Form 3
Annual Report
LaMer, Ehime University
Date (08.02.2017)
To Director of LaMer
Principle Investigator: K. Vimalkumar
Affiliation:
India

Bharathidasan University, Tamil

Nadu,
Position: Ph.D Scholar and UGC Project Fellow

Include the report on the result of the project/meeting in a separate sheet.
1. Project / Meeting title
Pharmaceutical and Personal Care Products (PPCPs) and Antibiotics in Aquatic
ecosystem and Sewage Treatment Plants in South India and their Risk
assessment – LC-MS/MS analysis
2. Members of project / meeting
NamePIMembers
K. Vimalkumar

Affiliation

PositionContribution part

Department of Environmental
Biotechnology,
Bharathidasan
University,
Tiruchirappalli,
Tamilnadu,
India

Ph.D
scholar andUGC ProjectFellow

Environmental
toxicology
andAnalyticalChemistry

Dr. R. Babu Department of Environmental Professor
Rajendran
Biotechnology,
and Head
Bharathidasan
University,
Tiruchirappalli,
Tamilnadu,
India
AN.
Subramanian

Department of Environmental UGC

Environmental
Chemistry
andEcotoxicology

MarineBiotechnology,
Emeritus
Bharathidasan
University, Professor
Tiruchirappalli,
Tamilnadu,
India
Dr.
Tatsuya CMES, 2-5 Bunkyo-cho, Professor
Kunisue
Matsuyama,
Ehime790-8577, Japan

Environmental
Chemistry

Environmental
Analytical
Chemistry

3 Contents (separate sheets)
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(1) Contents should be written in separate sheet, A4-size.
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Bunkyo 2-5,, Matsuyama, Ehime
JAPAN 790-8577
8577
Tel: 81-89-927-8187
8187

Joint Usage / Research Center “Leading Academia in Marine and Environment
Pollution Research (LaMer)”
Center for Marine Environmental Studies (CMES), Ehime University

Annual Report for 2016

Submitted byK. Vimalkumar
Department of Environmental Biotechnology
School of Environmental Sciences
Bharathidasasn University
Tiruchirappalli 620 024

Pharmaceutical and Personal Care Products (PPCPs) and Antibiotics in Aquatic ecosystem andSewage Treatment Plants in South India and their Risk assessment – LC-MS/MS analysis
K.Vimalkumar, UGC Project Fellow, Department of Environmental Biotechnology, School of EnvironmentalSciences, Bharathidasan University, Tiruchirappalli, Tamil Nadu, India

1. Aim:Recently, the occurrence of “Emerging Contaminants” in the aquatic environmental has become a worldwide issue;
among these pharmaceuticals personal care products (PPCPs) are of great concern. PPCPs include a diverse
collection of chemical substances used for human and animal diseases, as well as disinfectants used as personal careproducts and house hold chemicals for improving the quality of life. During the last decade, the focus onenvironmental research has been partly turned from the conventional priority pollutants to the so-called emerging
contaminates among which Pharmaceutical Personal care Products (PPCPs) are particularly one of the mostimportant groups of contaminants of emerging concern. PPCPs are generally only slightly transformed or evenunchanged in the wastewater treatment plants (WWTPs) and then enter the aquatic environment. Other possible
sources were attributed to the direct input by use of drugs in aquaculture facilities and the indirect input throughapplication of manure during agricultural activities. Release from manufacturing sites, hospitals and nursing homes
were other sources of PPCPs. PPCPs have been detected frequently throughout the world. They are of particularconcern since some of them are produced and used in large quantities, and several investigations have indicated thatmany of them cannot be degraded during water treatment process. Many PPCPs are persistent or pseudo-persistent(due to continuous emission) in the environment and toxic to non-target organisms. They also have the potential forbioaccumulation in organisms of different tropic levels.
1.1 Objective
1.

