0.50 5 Wastewater Efuent
Articial sweeteners USA ~17.030.0 9 Wastewater Efuent Buerge et al. (2009), Oppenheimer et al. (2011), Alidina et al.
Saudi Arabia 0.41528.0 4 Wastewater Efuent (2014)
2.065.0 10 Wastewater Inuent
Switzerland
nd-46.0 10 Wastewater Efuent

in excess of 4.5 million. The annual wastewater treatment capacity of 2. Experimental

the city is estimated at 571 million liters per day (MLD) while projected
daily water requirement is between 710 and 900 MLD (Vedachalam,
2012). With this shortage between demand and supply, the city will
be forced to consider alternate strategies for water replenishment in-
cluding water reuse. While several studies have analyzed bulk water pa-
rameters like pH, total organic carbon, total nitrogen, and others very
few studies have measured individual organic contaminants in India
(CPCB, 2004). Recently, work on analyzing pesticides has been per-
formed in some regions of the country (Dsikowitzky et al., 2014), and
TOrCs have been detected in surface waters (Ramaswamy et al., 2011;
Selvaraj et al., 2014; Shanmugam et al., 2014). Larsson et al. looked at
the presence of pharmaceuticals in a wastewater efuent servicing
over 90 pharmaceutical manufacturers in a town in India and reported
some of the highest concentrations seen in the world (Larsson et al.,
2007). However, no data on a large variety of indicator TOrCs is avail-
able for WWTPs in the region of study (South India). While, devel-
oped countries are swiftly adopting advanced treatments like
ozone and high pressure membranes to attenuate TOrCs from
water (Wert et al., 2009; Yang et al., 2011), the overwhelming ma-
jority of plants in India adopt only secondary treatment before dis-
charge (CPCB, 2004). Thus, with potential growth in water reuse
schemes in the country, studies on occurrence, and fate of TOrCs in
water is critical.
The aim of this study was to characterize the concentrations of a
suite of indicator TOrCs that represent a larger category of organic con-
tamination in three diverse wastewater treatment plants (WWTPs) in
Chennai inuenced by domestic waste, farming and point source
discharges that are typical of the country. Three sample campaigns
were conducted at the three WWTPs that varied in treatment capacity,
type and size of population served and treatment train. Further, removal
efciency of the three WWTPs were calculated after each treatment
stage and average WWTP efuent concentrations were compared to
those in the USA and other countries. Diurnal variability of TOrCs at a
small wastewater plant serving a unique community was also studied
to compare with results from other regions in the world. This is the
one of the rst studies looking at TOrC concentrations in South India
in wastewater and will serve as a guideline for potential regulatory
action in the country.
2.1. Materials
All standards and reagents were procured at the highest purity that
was practically feasible. The TOrC standards were acquired from a vari-
ety of vendors and have been described in previous literature (Anumol
et al., 2013; Anumol and Snyder, 2015). Water and acetonitrile (both LC-
MS grade) were purchased from Burdick & Jackson (Muskegon, MI),
while formic acid (N 95%) and acetic acid (N 99%) were purchased from
Sigma-Aldrich (St. Louis, MO).
2.2. Methods
UV absorbance and uorescence spectroscopy was analyzed with a
Horiba Aqualog spectrophotometer. Light scattering and inner lter
effects were corrected as described previously (Lakowicz, 2007). Bio-
chemical oxygen demand (BOD), chemical oxygen demand (COD),
total suspended solids, ammonia, total phosphate and nitrate were
analyzed as per the Standard Methods for the analyses of water and
wastewater (APHA, 2012). Total nitrogen was measured using TOC ana-
lyzer equipped with total nitrogen module (Shimadzu, Japan). Two
methods using fully-automated online solid phase extraction with an
Agilent Flexcube module and large volume direct injection were used
to analyze the 22 TOrCs in this study (Table 2). All TOrC analyses were
performed on an Agilent (Santa Clara, USA) LC-MS/MS system and quan-
tication was performed using MassHunter software (Ver. 06.00). The
instrument operation conditions for both methods are provided in the
supplementary materials. Details of the methods including compound
transitions, mass spectrometer conditions, MRLs and QA/QC have been
published earlier (Anumol and Snyder, 2015; Anumol et al., 2015).
