This study was undertaken to know the presence of pesticide residues in river water & sediment samples collected from the major rivers across India which are traditionally used as a source for irrigation. The study aimed to identify the presence of residues of most commonly used pesticide, endosulfan. The results showed no detection of endosulfan in any of the samples analyzed.

1. REPORT
on
ANALYSIS OF PESTICIDE RESIDUES IN RIVER WATER I
SEDIMENT SAMPLES FROM INDIA
'For
,4
t~
CENTEGRO
CENTER FOR ENVIRONMENT & AGROCHEMICALS(CENTEGRO) Kanta
Niwas, 11 th Road,
Khar (West) Mumbai - 400 052.
lJJy
SG$
Environment Division,
SGS India Private Ltd.,
Chennai
JANUARY 2a10

2. Analysis of pesticide residues in river water/sediment samples from India
Report .
Analysis of pesticide r!?sidues in riVer water/sediment samples
. from India
Sponsored by
Centre for Environment & Agrochemicals
(CENTEGRO)
Ready Money Terrace, 167, Dr.A.B Road
Worli, Mumbai 400018
INDIA
Study Performed by
SGS India Pvt., Limited
1/509A, Old Mahabalipuram Road, Thoraipakkam,
Chennai " 600097, INDIA
~-GSr SGS India Pyt Ltd., Environment Division, Chennai
1

3. Analysis of pesticide residues in river water/sediment samples from India
CONTEIHS
, ,
I S.No
,
: Description Page No.
,
,
, 1 Declaration ,
3
I
,
,
2 Quality-Assurance Statement 4
,
, 3 Certificate of Affirmation 5
,
,
,
I 4 i Summary of the Project ----------------~ ....
6
------,_... ---­
5 ' Project Details 7
6 Introduction 8
'''''­
7 About S<:;S India Pvt Ltd ,
8
,
, ,
,
,
, 8 Identification of Study Areas & Sampling Sites ,
, 10
, ....
9 list of SampLing Locations (Sediments and Water) 12
10 Sampling Procedure for River & Surface Water 18
11 ! Records Management 20
,
,
12 Quality ControL & QualityAssurance ,
, 20
13 • PartiaL Valid,ation Document for Pesticide Residue AnaLysis 21
14 Procedure for Sample AnaLysis 24
~---------
15 Results of River Water Ii Sediment Samples 26
.. -.-.... ,
,
16 Conclusion ,
, 34
,
,
...................,..
~naLYSiS
,
, ,
(FAO)
,
,
I
,
, B i Chromatograms for result along with the caLcuLations ,
,
, II
,
,
,
, C GlP certificate III
,
D ISO certificates IV
E • NA6L certificate V
F • MoEF certificate VI
SGS India Pvt Ltd., Environment Divis;on Chennai
j

4. Analysis of pesticide residu.€sin river Wllte(/sedirllent samples from India
OECLARATION'
Thi~ .is . to certify that the study "Malysis. of pesticide residues in river
water{sediment samples from hiia" , sponsorild by Ceriter for En-iironment and
Agrocnemicals ( CENTEGRO)' t)aving its. Registered office at Ready Money
Terrace, 167, Dr,A.B. Road, Worli, Mumpai, India. was carried out at SGS India
Pvt .. Limited, Chennai, india,. inaccordahce .with National GLP principles.
Place: Chennai
SGS' tndia-pvt, Ltd., Environment- Division, (henna,
3

5. Analysis of pesticide residues in river waterIsediment samples from India
. QUALITY ASSURANCE STATEMENT
Study No. 0101:1009
Study Title Analysis of pesticide residues in river
water/sediment samples from India
The Quality Assurance Unit of SGS has reviewed this report.
The final report completely and accurately reflects the analytical results as analyzed
in the lab for the above referred study.
The study inspections were performed on the following dates.
Date:
SGSlndia Pvt Ltd., Environment Division, Chenoa,
4

6. .- " , ----­
9;~~~Orqf:,'"'''''' >
,--_.- ...• , . : .,!- •... "< <,' C
..1 . .1na~si§"<i{b~csi:iddiii'feMdues in rlver
-- .. ;.
".' ¥iitJ'rlS'¥~iitl!!'rlf~tmQl~§'ff6inl riara .
'-; " . '. """:'_ >", >? ,_,_",< ,:' ',-; -'._ - .' .:,,-.--;"".7
.j.,' ',. ,_ '., -:--_.-' _,'
, ' " '--
'.'-- ,:.
, .c-
" ,,
',' ) ....... .­
It' i;':ci,;,tiflg'q; ih~t thesttidyihit~~ntiretY was performed in accordance with the
..r!rihciple;;:QfGpod taDor~tory Practice,. an':Hhe.fi~al report stands complete in its
origi!1~i;tya:ndaccuraCjlas per th~~rjriciples of GLP.
".
, ' - ' , "
..... ~:......
;.1 ,.~....,..
, - - ",', '. .
SG~ 'In4.ia' Fivt·l,..ti·, Environment i>-,vj~iCm; (henna;
" , " .' . ,
5
,,".' '
, ' ­
. ' ,