To gather data on Pharmaceuticals and Personal Care Products (PPCPs) including antibiotics,
pharmaceutical drugs and cosmetics in environmental and biotic samples from major cities in India which
are contributing such compounds in considerable quantities to the Indian environment and also globally,
wherefrom no data is available. The present sampling sites will be Bangalore and Chennai situated in
Tamil Nadu, a south Indian state. The samples collected by the PI and also that are now archived at the esBANK of Ehime University will be used.

2.

To determine the PPCPs levels in surface water and compare with the concentration levels between thetwo major cities, Bangalore and Chennai from South India and also to compare the data with othercountries’ data.

3. Assessment of androgen and estrogen levels that are induced by organic pollutants such as PPCPs, in fresh
water fish collected from and near the sampling sites.

2. Procedure:
2.1 Sampling location

Fig.1: Location of the sampling points
Sample were collected from the Chennai (n=11) and Bangalore (n=8) including waste water treatment plants and anestuary.

Table.1 Target Analytes
S.No

Category of compounds

Name of the compounds
DFDiclofenacIND

Indomethacin

3MF

Mefenamic acid4

IBP

Ibuprofen

SMXZ

Sulfamethoxazole

6

SMT

Sulfamerazine

7EM

Erythromycin

8RM

Roxithromycin

DIL

Diltiazem

PRP

Propranolol

LS

Losartan

CBZ

Carbamazepine

HLP

Haloperidol

125

NSAIDsAntibiotics

910

Hypertensive agent

1112

Antiepileptic agent

1314

Antihyperlipidemic agent

BZF

Bezafibrate

15

Fenofibrate metaboliteFA

Fenofibric acid16

Antihistamine agent

DPH

Diphenhydramine

17

Anti-itch agent

CTM

Crotamiton

18

Anticoagulate agent

WAR

Warfarin

19

Antimicrobial agents

TCS

Triclosan

20

TCCTriclocarban

21

MeP

Methyl paraben

EtP

Ethyl paraben

23

PrP

Propyl paraben

24

BuP

Butyl paraben

DEET

N,N-diethyl-3-toluamide

22

25

Preservative agents

Insect repellent

2.2 Extraction method for Surface water
20 ml of water sample with added internal standard was filtered and the pH was adjusted to be between 6-8. Using
solid phase extraction technique water samples were filtered through Oasis HLB cartridge.3 mL 5% methanol in
milli-Q water (7:3) was passed through the cartridge for washing. The sample was concentrated and reconstitutedwith 2ml of Milli-Q water and the syringe spike was added. Finally samples were injected in to LC-MS/MS.

3. Results and Discussion
3.1Monitoring of Pharmaceutical Personal Care Products (PPCPs):(PPCPs)
Pharmaceuticals were determined in surface water samples from Chennai and Bangalore.. Among 20 pharmaceutucal
drugs tested (Table 1)16
16 have been detected(Tabledetected2). Those which were below detection levels wer
weresertaline,
nonsertaline, sulfamethazinee and sulfamerazine. Mean concentraction of the detected chemicals ranged between
400ng/L and 1100 ng/L. Ibuprofen was detected at high concentraction in both cities probabl
probably because ofanthropogenic activity viausage
ge of drugs in the hospitals thatt
relased through the sewage water to the rivers.The
highest concentractions were 392.7 ng/L at Chennai and 1079.5 ng/L in Bangalore (Fig.2).High
High concentration inBangalore may be due to its higher population and more anthropogenic activities. Moreover, Bangalore has many
hospitals and other medical facilities, thus having more of phramaceuticals in its environment. Moreover, the peopleof Bangalore are more aristocratic using more of personal care products thus increasing their levels in theenvironment.
Levels of Personal Care Products (PCPs)(PCsuch as Antimicrobial agents, preservatives and insect repellent
repellents weredetected at levels 48.8 ng/L, 81.4 ng/L and 152.6 ng/L, respectively at Chennai. At same time, in Bangalore city
Triclosan and Triclocarban 592.3 ng/L,ng/L Methyl Paraben, Ethyl Paraben, Propyl
yl Paraben and Butyl Paraben were atlevels592.3 ng/L and 101.3 ng/L, 490.4 ng/L, 105 ng/L, 217.5 ng/L and 11 ng/L, respectively. Bangalorehashigherlevels
erlevels of detergents, cospmetics, etc. because of their higher usage by the more affluent people there thanat Chennai where still people use more of natural products.