2.3. Study area
Samples were collected from three WWTPs, in Chennai city that
discharge into the Adyar River. WWTPs 1 and 2 have 54 and 40 million
liters per day (MLD) treatment capacity. Both plants employ conven-
tional treatment units including activated sludge (AS) process with
WWTP 1 having a nitrication process and consequently longer sludge
 T. Anumol et al. / Environment International 9293 (2016) 3342 35

Table 2 parameters are commonly used to assess the overall treatment efcacy
Trace organic compounds selected for evaluation along with some relevant properties. of the wastewater plant and some have regulatory limits around dis-
Compound Class Molecular LogP^ charge to water bodies. For instance, the biological oxygen demand
weight after 3 days (BOD3) is regulated in India when a treatment plant
Acesulfame Articial sweetener 163.15 0.55 wants to discharge into a water body. While, uorescence data can be
Atenolol Pharmaceutical 266.33 0.43 used to predict treatment process efcacy and has been correlated to
Atrazine Herbicide 215.68 2.2 specic TOrC attenuation by other studies (Singh et al., 2009; Roccaro
Caffeine Stimulant 194.19 0.55
et al., 2011; Gerrity et al., 2012).Similarly, the nutrient data and loading
Carbamazepine Pharmaceutical 236.27 2.8
N,N-diethyl-m-toluamide (DEET) Insect-repellant 191.27 2.5 is essential so as to not cause adverse effects to aquatic species in receiv-
Diclofenac Pharmaceutical 296.15 4.3 ing water bodies. The nitrogen speciation gives us a good idea about the
Diphenhydramine Pharmaceutical 255.36 3.7 nitrication and denitrication processes taking place at the WWTP too.
Gembrozil Pharmaceutical 250.33 4.4 Six parameters often used for assessment of wastewater quality includ-
Iohexol X-ray contrast media 821.14 2.0
Iopamidol X-ray contrast media 777.09 0.70
ing chemical oxygen demand (COD), biological oxygen demand (BOD),

Iopromide X-ray contrast media 791.11 0.40 total nitrogen (TN), ammonia (NH+ 4 ), nitrate (NO3 ) and total phospho-
Meprobamate Pharmaceutical 218.25 0.90 rous (TP) were evaluated. Fig. 1 summarizes the inuent and efuent
Naproxen Pharmaceutical 230.26 3.0 concentrations along with removals of the water quality parameters
Simazine Herbicide 201.66 1.8
measured. COD and BOD concentrations, as organic water quality pa-
Sucralose Articial sweetener 397.63 0.47
Sulfamethoxazole Pharmaceutical 253.05 0.79 rameters, of the inuents of WWTP 1 and WWTP 2 displayed similar
Tris-2-chloroisopropyl- Flame retardant 241.40 0.99 values (~820 mg/L) whereas WWTP3 had approximately half their con-
phosphate (TCPP) centration in the inuent. This difference could be likely due to the fact
Testosterone Hormone 288.42 3.4 that WWTP 3 specically treats a small community which is expected to
Triclocarban Anti-microbial 315.58 4.9
be different in water quality from general domestic wastewater. WWTP
Triclosan Anti-microbial 289.54 5.0
Trimethoprim Pharmaceutical 290.31 1.3 1 and 2 exhibited similar BOD and COD concentrations, which implies a
^ similarity in origin of waste. BOD removals of WWTP 1, 2 and 3 are 93%,
Calculated from ChemAxxon (www.chemicalize.org).
95% and 88%, respectively, which are greater than average 30-day BOD5
removal stated in the regulatory standard of secondary treatment in the
retention time (SRT). Chlorination is used for disinfection at WWTP 2
USA (Tchobanoglous et al., 2002). The efuent BOD5 concentrations
whereas a maturation pond is used in WWTP 1. A 1.4 MLD treatment
measured at WWTP 1,2 and 3 were 24, 16 and 20 mg/L respectively
plant (WWTP 3) handling the wastewater generated on a University
which is lower than the minimum average 30-day BOD5 concentration
campus serving a population of 15,000 inhabitants was also evaluated.
allowed the USA (i.e., 30 mg/L) as well as the maximum BOD3 at 27 C
Treatment units include aerated lagoons followed by clariocculation
for the Indian standard of discharge into inland surface waters.