7. Analysis of pesticide residues in river water/sediment samples from India
SUMMARY
Agalysis of'pesticide residues in. river water/sediment sgmples from
. . . India
This study was 'undertaken to 'know the_ presence of pesticide residues in river water ft
sediment samptes coUected from the major rivers across Indla whiCh are traditionally
used as a source for irrigation. About 70 ~ocations were identified by in 6 different
states oflndia . The samples were collected and analY"ed for pesticide residues as per
national GLP( Good laboratory Practices) using state of art analytical fa!=ilities (GeMS
and lCMSMS) at our laboratory. The study was aimed to identify the presence of
residues of two most commonly used pesticides viz.} Endosulfan and Imidadoprid.
While Endosutfan, is a conventional pesticlde, Imidadoprid is a new generation
pesticide. Both are widely used in Indian agriculture. The samples were analyzed as
per US- EPA 3510C a EPA 3545A for presence of folloWing residues.
• Alpha Endosulfan
• Beta endosulfan
• Endosulfan sulfate
" lmidadoprjd
• The detection limit: 0.00001 mgll
The result:
Endosulfanllmidacloprid residUes were not detected in any of the samples analysed (
BDl' : 0.1 ppb)
• BOL: Below Delectablu limit
SGS India Pvt Ltd., Env;ronment Division, Chennai
6

8. Analysis of pesticide residues in river water I sediment samples from India
PROJECT DETAILS
I. GENERAL INFORMATION
•• Date of Initiation 1410712009
b. Date of Completion 30{1212009
c. Name of the sponsorer : Centre for Environment a Agrochemlcals
(CENTEGRO) , Mumbai , India
d. Name of the research centre: SGS India Pvt Ltd.,
Ufe scienc.e Services)
Ticel Bio park, Taraman;
Chennal - 600 OB,INDIA
N,onitoring Team SGS India Pvt Ltd., Chennal
S. Suresh Kumar, Tech. Manager
Mr.J.Palani, Sr. Executive
M.Pugazhandi, Operation lncharge
Anand, Field Chemist
SGS India Pvt Ltd., Gurgaon
Mr,Utpai Mazumdar, Operation Manager
Mr.Amit Ranjan, Operation Incharge
SGS India Pvt Ltd., Thane
Dr.Santhosh, Section Incharge
MLNikhil, Field Chemist
SGS India Pvt Ltd., Kolkat.
Mr. Desarkar, Operation Incharge
Mr. Amit Dutta, Field Chemist
so) India Pvt Ltd' l environment Division, ChenoGi
7

9. ,Analysis of pesticide residues in river waterfsedimentsamples from India
1.0 INTRODUCTION,
Around 226 pesticides are registered for use, in agriculture in India as of 2009, against
" , ,,' - ­
various pests and, diseases. These pesticides can be broadly classified into
. . " - . .
Ihsecticides(used for controlling insect pests), Herbiddes (used for controlling
weeds) a'nd Fungicides (used for controlling fungal pathogens ). All the pesticides
under~o rigorous toxlcologkal, inc,luding eco-~oxico'ogical risk assessments prior to
commen;ial introduction. However I the general public have apprehensions about
contamination ofwafer sources with pesticide residUes espeCially due to run off from'
•
agricultural fields following rainfall.
Hence., this study was undertaken to determine the pesticide residues in river water
8: sediments. Two most commonly used pesticides were seiected for the study~
Endosulfan and Imidacloprid. The former is a conventional pesticide and· the latfer is
a new generation pesticide. Both are widely used in Indian agrkulture. The study
involves samples taken from rivers across India and is the first of its kind,
2.0 ABOUT SGS INDIA PYT LTO.,
SGS India Pvt. Ltd is a member of SGS, the world's largest control and Inspection
Company. Represented in more than 140 countries, by 210 affiliated companies this
j
vast network of companies yields more than 2,000 offices (66,000 employees) that
maintain over 340 laboratories.
SGS is globally recognized for analytical an~:r technical. excellence in environmental
assessment. This undisputed reputation is based upon an exceptiohat record of
progressive growth ana development by continuing to exceed the standards of most
full -service environmental laboratories.
SGS Chennai Laboratories have been accredited by various organizations like GLP,
NA6L, 61S, APEDA, EIC etc" and provide wide range of testing of Air, Water, Soil,
Solid Waste) Pesticides Residues etc.
SGS india Pvt Ltd., Environment Division, Chennai
8

10. Analysis of pesticide residues in river water/sediment samples from India
Analytical Capabilities
a
SGS Indra Pvt. Ltd. is fult-service,environmentallaboratory. Analyses are performed
locally on a variety of matrices, inc,luding; soil, sediment, sludge and other solids, air}
indus~dal and riiunic:ip13J effluents and w~-stes1_ groundwater and surface water 1
dr-inking water capacitor and transformer oils.
1
SGS India Pvt. ltd. personnel are proficient in diverse methodologies, including:
» Solid Waste (SW 846) Procedures for Metals, TOC, AVO, HVO, voe, SVOC,
» Pesticide and PCBs, EP Toxicity Et TelP
» EPA and Standard Methods for the Examination of Water and Wastewater
» NIOSH Methods for Air Testing
~ US EPA Methods for stack emission
~ Pesticide and PCBs' USEPA 8000 Series, SW 846, SW 8082, EPA 525.2
» Water and Waste Water - EPA 525.2
~ Air Testing - NIOSH, OSHA, BTEX - NIOSH
» Volatile Organic Compounds - EPA I ASTM I NIOSH
» PAH s - EPA 8270
~ US EPA Methods for stack emission
SGS laboratories are well equipped with facilities to perform the foHowing
experiments
» Ambient air analysis
? Process I work zone analysis
-.,. Stack emission analysis
):> Outsourcing of manpower for environmental monitoring.
~ Volatile Organic Compounds.
» Heavy metal detections.
};> Drinking water, raw water and process water analysls
:>- Biodegradability studies
SGS India Pvt Ltd q Environment Division l Chennai