Fig.2.Mean concentrations of PPCPs determined in the surface water samples in South India

Pharmaceutical and personal care products were globally found in the surface and waste water influent and effluent
samples at various concentration levels in China, Korea, UK, Romania, Japan, Germany, Italy, etc.
(Table.1).Compared with the present study, higher concentrations were observed in UK (surface water) andGermany(influent). It was shown that ibuprofen levels were lower in these cities when compared with both cities ofthe present study (Chennai and Bangalore) and the levels in other Asian countries such as Korea and Japan are high.
Among the 16 compounds Ibuprofen, Carbamazepine, Mefenamic acid have been observed more because in daily
life these drugs are freely available in India and peopleconsume them even for small ailments. Likewise PCPs areused in many cosmetic products especially the Antimicrobial agents (TCC and TCS) and as preservatives (MP, EP,PP and BP). Antimicrobial agents are commonly used in all shampoos, soaps and detergents as ingredients andpreservative chemicals are widely added to food materials. According to global data (Bu et.al, 2013) mainly surface
water samples from China contained such compounds up to milligram levels. For example, the mean levels of
personal care products in the present study ranged from ND to 592.3 ng/L whereas in China they were detected up to<LOQ – 2142ng/l (Bu et.al, 2013).

Pharmaceuticals (ng/L)
Sampling NameDF

Other Countries
Surfacewater,
Korea, 2007
SurfaceUK, 2004

IND

MF

IBP

ND33.5

ND326

ND414

<50366<205044

water,

BZF

FA

DPH

CBZ

HLP

DIL

ND-595

PRP

175.3

339

9.17

1.93

3400±
1700

2000±1300

510±350

4.8

45.9

392.7

N
D

6.3

3.5

79.2

SMTZ

EM

<101022

20.0

STP
influent,
Germany, 2007
Present study (Mean)
Coovam River and 71.1
lake,Chennai,
India

SMXZ

<10-215

Surfacewater,
Italy, 2000
157

WAR

ND-137

LOQ115.2

45.1

CTM

ND-40.1

Surfacewater,Romania, 2003

STP
influent,Japan, 2006

LSRM

4.5

ND

Vrishabhavathi
171
17.37 277
1079.5 1
119 10.4 379.7
2.6
river and WWTP,.1
Bengalore, India
Table.2 Comparison of Pharmaceutical drugs levels with other countries data

830±27
0

3

2.3

29.8

3.7

11.8

48.6

6

10.7

15.2

34.4

2.2

103.6

12.9

5.3

473

20.6

36.2

28.5

DF- Diclofenac, IND – Indomethacin, MF – Mefenamic acid, IBP – Ibuprofen, BZF – Bezafibrate, FA- Fenofibric acid, DPH – Diphenhydramine, CBZ– Carbamazepine, HLP – Haloperiol, DIL – Diltiazem, PRP – Propranolol, LS – Losartan, CTM – Crotamiton, WAR – Warfarin, SMXZ –Sulfamethoxazole, SMTZ – Sulfamethizole, EM – Erythromycin, RM - Roxithromycin

Table.3 Comparison of PCPs levels with other countries data
Personal Care Products (ng/L)
Sampling Name
TCC
China
Pearl river, Guangdong, 2008
4.9-155
Liuxi river, Guangdong, 2010

TCS

MP

EPBP

PP

7.7-218

0.9-66.1

0.223.1<0.1-5.3

1.2-86ND<LOQ2142

Guangdong,<LOQ13.9
4.5-46.2<LOQ26.2
6.5-31.1

Shijing river, Guangdong, 201068.3-388

90.2-478

Zhujiang
2010

river,Victoria Harbor, Hong Kong,2007
Other countries
Effluent, Spain, 2010
Effluent, Hong Kong, 2011
Effluent, France, 2013
Effluent, USA, 2014
River water, Spain, 2011
Present study
Coovam River and lake,
Chennai, India
Vrishabhavathi
river
andWWTP, Bengalore, India