and ltration. At WWTP 3, the efuent was stored in a large basin
When looking at nutrient loads, TN concentrations in the three
where chlorine was dosed at ~ 2 mg/L and allowed to sit for about
WWTP inuents were very similar (~ 50 mg/L-N). WWTP1 exhibited
30 min in a batch mode. Details of each WWTP including capacity, and
the highest NH+ 4 concentration whereas WWTP 2 displayed the highest
treatment trains are shown in Table 3. Efuent of WWTP 2 plant is
NO 3 value. WWTP3 showed the highest TP, but much lower NH4 and
+
discharged into the Adyar River whereas efuent from WWTP 1 drains
NO3 concentrations compared to the other two inuents. Comparing
into Bay of Bengal while major amount of the efuent from WWTP 3 is
removal data for the nutrients, TN removal at WWTP 1 was lower com-
reused for gardening and ushing purposes. The remaining water from
pared to WWTP 2 and 3 (b 40%). This coupled with the low concentra-
WWTP 3 is let out to Buckingham canal, which joins Adyar River.
tions of NH+ 4 and NO3 implies higher presence of organic nitrogen
and/or NO 2 in the WWTP1 efuent and could have implications on
2.4. Sample collection nitrogenous DBP formation when the water is disinfected. The presence
of an aerated lagoon with a large retention time in WWTP3 effectively
Samples were collected in 22 mL amber glass vials that had been removed the NH+ 4 as good nitrication was achieved. This data indicates
previously furnaced to 550 C for 5 h. All samples were stored at 4 C that nutrient loading was vastly different at the three WWTPs and
with ice packs upon collection and shipped to the analytical lab within removal was highly dependent on the treatment scheme. Further
48 h. Grab samples were collected after each treatment unit from all study over larger periods and seasons is encouraged to understand the
the WWTPs for the three sample campaigns (late summer 2013, winter cause of nutrient loads entering these WWTPs and also their effect on
2013, early summer 2014). In the third campaign, additional bi-hourly the receiving bodies.
samples were collected at WWTP 3 to study diurnal variations of Total uorescence (TF)integration of uorescence intensities over
TOrCs for a small community. Schematic diagram of treatment units excitation and emission wavelengthscan be another indicator of
for each WWTP is shown in the supplementary materials (Figure S1). organic content in water. In contrast to BOD and COD, TF in the inuent
of WWTP 3 was greater than those of WWTP1 and 2 (Fig. 2). Fluores-
3. Results and discussion cence intensity is heavily dependent on functional groups of organic
matter, particularly stronger with electron-donating functional groups
3.1. Water quality parameters such as amine and hydroxyl groups (Leenheer and Crou, 2003). This
result infers that WWTP 3 inuent contains more organic matter
Bulk water parameters were analyzed during the last campaign to content with electron-donating functional groups than the other two
evaluate the overall performance of the three WWTPs. These wastewater inuents. Fluorescent excitation-emission matrixes (EEM)

Table 3
Description of the three WWTPs studied.

WWTP# Capacity (MLD) HRT (hrs) SRT (days) Primary Treatment Secondary Treatment Final Treatment

1 54 6 10 Grit chamber/clarier Conventional activated sludge Maturation pond

2 40 6 6 Grit chamber/clarier Conventional activated sludge Chlorination
3 1.4 74 3.1 Aerated lagoon Clarication/occulation Filtration with chlorine addition
36 T. Anumol et al. / Environment International 9293 (2016) 3342

3.2. Trace organic compounds

Fig. 1. Water quality parameters in the inuent and efuent for the three WWTPs (bar
graph, left y-axis) and their removals (line and marker graph on right y-axis).
also show that WWTP3 inuent has relatively broader and stronger
uorescent peaks at the soluble microbial byproduct-like region,
conrming that WWTP 1 and 2 are different from WWTP 3 in water
quality. These EEMs can serve as aqualitative indicator of treatment
efcacy or change in plant operation by monitoring the change before
and after treatment with time.