11. ',AoarYSisof pesti~ide (e~id~esiQrj"e( waterlsedirnent:amplesJrotn lodia
}>~r~siificles ana~~~iS " '...' ;
. '!;' 'Stijl;'S9lid .atld'fI~zi,rdous-W~sti!a~al¥:,ijs
:> ,i>i i~iryand~hi!r sPeCialil'eq par~m et!rs.. .
,"0-- _,. _ ,'- ,.'... '-','
' ..' ~ .' l~dooiair.qu;iliW .
" . EnviiorimentalAudit
3.0IQENTIFICATION OF~TUbvAREAS ANI) SAMPLING SITES,
The. shJdY area' and sat]1pling' loc.ations were indentified based on the possible
potential· for "fl,iater contamio.ations by· pestiddes. . The _sampling lpeations were:
. . - . "
seLected closer to., the pla~es- w~ere _ jntensi~e ag~tcultural actiyities. are practiced as
suggested by sponsor. 70 sampling sites (rivers) 'were selected for this study from 6
different states across the. country cov~ring diff~r~nt climatic and agricultural
regions.
50S India f>v! Ltd., Environment Division, Chenna;
10

12. Analysis of pesticide residues in river water/sediment samples from India
SAMPLE COLLECTION AT TAPI RIVER NEAR KAMREJ (35 KM FROM SURAT), GUJARAT,
INDIA
OVERVIEW Of PURNA RIVER AT CHANGDEO, MUKTAINAGAR.
JALGAON DlST, ,MAHARASTRA ,INDIA (60 KM FROM JALC ",'(i)='=F"1[
~.,:
i,
'i
'ft. G V
UKAS : I
~'_" SGd .....'t~'!.1~~ II
~ 'f>:;:..J I
I
I
SGS India Private Limited En.vironmenral S~r'ke.'i. 101, Signature_ I, e,p.c. Road, Urrni Char RaSia, A1k$.puri. Baroda - 390 007. t 191·2GS}
233.35.09. f (91·265) 233"'j::3R;.81~.""""",_ _...."
-.",M"'",~-''''·lt''hi'''ol",,:(~'~rl'"''.b~."',b';!1;-4 '",,",,"e3>-.''''1''91''''''~'''''5"''79H'!4'''.'''1 -fi91 22) i!S.79.e~.3",
..
SGSi SGS India Pvt Ltd., Environment Division, (henna;
11

13. Analysis of pesticide residues in river water/sediment samples from India
4.0 DETAILS ABOUT THE SAMPliNG LOCATIONS AND DATE OF SAMPLINGS.
LIST OF SAMPLING LOCATIONS (SEDIMENTS)
. 1.' Valgal - Kochadai, Madurai.
2. Bhavanj - Palljpalayam, (Agragaram), Erode.
3. Satluj River· Ludhiyana(Pufljabj - Down Stream, Near Bridge
4. Satluj River· Lohiakhas(Punjab) - Down Stream, Near Bridge
5. Chambal • Chambal, E.tawa Distt. Near Bhind Road Bridge
6, Yamuna· Mathura, Near Rail Bridge
5.0 DETAILS ABOUT THE SAMPLING LOCATIONS AND DATE OF SAMPLINGS.
.
5 1 UTRAPRADESH STATE
""""""", " . ,
, I ,
I ,
, ,
Sampling Sampling Total
SI.No River location
-­ .. __... Location Date
-----_...
Sample
Varanasi
1 Varuna Varanasi . . 22.10.2009
. Town .
·
·
I
Away from
2 Ganga •
•
•
Varanasi 3km from 2Z.1(tz009
•
• 180 Ghat
I,,, Near
3 Gomati ,
, Pilibheet Surajpur 23.10.2009 1
,
,
, Village
4( Deva Pilibheet
Near road
Bridge
23.10.2009 1
~.
Ganges ,
,
Daal Mau Daal Mau 28.10.2009 1
,
-,, ,
Bahraich I
I 6 !
,
,
Sarayu Bahraich 28.10.2009
, District .
, Lalitp~r Near Grash
7 Dhasan , 29.10.2009 1
,
, District , Village
,
, Etawa Distt.
8 ehamoal enambal Near Bhind 30.10.2009 1
Road Bridge
Near Rail
9 Yamuna Mathura 30.10.2009 1
Bridge
·-
·
· Near Hapur
Bhoipur 01.11.2009
Road Bridge
Total Number of Samples 10
SGS India P'(l Ltd., Environment Division. Chennai
12

14. .,
,. ' 1,
,
,
,
5 .10)0'09
6 Be~~-j{i)er 1
"
7 ,Rav.j Rjver
"'
,.,, 14: 10:2009' 1
"
"
14,)0:20D9 1
1
,
,
,
, 10 1
,10
, ,
" •
.J­
'sds In'ifii;,,-~'t'J:td~::-E~vir~h~,~ht'-~i~;r5ioh'; Chen~(i
" ".', ',; " . ' , .:,~
13
,,'. ':: >,' ,,",
~ :'.' ";
.-;: :,~
•
'/­