31.9-99.3<LOQ1062
401-1.1<LOQ-70.141.47
16

ND
ND
<LOQ
0.363.55
144.8
3.3-6.8<LOQ-6
0.36-4.90

DEET

4125
6.9-7.1
10-13
0.141.73
119

48.8

19.4

81.4

80.3

ND18.3152.6

101.3

592.3

490.4

105

11217.5

55.7

145

TCC – Triclocarban, TCS – Triclosan, MP – Methyl Paraben, EP – Ethyl Paraben, BP – Butyl Paraben, PP –Propyl Paraben, DEET – N, N – diethyl – 3 – toluamide
4. Perspectives for the future:
The present study and the past data clearly indicate the widespread occurrence of PPCPs in Chennai and Bangalore,
the two metropolitan cities in southern India. Some of those compounds do occur in higher levels when comparedwith some other Asian and European countries. Among these two cities, Bangalore, the more aristocratic city with
an affluent population has more of many of these compounds than Chennai where the people use more of naturalproducts as preservatives and beauty-care products showing the quality and way of life as one of the major way ofentry of such compounds in to the environment and non-target organisms. This indicates the necessity for switchingover more to natural products of PPCPs in future and also for continued survey of PPCP chemicals in the entire
major cities of India as well as other developing countries wherefrom such data are meagre.
5. List of publication and Conference presentation
5.1 Publications:

1. Srimurali .S, Krishna Kumar, S., Govinda Raj.S, Vimalkumar.K, Paromita Chakraborty andR.BabuRajendran (2015). Evaluating spatial distribution and seasonal variation of phthalates using passive air
sampling in southern India. Environmental Pollution 1-11 (IF. 4.839).
2.

Nikhil Nishikant Patil, S. Krishna Kumar, K. Vimalkumar, E.Arun, Babu Rajendran, R. Organochlorine
pesticide contamination in the Kaveri (Cauvery) river, India: A review on distribution profile, status, andtrends. In: Water Challenges and Solutions on a Global Scale (Ed. Satinder Ahuja), ACS Books, Washington,DC, 2015: 447p
3.
5.2 Conference presentation

1. K. Vimalkumar, S. Govindaraj, S. Krishna Kumar, S. Srimurali, Nikhil NishikantPatil, E. Arun andR. BabuRajendran.Nonsteroidalanti inflammatory drugs (NSAIDs) in major rivers of Tamilnadu,India. International Conference on “Recent Trends in Bioscience”. (07th – 09th February, 2016) at
Alagappa University, Karaikudi, Tamilnadu, India.

2. Vimalkumar K, Bhuvaneswari R, Govindraj S, Arun E and BabuRajendran R. Human andEnvironmental Risk Assessment of Organochlorine pesticides in Water and Fish from River Cauvery,Tamilnadu. Two days workshop on “ Micropollutants in water and their hazards” (12th – 13th January,2015) at IIT, Madras, Tamil Nadu, India.
3. Vimalkumar K,Srimurali S, Krishna Kumar S, Govindaraj S, BabuRajendran R.
Determination of PCDDs, PCDFs and dioxin like PCBs in bovine milks and ash samples by using
CALUX Assay in Tamilnadu, India. International Symposium On Halogenated Persistant OrganicPollutants (IEEP-2014) (January 16-17 2014) at CSIR-NEERI, Nehru Marg, Nagpur, Maharashtra,India.
4. Vimalkumar K, Buvaneswaran C. Study on effect of elevated CO2 on growth and nutrient
accumulation in important indigenous in the International Symposium on Environmental Risk
Assessment (ISERA - 2011) (17 – 19 October, 2011) at Bharathiyar University, Coimbatore, Tamil
Nadu, India