3.2.1. Inuent
Eleven TOrCs (acesulfame, atenolol, caffeine, carbamazepine,
diclofenac, iohexol, naproxen, sucralose, sulfamethoxazole, TCPP and
triclocarban) were detected in all inuent samples at the three WWTPs
while only one pharmaceutical (meprobamate) and two pesticides
(atrazine and simazine) were not detected in any WWTP sample. The
most prolic TOrC detected was caffeine with average concentrations
between 56 and 65 g/L in the three WWTP inuents. These concentra-
tions are similar to reported levels in WWTP inuents around the globe
(Thomas and Foster, 2005; Daneshvar et al., 2012; Qi et al., 2015). X-ray
contrast media, Iohexol was detected at high concentrations (4.3
9.6 g/L), probably due to several hospitals and medical facilities located
in the area that discharge to the WWTPs. Diclofenac (3.15.3 g/L)
and atenolol (1.16.9 g/L) were the most abundant pharmaceuticals
detected while other pharmaceuticals were at signicantly lower
concentrations. Much lower diclofenac concentrations were reported in
several inuents located in Spain, Germany USA, Singapore and China
(Ternes, 1998; Sui et al., 2011; Tran et al., 2013; Camacho-Muoz et al.,
2014). Average carbamazepine, sulfamethoxazole and naproxen concen-
trations at the 3 WWTPs were between 310 and 920 ng/L. While a large
variability of these pharmaceuticals was noticed in different studies, the
values are in the same order of magnitude as reported by others around
the globe (Carballa et al., 2004; Tran et al., 2013). The anti-cholesterol
drug, gembrozil was detected at average concentrations b 100 ng/L,
while concentrations in the US have been reported at several g/L (Lee
et al., 2005; Fang et al., 2012). Average inuent sucralose concentration
(1.11.9 g/L) at the three WWTPs were similar to levels reported in
Europe and China (Buerge et al., 2009; Scheurer et al., 2009; Qi et al.,

Fig. 2. (a)Fluorescent excitation-emission matrices (EEMs) of inuents and efuents of three WWTPs. The top left EEM shows operationally-dened uorescence regions. Region I, II, III, IV
and V refers to tyrosine-like aromatic protein, tryptophan-like aromatic protein, fulvic acid-like, soluble microbial byproduct-like and humic acid-like regions, respectively. (b) Total
uorescence (i.e., integration of uorescence intensities over excitation/emission wavelengths) of the inuents and efuents of three WWTPs.
 T. Anumol et al. / Environment International 9293 (2016) 3342
2015) but were substantially lower than concentrations reported in the
US (Subedi and Kannan, 2014). Another articial sweetener, acesulfame
(0.560.86 g/L) was detected at signicantly lower concentrations than
studies from Europe (Buerge et al., 2009; Scheurer et al., 2009) but at
similar levels in US, Korea and Saudi Arabia (Alidina et al., 2014; Subedi
and Kannan, 2014). These variations are due to local consumption pat-
terns and highlight the need for country and region specic monitoring
of TOrCs in water. Triclocarban concentrations were between 1.0 and
1.8 g/L at the 3 WWTPs with little variation however, large variations
have been reported in US efuents with concentrations N4 g/L in
some studies (Heidler and Halden, 2009; Hedgespeth et al., 2012) and
b0.4 g/L reported in others (Trenholm et al., 2008; Kumar et al.,
2009). Such variations again illustrate the need for location-specic
monitoring of TOrCs. The mean concentrations of all TOrCs with detec-
tion frequency for all WWTP inuents across the three campaigns is
shown in Fig. 3.
The average total concentration of the twenty-two TOrCs entering
the three WWTPs were 83.7 g/L (plant 1), 93.1 g/L (plant 2), and
76.5 g/L (plant 3). WWTP 3 had the lowest total TOrC concentration
in all three sampling campaigns mainly due to lower inuent pharma-
ceutical concentrations going into the plant. WWTP 3 is a smaller
plant that serves an educational institute with a younger population
that would be expected to be healthier. This along with the lower med-
ical waste released into this plant compared to other 2 WWTPs resulted
in lower concentrations. The average detection frequency of TOrCs in
the 3 WWTPs followed the same trend with 68% (WWTP 1), 75.6%
(WWTP 2), and 63.5% (WWTP 3) observed across all campaigns.
The composition of TOrCs entering the three plants were very simi-
lar. The average composition at the three plants across campaigns is
illustrated in the supplementary materials (Figure S1). On an average,
Caffeine accounted for over 65% of the incoming TOrCs measured in
this study at all three WWTPs. WWTP 1 and 2 had very similar levels
of all six classes of TOrCs (anti-microbial agents, articial sweeteners,
pharmaceuticals, stimulant, x-ray contrast media and miscellaneous)
while WWTP 3 had a lower pharmaceutical load as mentioned earlier.