15. Analysis of pesticide residues in riv~r water !sediment samples from Indla
5.3 ;TAMIL.NADU SlATE
1 -Thamirab,harani Kokirakulam '-: K6kirakulam 09.09:200:9 1
.' :
·
, · I
+
·
~~--~--~.--~~--~~T.!.~------'·~--~--~
~2---1'~~Va~ig_ai
. .
Modurai Kochadai 09.09.2009 1
ir.
,3 Cauveri Tiruchirapalli Tiruchirapalli, . 11.09.2009 1
· Srirangam ­
·
·
·
·
;
I 4 Pennaiyar Villupuram Th'jrukovilyur 13.11.2009 1
;. Pallipalayam
5 Bhavani Erode 13.11.2009 1
(Agragaram)
I
I
: 6 i BhavaniSagar : Bhavani sagar Bhavani 14.11.2009 1
·
·
·
Noyyal Karur Kombupalayam 14.11.2009 1
8 Paiar' Chengalpattu Dimmavaram 16.11.2009 1
. ·
---~-~""""':""
·
· .
.
·
·
9
.
.
I
Pennaiyar I Cuddalore
·
·
· Thiruvevdipuram 22.11.2009 1
Total Number'of Samples 9
SGS Indio Pvt Ltd., Erfvit'onment DiviSion! Chennoi
14

16. Analysis of pesticide residues in river water/sediment samples from India
5.4 MAHARASHTRASTATE
Sampling Total
SI.No. River Location
. Sampling Location
Date . Sample
TAPOVAN, NEAR 25.10.09
PANCHVATI, 25 KM FROM
1 Godavari Nasik 1
NASIK CITY
DIST-AHEMADNAGAR, POST 25:10.09
Western RANDHAWESTERN
2 Parvara 1
Maharashtra MAHARAS.HTRA
.
.DIST-AHEMADNAGAR 26.10.09
Western
3 Parvara (WESRTERN MAHARASHTRA: 1
Maharashtra
70 KM FROM RANDHA.
WAI, NEAR
4 Krishna Pune 1
MAHABALESHWAR 31.10.09
AUDDUMBER, NEAR SANGLI 01.11.09
5 Krishna Sangli, 1
. POST MHAPUR, TAL-LATUR, 02.11.09
DIST-LATUR;
6 Manjira Latur 1
15 KM FROM LATUR CITY
Amaravati, 11.11.09
POST CHANGDEO, TAL·
Akola,
7 Purna MUKTAINAGAR, DIST­ 1
Buldhana &
JALGAON
Jalagaon
70 KM FROM JALGAON CITY, 12.11.09
8 Tapti Jalgaon 1
35 KM FROM CHANGDEO
Yavatmal, 16.11.09
Nanded,
POST MAHUR,DHANODA
Hingoli,
9 Penganga PHATA,75 KM FROM DIST­ 1
Washim and
YAWATMAAL
Buldhana
districts
PAITHAN, 56 KM FROM
10 Godavari Nasik AURANGABAD 29.11.09 1
Total Number of Samples 10
SGS India Pvt Ltd., Environment Division, (hennai
15

17. Analysis of pesticide resiciuesin- river ;';il.rer Isedjln~ntsamples from .IDdia
. -
"
-- - -
. ~;5GU~ARAT STATE
: ; ::-., -,. .
.
,
" , ',­ -
, . Sampling Total
SarnPli.i!l1,9~~tioh .·o.• w··
.
: ~r. No." RiVer !,ocati6n .'
- .' , " " (" .. · sal,lPle
.. ,' ­
, ,'" ,
I
,
,
,
I - -
, .
,
:', - - I .1) NEAR EUS BRIDGE,
1 . Sabarama!; Ahmedabad; , AHMEDAMb
. .1
'. I
, Vadocara , VASADi 25:~ FROM
Mah; '" VADOOARA '. 29.10.09 1
Nar:maSia l
'­
.6AHRUCH. ,
3 Narmada· VadoiWa 6: : 30.10.09' 1
Bharuch .'
Shetrunj : 15 11M FROM 21.11.09
4 Palita~a
., PAlITANA,'G1)JARAT
,
. Nadi, ·2HMFROM
I 5 Bhagad 21..11.2009 1
D~ng?lrpur D!.!NGARPU R
6 Bhogavo' , , Surendra 15KM FROM
21.11.09 1
I Nagar SUREI'iORANAGAR
. DHARAGIRI {1011M
Dhupeshwar
l
J -
FROMDIST,NAVSARI,
Puma Malkapur, GUJARATj
22.11.09 1
7 Navasari
1)PQST RANDHER, TAL 22.11.09
Multani, ({11 KM FROM SURAT
8 Tapi CITY)
1
Betul
I
CH)-IQTI CHILDD, 25
9 Sabaramati. Garidhinagar KM FROM PALITANA, 1
I .' GANDHINAGAR
5.12.09
Multan;, NEARKMlREJ( 35 KM
10 Tapi 1
Betul fROM SURAT 12.12.09
I Tot.l.Humber of Samj>l::::e,,-s_ _ _ _ _ _ _ _'-_1"'O'-..J
SGS India Pvt Ltd:, Environment Division, Chenna;
16

18. Analysis of pesticide residue.sinriver water/sediment samplesfrom India
. . -. . '. ". . . ."
5.6.ANDHRA pRADESH
:. , ,
,
, SAMPLING
,
,
, N~. ~f
, ,
.
! 51. No. .
NAME Of
RIVER' I location I' SAMNN(i ,
. DATE
.
,
,
, Samples
,
·
·
· ·
·
·
. LOGATION .. ,
· '1
~""""MUSi
"""""~
Suryapet. $ury~pet 17.11.09 1
.. ..
I I
I 21 Paleru Suryapet
I
27.11.09
I
1
3
Sabari . Shadrachalam Bha:dracha,lam 27.11.09 1
, ..- .... __.
4 . Pranahita Ad,ilabad Adilabad 27.11.09 1 •
, ,
,
I .. """"~
,
5 Swarnamukhi Srikalahasthi . Srikalahasthi ,
,
,
27.11.09 ,
1
, ,
,
,
,
6 "! Tungabhadra , Karnool Karnool 27.11.09 1
,
........................... 1 I
iDindi_-
.. ..
..
.. ..
..
..
7 Dindi Dindi 27,11,09 ..
..
..
1
..
..
.._ . .. .... _....
. ..
..
..
8 Manjeera Sangareddi Sangareddi 27.11.09 1
I
..
..
..
..
9 i Pennar River
..
..
..
..
..
Nellore Near Bridge 02.12.09 ..
..
..
..
1
.. .. ..
,
,
..
Gundlakamma
10 Ongole Ongole 03.12.09 1
River
,
,
,
, Vijayawadaand Vijayawada and Nagarjuna
11 . Krishna River , 03.12.09 2
NarAgjuna sagar sagar
Karimnagar and Kar5m Nagar and
12 Godavari River 04.12.09 2
Rajamuridry Rajamundry
13 Sileru River SriKaKulam Srikakulam 05.12.09 1
• Total Number of Samples 15
.~----
SGS India PVt Ltd., Em'ironment Division! Chennai
11