The nine pharmaceuticals corresponded to 14.1%, 15.9% and 7.3% in
WWTP1, WWTP 2 and WWTP 3 respectively. X-ray contrast media
were the third most dominant class accounting for 811.6% of the
inuent in all three plants. The two articial sweeteners for 23.3%,
while the anti-microbial agents ranged between 0.5 and 2% of the load
at the inuent of all the WWTPs. As with the bulk organic parameters
a similar composition of TOrCs in WWTP 1 & 2 was seen. No clear trends
in seasonal variation of TOrC concentrations were noticed and this may
Fig. 3. Average concentration of TOrCs in (a) inuent and (b) efuent of WWTP 1 (red), WWTP 2 (green), and WWTP 3 (blue). Detection frequency: 100% (square), 67% (triangle), 33%
(cross). Non-detects: atrazine, simazine and meprobamate. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)
37
be due to there being no clear seasons in this region between summer
and the monsoons. While some TOrCs were higher in the inuent in
winter, others had the opposite trend while some were similar in all
three campaigns. Seasonal variations have been reported in other
parts of the world but this is highly dependent on the compound,
water ow, consumption patterns, degradation rates, temperature and
other factors (Sui et al., 2011; Yu et al., 2013). More frequent sampling
over larger periods would be required to make an informed conclusion
and the authors suggest more work go into this at the Indian WWTPs.
3.2.2. Efuent
Only ve TOrCs (acesulfame, atenolol, caffeine, iohexol and sucra-
lose) were detected in every efuent sample from all three plants.
When looking at each individual plant efuent, twelve (WWTP 1), ten
(WWTP 2) and seven (WWTP 3) TOrCs were ubiquitous across all
sample campaigns. The average total efuent TOrC concentrations
were signicantly lower than the inuent for all three plants with
total concentrations of 23.5, 19.9 and 5.5 g/L in WWTP 1, 2 & 3 respec-
tively. Iohexol was the most abundant TOrC in the efuent of all three
plants with average concentrations of 8.7, 6.3 and 2.1 g/L respectively.
Sucralose concentrations varied between 0.79 g/L (WWTP 3) and
1.87 g/L (WWTP 1) which is lower than most efuents in the US
(Oppenheimer et al., 2011; Lester et al., 2014) but similar to efuent
sucralose levels reported in a study of 90 wastewater efuents across
Europe (Loos et al., 2013). Acesulfame was present at concentrations
between 0.45 and 0.89 g/L in the efuents of all three plants, while
caffeine was present at 5.4 and 4.8 g/L in WWTP 1 & 2 but only
0.11 g/L in WWTP 3. Levels of acesulfame were much higher in
Europe while concentrations in USA were similar (Loos et al., 2013;
Anumol et al., 2015). Like the inuent, diclofenac and atenolol were
the highest detected pharmaceuticals in the efuent too. Average
diclofenac concentrations in WWTP 1, 2 & 3 were 2.3, 1.7 and 1.1 g/L
respectively. These concentrations were signicantly higher than sever-
al efuents reported in USA, Europe and China (Gros et al., 2006; Vieno
and Sillanp, 2014). Average atenolol concentration in WWTP 1 and 2
was 1.6 and 0.91 g/L respectively, while WWTP 3 had only 0.08 g/L in
the efuent. WWTP 3 serves an educational institution with a largely
young population that would not be on blood-pressure regulation med-
ication thus explaining the lower concentration (same trend was seen
in inuent as well). Kostich and colleagues found a mean atenolol con-
centration of 0.94 g/L in 50 US WWTP efuents (Kostich et al., 2014),
which was similar to WWTP 1 & 2 that represent a typical domestic
population. A larger average concentration of TCPP was detected in
38 T. Anumol et al. / Environment International 9293 (2016) 3342
Fig. 4. Average composition of three WWTP efuents sampled with comparison to average efuent concentrations in USA.
WWTP 3 (1.75 g/L) compared to WWTP 1 (0.23 g/L) and WWTP 2
(0.24 g/L) while DEET concentrations were in the same order of
magnitude as reported from several efuents in the US (Merel et al.,
2015). The concentrations of TOrCs in the efuent is depicted in Fig. 3b.
Fig. 4 represents the average efuent composition of the 22 TOrCs
studied in the three plants along with a comparison of data from
secondary efuent concentrations in US derived from a literature
review previously published (Anumol et al., 2015). The percentage
composition of TOrCs for the plants in USA was calculated assuming
that the 22 TOrCs measured in this study comprised 100% of the TOrCs
in the sample to give a direct comparison with the data from the three
WWTPs in this study. Like the inuent, the efuent composition of the
3 WWTPs was similar with respect to the TOrCs especially in WWTP 1
& 2. This could be expected as both plants employed AS treatments.
The largest class in the efuent was the x-ray contrast media with aver-
age compositions of 34.9%, 37.9% and 25.3% in WWTP 1, 2 & 3 respec-
tively. This was higher than the average (14%) in US WWTP efuents,
however in terms of mass loading discharged from the plant, the values
are similar due to large total TOrC concentrations in US efuents (avg.
conc.: 39.4 g/L) for these 22 TOrCs. The articial sweeteners ranged
from 9.7% (WWTP 2) to 17.1% (WWTP 3), which was signicantly
lower than the 49.8% seen in US efuents on average. In fact, the arti-
cial sweeteners (sucralose in particular) account for a large amount of
TOrCs discharged from WWTPs in the US due to high consumption
patterns and poor removal by water treatment processes. Pharmaceuti-
cals monitored accounted for approximately a quarter of the TOrC
concentration being discharged through the efuent in all three
WWTPs studied (28%, 26.5% and 25.3%) as against b10% on average in
US efuents. Caffeine composition was N20% in efuents for WWTP 1
& 2, while only 2% in WWTP 3. The lower nal composition of pharma-
ceuticals and caffeine, not considered to be recalcitrant TOrCs could in-
dicate more efcient treatment trains for TOrCs attenuation in the US.
Considering similar inuent composition of caffeine in all three plants,
the lower efuent concentrations in WWTP 3 could be accounted to
more efcient treatment with the use of an aerated lagoon operating
at the much longer hydraulic retention time (HRT) compared to AS sys-
tem in the rst 2 plants. The different compositions observed between
the three plants in India and average concentrations in the US is impor-
tant in assessing potential impacts to the surrounding environments
and suggesting site and region specic remedial treatment actions.
3.3. Removal efciency of TOrCs
Fig. 5 shows the average removals after primary, secondary and nal
treatment of the eleven TOrCs that were detected in every inuent sam-
ple at all three WWTPs. Average removal efciencies varied signicantly
based on TOrC and treatment type. Primary treatments generally had
low total mean removals for the eleven TOrCs at WWTP 1, 2 and
3(2.5%, 4.9% and 37% respectively), consistent with other reports
(Gbel et al., 2007). Primary removals at WWTP 1 & 2 were much
lower than in WWTP 3 which employed an aerated lagoon as compared
to a grit chamber and primary clarier. The biological removal resulting
from the aerated lagoon results in enhanced removal of some of the
biodegradable TOrCs like atenolol, caffeine, naproxen and triclocarban.
The removals for most compounds in WWTP 1 & 2 after primary
treatment were negligible and b 10%. Some removals were seen due to
physical processes like adsorption onto larger organic matter which
were removed by ltering and settling.
WWTPs 1 & 2 employed AS systems as the secondary treatment.
WWTP 1 had a nitrifying AS system with a sludge retention time
(SRT) of 10 days and WWTP2 employed conventional activated sludge
(CAS) treatment with an SRT of 6 days. WWTP 3 had a clarier/occula-
tor after the maturation pond. Signicant improvement in removals for
atenolol, caffeine, diclofenac, naproxen and triclocarban were noticed
after secondary treatment compared to primary treatment in WWTP 1
& 2. This is probably due to the microbial degradation of these com-
pounds in AS. Du et al. also reported signicant removals of caffeine,
atenolol and diclofenac after AS treatment (Du et al., 2014). WWTP 3
however, had very little additional removal of these compounds in the
secondary treatment because the biological degradation of these
compounds had already taken place in the aerated lagoons. WWTP1
had additional removal of recalcitrant TOrCs like iohexol and TCPP
compared to WWTP 2. Earlier research has suggested that increased
SRTs have a positive effect on removal of recalcitrant TOrCs including
x-ray contrast media (Batt et al., 2006; Gerrity et al., 2010). Interestingly
carbamazepine removals reduced (negative removals) after secondary
treatment in WWTPs 1 & 2, while this was not seen in WWTP 3. This
could indicate that the biological treatment taking place in the CAS
system may actually be degrading carbamazepine precursors into the
parent compounds. Indeed, other researchers have also noticed increased
concentrations of carbamazepine through the plant (Spongberg and
 T. Anumol et al. / Environment International 9293 (2016) 3342
Fig. 5. Average removal efciency of conventional treatments in the three WWTPs for selected TOrCs. * denotes one or more concentrations at this sampling point were bMRL. In this case
1/2 the MRL was used to calculate the average removal of the TOrC.