19. ,,',
" -',
','
--',".; ,:.
O(,:u5,tbdy se.ais
·1'-~_(A~("PJ:as.~),~::Jars', ',_ '.
-' ,-.;
Alum,in'l.Jm foW
. Ut:ITtdsf ;care, was..t,~lSeri, : to- ,avpi~ 't6n-tamina~i'oh ,by~ rld~ tq'uchlrig the' containers"
~·a~p.les 'e~'~,:
. '
W~e'n.;_c:~e~nng, '~a8p.l'.i'ng. '~.q~ipi:n~~~', aU- .the--. safety' p~ocedur,e~
.' " ,,'.'.- '.
" " ',,' - ',- ,-,," '" ,
were
,folloWed a.s~p_er Etqlogy ,Cheniitat:Hyg{ene Pi~an':as_ gi:V,~n below.
',' ,-', - .'.,' -'.' -,' -' . . . - ,"
,"., '-~Wa's,ke:d-wj'th/h~'t, ~at¢'r.~,;:~-rJ~'::8r:ij~h_~ci,w.i.th '~iqu_l~:~i d~ierg~nt. '.
• '::,Ri~~~d?0Ah;-':th-~-:·0'~t~f.'fci{:~b:6~-t3-_fi~~·~'.,".,'::_, '.:--',"- '.
-,-~:''-''
','.<--: ',,:,' '-~ ,.... :,':, -.: ':
,'i-_:."Y~'--,-,->,:-;:,--_'r_:-.:~:~-:,:.'.,} i" :
.' _Rin,sed '~ith d~ibnized'»,ater': 3-',Jimes._-antl drained.
• Ri'~}~d':With~pe'~t'i~_id'~--g-t:a'~:~~~-~~~td~'e',-~a~d:d_tied:'iri -f~~e, hb~,d.
~ w.ra~:te·d -i~:,~l~~'i,~dR(f"~H-:~j_~~-: 40,ll: si,~_~:-t~W~r.ds_ _ sah~prln'g:-:equ_ipment~
r :.-',
,.,>
-'- ,,­
;'.'
;;,,-,.
:'" ,
- ..
.
","
,
/". ", ,,-' .';
[S
'-_',c_ " .
,- -.­
.,,'
,C'.­
',-' ,
,:;,;,,-'
" - ,.
':<'-.:';-> 'i_:
',-',
,-',"
'i" --
;,.-, _ .- _.
',' - ­
,_ : c
- '; i",
"'I,
~,_-'

20. Analysis of
. pesti~ide resio~es i~ - riv,!r~ater /sediment samplesfrom India
"., - , ' ,'- , .
'-' "',
6.3.1 General Sample C6liei:ti6!l Techniques
. -. .. , .
.
~ '­
River "later and· sediments sampl;'s wetecoll<ideo,at thequart"r point transects
c6rsii:Mring the width~f the rive;. three'di(ie'r~ni,sa;"pling poi~tswere identified as
right bank, left bank and center of
~he river.' Samples were collectedfadng upstream,
.to avoid collecting the recsuspended partiCles Dy wading.
Sterilized containers we,re ~,~d for sample -coHe~t~on_.. -Nitrlt~ g~6ves were used while
sampling to protect the samples from contamination. Care was taken to avoid
collecting a disproportionate quantity of w~ter or suspended sediment at the surface
of the river or stream'. Care wa,s also taken, nbt to disturb the subslrate with the
transfer bottle 6r collect anything from the substrate.
To collect water samples 1 liter ja~s were used in area where water level was less
than or equaLto 1 foot grab (manual): River, samples were taken from locations far
away from the bank as possible and" by submerging sampling bottles about 1 m deep.
In some places, 'however 1 this was not possible due to shallow water levels.
Water Samples were collected and poured into the containers tm top of containers
(leaving no headspace). Sample conta,iners wer~ dosed wi~h the tid immediately on
the spot to avoid contamination from the atmosphere, rain, wind etc. The samples
were labeled immediately. The samples were subsequently placedi" the cooler box
to bring'down the· temperature and to preserve the samples. till they were extracted
and analyzed.
Sampling, details viz., mime of the person, date of sampling, locations, time of
sampling, weather conditfons. at, the time· sampling etc were recorded by the
sampling person.
The water/sediment samples were stbred in ice box during transport «6 h) and were
kept at 4"C in the laboratory «2 d) until SOlid-phase extraction. Sediment samples
were taken 'from river positions where an accumulation of fine-textured substrate was
observed. Samples were taken an'd compos1te samples were pooled from four or five
.ubsamples (0-10 em) of a 10·m' area, homogenized, and wrapp€'d in aluminum foil.
SGS india Pvt Ltd., Environment Division, Chennai
19

21. ".- ,
',"" -
", '
" " :"
;", '. pre~a(e~:iRY fii [jOg a.."arpple.·
to {die~kfor: poSSible
." . .. ' .
'
,;
,_0.
, .'.' -, ',',-:
.
. . ,::
' "', .' .- .
',' - ''- ':
:;.
,',
, ,
, "" ",. '-"

22. An~lysls of Restitide residues .in river ""att;rlsediment .samp}esJrom India
. . . ". '. .. .
After·reYlewing,the, n'portit was handed.ovN to the prp)ect l~a<ler for fjrial report
pre'pa'ratidn~
. .
6.7 Safet~
. 0,.
Field work done in. connectlonwl,h collecting water/sediment samples In surface
waters'follow~d the protocols described in the Environmental Assessment Program
. '. . - ­
. Safety Manual."
7.0 PARTIAL VALIDATION DOCUMENT FOR PESTICIDE RESIDUE ANALYSIS
7.1.Scope:
'. This ,Is a genl'ral purpose method that provides the procedure for determination of
pestkld"s residues in wa~~;, The method is applicable to a wide range of pesticides
that 'are effectively partitioned from the water sample and sufficiently volatile and
thermally stable for gas chroinatography. The method is used to extract; indentify
a~d qu~ritify the foUo';"lng pes't:iddes. 'A'ldrin,. Dietdrin, 'Endr'jn~ a BHe, 8 BHC, y BHC,
~HC" End~sulfan, Ethion, Chl0'l,yriphos, Phorate, Butachlor, Malathion, o,p DDE, p,p
.DOE, D,p DOD, p, P DDD, Chlordane an~ Methoxychlor.
7,2 PriiJ'iPI~:
Pesticide resiDues are,extract~d with a mixed solvent ( hex'ane I methylene chloride)
'using"separ-ating funneL The .extract is concentrated by evaporation.-The sample
components are separated, identified and rnea~ured by injecting an aliquot of the
concentrated extract. into a high resolution fuseQ sRica capillary column of gas
chromatography - Mass Spectrometry system, Compounds eluting from the GC column
are, identified, by·' comparing th~jr me:asured mass spectra and retention time to
reference spectrum and retention times in a'data base.
Reference spectra- and retention times for analytes are obtained by measurement of
calibration of standards under same conditions used for samples. Concentrations of
each identified component is measured by relating the mass spectra response of the
quantltatlon ions produced by that Compound in the sample to the mass spectra
response of the quantitatibn ions produced by the compound in the standard,
SGS India Pvt Ltd., Enyironment Division, Chennoi
21

23. Analysis (jf pesticide residues ihriver water/sediment samples from India
7.3 GeMS conditions:
Carrjer Gas : Helium.
Inlet Temperature : 250 'C .
Injection volume : 3 ~I
Mode : Split less
Oven Temperature: 80 'C hold for 1 min.
10 ·C/min. to. 250 '(hold for 1 min.
10 'Clmin. to 280 'C hold for 10 min
GC Column : HP 5MS (30m X 0.25 ~ X 0.25 mm).
7.4 Reagents;
1. Methylene chloride
2. Ethyl Acetate
3. Acetone
4. Toluene
5. Sodium Sulphate anhydrous
7.5 Extraction Procedure:
Shake sample weH and accurately measure sampte_ in a one titer graduated cylinder.
Pour the sample into a two liter separating funnel. Ri",e the cylinder with 60ml of
solvent (15% DCM in hexane). Pour the solvent into extraction device. Shake the
separating funneL vigorously for 2 mjnutes. Allow the Layers to separate for at least 10
minutes. Drain the water phase Into sampLe bottle and carefully pour organic phase
through a 2cm OD glass column that contains 8 to 10 mm of anhydrous Na2S04 into a
turbo vial. Pour the sample back Into separating funnel. Rinse sample bottle with
60ml of solvent.
Repeat extraction and pass organic phase through same sodium sulphate. Wash
sodium sulphate with several portions of hexane and drain well. Evaporate to dryness
under nitrogen and reconstitute to 1 ml with ethyl acetate.
Inject 3 ~l of extracted solution into GeMS.
SGS India Pvt Ltd., Environment Divisi01'l, 'henna!
22

24. .
- - .
'Analysis of RestJ~id~ resid~es in riverwat~f I sediment samples from India
. . .."" ,'"
" " '" .' " ..
_., :
7.6 S.tandards;
The primary ~toc~ sta.nqard ~as'ma~e accurate!y'from standard pesticide mixture and
then dilUted to1~ml'gi"'ingas~aijd~rdoi100 ppm. Working standard 1 was made by
. dHuting 1mlb! pr{marystoCksfandard t010rnl with toluene giving.concentration of
10 ppm. Wb;king st<lndardZ w~smade by diluting 1 ml of WS1to 10 mlwith toluene
----' . . , '
giving·,oncentration of1 p~m: Working standard 3 was made by diluting 0.1 ml of WS2
. to 1 ml with tOluene giYingconcentration anOO ppb.
, . ," .
.7.7 Method Valida t;on:
The Method used for analysis was validated as per the EU, Eurochem, AOAC and
[SOllEe 17025:1005 requirement.
7.7.1 Selectivity
SeLectivity of a method refers to the extent to which it can delermine particulate
anatyte(s) in a compLex mixture without interference from other components i,n the
mixture. The term selective refers to a method that provides responses fOT a number
of chemical entities that mayor may not be distinguished from eacn other. If the
response 15 distinguished from all other responses the method is said to be selective.
The analysis was carried out in SIM (Selective Ion Monitoring) mode, three ions were
taken for confirmation. and reiative intensities of the detected ions are compared with
those of matrix matched standards.
7.7.2 Linearity:
Matrix matched 5 point linearity was plotted from 3 ng/ml to 500 nglml as shown in
ANNEXURE 2. for plotting the linearity several one liter portions of water was
extracted and evap9rated in the turbo vials. When the voh.,lmes were tess than 0.5 'ml
pesticide standards were added to the vjals and evaporated to dryness. These were
then reconstituted with 1 ml of ethyl acetate. This helps to equalize any possible
matrix effects in the chromatography or fragmentation between standards and
samples.
SGS India Pvt Ltd.! Environment Qivision, Chenna1
23