Witter, 2008; Kwon and Rodriguez, 2014). A similar trend was seen for
sulfamethoxazole as well after secondary treatment in WWTP 1 & 2
while not in WWTP 3. Both articial sweeteners tested had very low
removals after secondary treatment in WWTP 1 & 2. Essentially, these
compounds had no removal through AS treatment as has been found by
other researchers too (Scheurer et al., 2009; Pasquini et al., 2013). Some
additional removal of sucralose was seen during secondary treatment in
WWTP 3 and this may be due to physical adsorption and removal by
the occulation process. The overall removal of acesulfame, sucralose
and indeed most other TOrCs after secondary treatment was higher in
WWTP3 compared to WWTP 1 & 2. The primary reason for this was
probably the signicantly higher HRT in the aerated lagoon versus AS
treatment. The HRT for WWTPs 1 and 2 employing AS treatment was
6 h while WWTP 3 had a HRT of over 3 days. Guerra et al. suggested
that better removals of pharmaceuticals are achieved with HRTs N16 h;
while other researchers have also noted greater TOrC attenuation with
increased HRTs (Guerra et al., 2014).
Disinfection was performed differently at each plant. At WWTP 1, no
oxidant was added in the nal maturation pond, while WWTP 2 & 3
used chlorination. Only WWTP 2 had a continuous disinfection step
though, involving chlorination. Sulfamethoxazole removals were
enhanced in this step at WWTP 2 because of its susceptibility to be
oxidized by free chlorine as has been reported previously (Dodd and
Huang, 2004). Naproxen and Diclofenac were the only other TOrCs to
show any appreciable removal on chlorination at WWTP 2, again due
to their rapid degradation with chlorine as has been reported earlier
Fig. 6. Bihourly concentration of selected TOrCs in the inuent and efuent of WWTP 3.
39
(Quintana et al., 2010). At WWTP 3, disinfection removals of sulfameth-
oxazole, naproxen and diclofenac were minimal. In this plant, liquid
chlorine was dosed in a batch mode into an equalization tank and let
sit for 30 min, hence depending on sampling time and depth the
efciency of removal may have varied. Most TOrCs though had no or
very little removal by the chlorine disinfection step in this study. How-
ever, it should be noted that pH, chlorine dose and contact time can
have signicant effect on removals of some TOrCs (Nam et al., 2014).
3.4. Diurnal variability of TOrCs at WWTP 3
Diurnal variability in TOrC loading can affect treatment plant opera-
tion and also the total mass load leaving these plants and consequently
being discharged. Studies in the US have indicated the daily variability
of pharmaceuticals and other TOrCs in large scale-treatment plants.
However, data from small isolated communities not affected by indus-
try is lacking. A total of eleven bihourly grab samples were collected at
WWTP 3 during the third sample campaign to investigate the effects
of diurnal variability both at the inuent and efuent of the plant.
Nine compounds were detected at each sampling in the inuent
(acesulfame, atenolol, caffeine, carbamazepine, diclofenac, iohexol,
sucralose, sulfamethoxazole and TCPP). Triclocarban peaks were also
seen in all inuent samples but issues with the surrogate standard in
these samples meant accurate quantication was not possible and
hence the data is not shown. The concentration of six TOrCs across the
day both in the inuent and efuent is depicted in Fig. 6 while the
40 T. Anumol et al. / Environment International 9293 (2016) 3342
concentration for remaining compounds is shown in the supplementary
materials.
The nine TOrCs detected in every sample at the inuent varied by
several orders of magnitude in concentration as detailed earlier. Their
diurnal variations though were compound specic and had different
trends and patterns. Iohexol and TCPP concentrations in the inuent
were fairly constant throughout the day and characterized by relative
standard deviations (RSD) of 9 and 15% respectively. The results could
indicate that these compounds have a steady and constant discharge
source into the WWTP. On the other hand, the four pharmaceuticals
(atenolol, carbamazepine, diclofenac and sulfamethoxazole) in every
inuent sample had RSDs N30%. This could be due to uctuations in
amount received to the plant based on individual preferences on timing
and dosage of medication taken coupled with excretion times. Almost
all the concentrations measured at different times for these compounds
though fell within the standard deviation of the daily mean indicating a
lack of a spike in concentration that could be caused by a sudden point
source discharge. The ingredients in food and beverages like sucralose,
acesulfame and caffeine were characterized by large RSDs and extreme-
ly high concentrations occurring around meal times of 11 am pm,
7 pm9 pm or early mornings (7 am9 am). A study at a municipal
WWTP in the US noticed highest concentrations of caffeine in the
early morning, however no discernible increase was seen during
meals (Brewer et al., 2012). These compounds typically had signicant
variability with spikes in concentration at certain times which were a
lot higher than the standard deviation around the daily mean.
The variability in the efuent followed similar trends with iohexol
concentrations being fairly constant (RSD: 11%) throughout the day.