25. Analysis of pesticide residues in river wat.erlsediment samples from India
. .
7;7.3 SPII(E.aR.E<:;9VERY:.·
Accuracy is estirnatedfromthe recoverY of spikedanalytes from the matrix of
intere~L Labofi;lto..y: perfon:nance in ~ dtiB1 m~trix is estimated from' the
recoverY of ( R)
%R = C, - Cu Xl00 I C,
where:
CS:>O Measured' concentratj~n'of th~ spiked sa~ple atiqt!ot
Cu= /lieasured c-oncentration' ot th_e unspiKed sample al~quot
Cn : : : The 'nominal cpncentration of the spiked aliquot
beta-Endosul!an 50.12 48.25 51.30 49.83 50.1 100.22
3 ·41.44 43.29 39.44 39.25 4.0.3 80.62
5ulfate
4 : Imidadoprid 48.50 49.20 49.50 49.20 49.00 49.1 98.16
8.0 PROCEDURE OF SAMPLE ANALYSIS:
Sample Extraction:
Water samples were filiered (using glass fiber filter) and subsequently solid
phase extraction column was. conditioned by eluting 5ml each of ethyl
acetate, Methanol and water. After extraction of the water sample the residues
were eluted from the cartridges by n-hexane (8 mL) and ethyl acetate (12 mL).
The eluate was concentrated by turbo wap and it was finally analyzed by Ge­
MS.
_SGS.- SGS India Pvt Ltd" Environm~nt Division, Chennai
24

26. ':> ;.
, .'....:,,",' ,.,:.;i,; ·,·h . ,~<::::"<,::;' ":::"i.~: ;':': ,."" . ,:"",'::',~.':_ :,': , ~i:"'f:": ,'·.r'·' ., '" .:.,.,,:';:',:"~', ':',' ",:::'"
'.' . ~~a,(Y~i~~t I's~ticjd!;: '~~~}cjl1es in.riv~r ,:"a1"t(~e€jirnE:~~ ~~.l]Jpll'sJr()r;I1lhd j ~.
".';:' .:~ ".-:{;::',;';f:~, " ',:;"'" ~;"':' ~.< ,,':,f/:,;'~~ ::' :::,~}.":';':;, ..~,~.,::; ': ~" '.,' ' ,',':';,?: :t/;;,.:'<':, :":~' ,:,:,:;.,.: ,:.: -.: ::~_ :':
1 ';':;";':: '; "-'" , , ,'"
.. ' ..>' Se]'lj!ll~ijt'.s:l!J'1pt~~;(aR8rpx'in)~terY;25g d.t~·i4eight}0;i"e extracted wi'th . a
"''':'','' ',', ,- " , ; ' ' , : ' .'" ' , " . " " .• , ,',.':"~,,,';:"'-I-"",', ",.,','":<.",, ,; , , , ' , ' , 1 " .. ,,,
... . . . .~j~tV~<i:~rac~)~Q,e;~~~ll~~<;~;t~~[;~?q;:.%'~~~r:')V'~r. ~~~~s.~i,~r:ip~:.~l1~kl)1~
.". ...fl~#~5>"'~r¢:5~htrjfU~~'<!.a~~~; ~h~n~[Tfl~;¢:i.1if7t,. ~as;}~'i'fi,?¢~~~~e~ . . a~d.·
.iitt<t",d,·· F91~ow)ng.th~r~ri)~~~kR(.{!W"bn«wic· " , " , ' ; ' , " , , ' ' ' , ' ' ' ' l !;a' -.,roPTY
," :"~ ,;:,';'- "~,,,' -"'>',:":",·,;.'>:"~"·"",:,,,,,;,·.,;,,,,,'''' ____ '',,'·r·,', "
sq.lYents.)I1ith ' ' .' ' ,:"
evaporator, tl1e .remainins·':water ph.se '·wa.s ,liquia-iqyjd extracte,d J :
.,__,-. ~'_,'1", c,.,,,',, ",.,1,/ 1>:,·" . . . . < • • ,;'____"",.'< I ' : , , - "
• '._
'wih
<jitHl6'omethime. 1' x):5 m~}" Tne .organic phase Was th~n dried'yYith sodium
'~:::':"',,'-':;"', ,''.",'',,'''!''--'.<,".".-,':,.:.,',,'. """'>"i-""',~.' :,: " ,,' '.:"
. sUlfaJ;e~n(j~topCe)1,rq~!,d~gaih'wih ar~1i'r¥eYiip.or.atlJr,.Afte't~e?a~pl"
.#kij",d·i1a~D¢.l~ .JI~nsf~Yr,~"f:•.!ithe,,cQllnnh:: ",',"",.,'>". .',:----.',:,:' ;Sliil,. ..of
'. .', .,:: ~-::::".-<", "c-, "", ,'~/,•• ,'. ',-" '-' .'.', ,,',_'.,"', :.': ';
"':in~ppr.o~iitWel~O
,~'.",'.'.,"",
t()r(r"h~;}he ~~stki(j~'s.wer~ :~9!,s~c~tively erUt",pH.om t~e: c.owrnh)"ith10 (l1l
ofn,hexan~·an1l10.mL of 'n;h~xai)e-aiethylether 1,1 (vlv). The 'eluate was
cOricetitrai~dwith a,rotar'{ ey~pilat9r~l1dttieO~nalyze9 by GC:MS. Glassware
usellduririgsa(l1ple priicessing;y;a{rinsed With ethy(~cet~ie and baked at 250·C
(>4h)befoieever'{use,
Pestici.d~ t~~idu~s weT~ .qua~tif'i~d. with GC-IS w~ich was ope~~ted in the
set~~ted jon~m9nito'ril')g' mO'de at the,.f6lto'Y'{ing conditions
" "
Carrier Gas : Hei;ur'n
Inlet Temperature : 250 '(
Injection volume : 3 ~l
Mode : Split less
OvenTemperature : 80·t: hold. for 1 min, .
10 ·C/min. to 250 'C hold for 1 min,
10 ·Clmin. to 280 'C hl)ld for 10 min
GC Column : H~·5MS(30mX 0,25 ~ X 0.25 mm).
Quantification and identific~tionQfsubstarices were achieyedby measuring one
target and two additional qualifler ions, ~espectively, per substance, The
calibrati,ori was performed With:' six-pofnt lirlE~ar "functions) with €;ternal'
standards.
Analyte peaks in Sil(l1ple eXtracts were identified by 'retention 'time, presence of
ta'r'g'et 'i;lhd"quaLifier ,ions, a'nd r~'s'pectlve ratiQs of target ~nd qualifier 'i~ns.
25

27. ,:. , '
AnalySis of pesticide residues in river water(sediment samples from India
. .. . ". ' .. " - ','" " " ',' ,',' "":~ "
Duringthe extraction olwaters~inples, bla0kswer~pro<;essed regularl{ Blank
cOnceritrationsweresubtracted fr~.nic~ltG(~t;;cts~h1ple20nceritrati()hsfbr the
respective pestiCides and processing lots; ,;sthey were thought to derive from
¢ondensationof pestitides, . surfac~s9f .
. . '" . , -
on '-_. - giass vessels within the laboratory .
','
9.0 RESULTS OF RIV'ERWATERSAMPlES:
All the collected fiver water samPI", ahd Sediments. were analysed for
pesticide residues 'viz Endosulfan (alpha, beta), Endosulfan Sulphate and
Imidadoprid and the results showed that Uiere were no· detectable
residues. (DL :0.00001 mgtl).
",..c_
-----.V.u~ SGS India Pv: Ltd.) Environment Division, Chenna;
26

28. .,;. ~
Sarayu­
.' ,:.
,
-';, -­
, '

29. Analysis of pesticid!'lre.siplJes in riVeT water /sedimentsaITlJ;>leS from I.~dia
.. .. .... ..
! STATI . , ." . : '.' .' .. . '. . . 1
; Satltlj" Riv.er
,,: .. ' ..' . .~:: ~",g! 1
(~unj~h) .
. ;".~".~
::. '~:~':;' :0' '. i ....... ~. ~:~'~+~:';l) !
Satlul:River
, '. I ~~DL:' .lm.JI):.
'~.~ .:~m.d)
~ '~m.111
12 (Punjabj
Ine~r bridge
J" I . m .DL: ... ",gil)
13
Satlu{River
(Punj~b) -
19hiaKhas. ­
, ~nstre~m, ~ :B~L ~~;;:~
; near bridg'e
~c' '~,""/ll
r.,...14-1-----l~~-'-~······--~-+Be-a's·,·"D·'ow-n--'-f~~Z"'· •~ . :~m'll '
6eas River Stream, ,Near - I mg/l)
: Joadl~r1dge ~~..m~! n
~15T~~r-~~t-~"-~iIHar
Har'G051ii1dpi;,:;,-jj~- '. :: ~~:~:;
Beas River
Down Stream, ~~.~ .; mg/l) ;
13.10.2009 ' Near Road , _: mg/t)
; 16:~Opm I Bridge ,
,
, : Rn! ri,.:, nrum, mgll) :
iI
16 : BDL Q!c~ m.111
: Kanuwat, Down '
13.10,2009 Beas River ; Stream-, Near . I BDL'tJh.:.O.OOOOI mglll
,
18:45pm I Road Bridge
". , mgll)
i
BDLIDL I mgll)
, ,.Down
LQtl2(l'l,m.,
17 I
RaYi Rive:r
Stream, Near,
Chandlgarb post
BDlfDl
JiglDl ).00001 mgll)
: 0.COOD1 mgll)
, : 14.10.ZC09 ,
, I [Pakistan
i
11:30am ' Border]
i
, , • Rh' m, : 0.00001 mgll
r- o
~1 ~!;:
-----
18 , •........
:'
i Ravt River
,
, • mgli)
I EDUDl :~ m.1
:
,
!BoLiDL.: . I mgl
19
I
:
, Seas.River
·~lDl:.
: I mgl
I mg,
I
,:
I Rm m : 0.00001 m.,
20
15.10.2009
Ha:rike, Down
~~~:~~;~II
Beas River Stream, Near mglll
13:QOpm
Dam
: , •
- I ' . - -.
_S.G~ SGS·Jndia Pvt Ltd., Environment DiYisi~n, Chennai
28