TCPP concentrations were also more or less similar throughout the
day except for one sample which resulted in an RSD of 29%. Teerlink
et al. found similar results where TCPP concentrations at a WWTP
efuent did not uctuate much across the day (Teerlink et al., 2012).
The pharmaceuticals in the efuent have intra-day RSDs between 33
and 71% with no particular common inection or peak points during
the day. This study noticed similarly high intra-day RSDs during efuent
sampling as compared to a study in the US for diclofenac but sulfameth-
oxazole RSDs were higher in the previous study (Nelson et al., 2011).
This could be because it is oxidized by chlorine and since the plant
had intermittent chlorine dumping into the nal efuent variations in
removal and nal concentration were noticed. Like the inuent, higher
concentrations in the efuent for sucralose were noticed around meal
times. Caffeine was very well removed through the treatment plant as
explained earlier however a large increase in efuent concentration was
noticed in the 5 pm sample, the reason for which is unclear. Acesulfame
had very constant efuent concentrations with an RSD of 15%.
Since the ow to and out of the plant vary depending on water
consumption patterns throughout the day, the loading of TOrCs can
vary diurnally too. The bihourly mass loading (in ng/h) of the nine
TOrCs is presented in the supplementary materials. In terms of total
mass loading to the plant, the pharmaceuticals had a fairly even daily
loading except for increased levels in the morning (9 am) and later in
the evening (7 pm - 9 pm) probably due to higher proportion of people
taking their medication at this time. Acesulfame had a U shaped mass
loading graph with highest amounts earlier in the morning followed
by a drop off throughout the day and an increase the following morning.
Caffeine and Sucralose had similar mass loading graphs but with a spike
in mass loading to the plant in the evening (7 pm9 pm) presumably
during dinner followed by a drop off in the night time. TCPP mass
loading to the plant inuent was fairly constant through the day. The
efuent mass loading for most compounds had less discernible trends
compared to the inuent. Since the plant has such a long HRT (74 h) it
is hard to make direct comparisons to the bihourly inuent trends.
Sucralose, iohexol and TCPP had similar mass loads throughout the
day. The other compounds had one of more spikes but at different
points during the day. Overall, the efuent mass loading variability
was a lot smaller compared with the inuent.
4. Conclusions
The presence of TOrCs at Indian WWTPs was conrmed in this study.
Numerous commonly detected TOrCs in the US, Europe and Asia were
also seen in the inuent and efuent at three WWTPs studied. The inu-
ent quality both in terms of bulk water characteristics and TOrCs was
signicantly different in WWTP3 that served a University compared to
WWTP1 and 2 that served a large domestic population and industrial
sources. Notably, pharmaceutical loading was a lot lower in WWTP3
compared to the other two WWTPs. Trends in concentrations of TOrCs
in the inuent did not all match those seen in US, Europe or Asia but
were compound specic. Hence, region and site specic monitoring of
TOrCs is important. The efuent composition of WWTP1 and 2 were
similar but differed from WWTP3 and from average US efuents. The
total efuent TOrC loading to the environment (based on the 22
monitored TOrCs) followed the order average US (based on previously
available literature) N WWTP1 N WWTP2 N WWTP3. Biological treat-
ment accounted for most of the removal of TOrCs at the three WWTPs
while a number of the recalcitrant TOrCs were poorly attenuated in
the WWTPs in accordance with previous ndings. Diurnal variability
of TOrCs concentrations was seen in the inuent of WWTP3 on collec-
tion of bihourly samples for most TOrCs (except iohexol and TCPP).
These trends were dependent on the type of TOrC, pattern of usage
and consumption. Efuent variability was a lot lesser than observed in
Nelson et al. (2011) in US efuents but some trends were visible. In
terms of the inuent mass loads (accounting for owrate), additives
to foods and beverages (caffeine, acesulfame, sucralose) had much
higher loading in the morning and during meal times whereas other
compounds had less obvious trends.
The results of this study should provide the regulatory authorities in
India with adequate information to decide on any potential remediation
strategies for TOrCs in wastewater that may potentially enter potable
water sources. It also provides a baseline of TOrC concentrations in a
heavily populated region that can be compared against other regions
in India and across the world.
Acknowledgements
The authors would like to thank Justin Habit and Theresa Nelson at
the University of Arizona for assistance in data collection and analysis.
The authors also acknowledge Agilent Technologies for their assistance
in instrument setup and technical assistance. We also would like to
thank the members of EWRE division at IIT-M for their cooperation
and support during the monitoring campaigns.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.envint.2016.03.022.
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