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
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
 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
 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
 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
.- " , ----­

9;~~~Orqf:,'"'''''' >
,--_.- ...• , . : .,!- •... "< <,' C

..1 . .1\na~si§"<i{b~csi:iddiii'feMdues in rlver

-- .. ;.
".''-; ¥iitJ'rlS'¥~iitl!!'rlf~t\mQl~§'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
,,".' '

, '\ ­
. ' ,
 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
 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
 ,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
 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
 ',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
 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~~

'f>:;:..J II

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
 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
 .,

,. ' 1,
,,
,

5 .10)0'09

6 Be~~-j{i\)er 1
"

7 ,Rav.j Rjver
"'
,.,, 14: 10:2009' 1
"
"

14,)0:20D9 1

,,
,, 10 1

,10

, ,
" •
.J­
'sds In'ifii;,,-~'t'J:td~::-E~vir~h~,~ht'-~i~;r5ioh';
" ".', ',; " . ' ,
Chen~(i
.:,~
13
,,'. ':: >,' ,,",
~ :'.' ";

.-;: :,~

'/­•
 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

 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
 Analysis of pesticide resiciuesin
. - ;';il.rer Isedjln~ntsamples from .IDdia
river
" -
-- - -
. ~;5GU~ARAT STATE
: ; ::-., -,. .
.
,
" , ',­ -
, . Sampling Total
SarnPli.i!l1,9~~tioh
.

: ~r. No." RiVer !,ocati6n .'

- . .·o.• w··
' , " " (" .. · 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
 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
 ,,',

" -',

','

--',".; ,:.

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~n\ng,
.' " '~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 :.-',
,.,>
-'- ,,­

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.
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,
/". ", ,,-' .';

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,- -.­

.,,'
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',-' ,
,:;,;,,-'
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 Analysis
. of pesti~ide
".,
resio~es i~ - riv,!r~ater /sediment
- , ' ,'- , .
'-'
samplesfrom India
"',

6.3.1 General
. - . C6liei:ti6!l
Sample .. Techniques
, .
.
~ '­

River "later and· sediments sampl;'s wetecoll<ideo,at thequart"r point transects

c6r\sii: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
 ".- ,

',"" -

", '

" " :"

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

,;
,_0.
, .'.' -, ',',-:
.. . ,::
' "', .' .- .
',' - ''- ':
:;.
,',
, ,

, "" ",. '-"

 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
 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
 .
- - .
'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.
----' . . w~smade by diluting
Wb;king st<lndardZ ,
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
 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 ~ dtiB\1 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= /li\easured 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
 ':> ;.
, .'....:,,",' ,.,:.;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:~r\ac~)~Q,e;~~~ll~\~<;~;t~\~[;~?q;:.%'~~~r:')V'~r. ~~~~s.~i,~r:ip~:.~l1~kl)1~

.". ...fl~#~5>"'~r¢:5~htrjfU~~'<!.a~~~; ~h~n~[T\fl~;¢:i.1if7t,. ~as;}~'i'fi,?¢~~~~e~ . . a~d.·
.ii\tt<\t",d,··
," :"~ ,;:,';'-
F91~ow)ng.th~r~ri)~~~kR(.{!W"bn«wic·
"~,,,'
sq.lYents.)I1ith ;a .'. ro\PTY
-"'>\',:":",·,;.'>:"~"·"",:,,,,,;,·.,;,,,,,'''' ____ '',,'·r·,', " " , " , ' ; ' , " , , ' ' ' , ' ' ' ' l ! ' ' ' - , ' ,:"

evaporator,
.,__,-. ~'_,'1",
tl1e .remainins·':water ph.se '·wa.s ,liquia-\iqyjd extracte,d 'wi\h
c,.,,,',, ",.,1,/ 1\>:,·" . . . . < • • , ; '____ "",.'< I ' : , , - " J :
• '._

<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'wi\h ar~1i'r¥eYiip.or.atlJr,.Afte't~e?a~pl"
.'.#kij",d·i1a~D¢.l~ .JI~nsf~Yr,~"f: !\ithe,,cQllnnh "':in~ppr.o~iitWel~O
.', .,:: ~-::::".-<", "c-, "", ,'~/,•• ,'. ',-" •. '-' .'.', ,,',_'.,"', :.': '; :: ",',"",.,'>".
;Sliil,. ..of
.',:----.',:,:' ,~'.",'.'.,"",
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-I\\S 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

 ,:. , '

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
, -
on surfac~s9f
,. '-_. - .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
.,;. ~

Sarayu­
.' ,:.
,

-';, -­
, '
 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 , •........
:'
Ravt River
,i
, • 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
 Analysis of pesticide residues in river water/sediment samples from India

. .
I"
.: :mgll)
• 09.09.2009
~:::~::
Thamin.jbarani !
21 i 8.30,9.00 Kokiraku{am
fThirunetvell)' :
I am }Qi;t.: I mgll
~
,
09.09.2009 , Img
4.4;·5.15
pm
Vaigal
(Mad~(ai) I
Kochad.i
,
_:O~m.
.:O~mg
Imgl l
.:
23 11.09.2009
, , : BOL(~1 mgll
7.45-S.15
I'
i liruchiJapaUi :BDL~ mgll ,
CaWen
am,
I (Srtrangam} :
, , : mgl!) :
: mgll) :
13.11.2009 I m'ill) :
Pen(1aiyar ,:,Imgll)
7,45-a.15 1hirIJkovilyur
{Villupuram)
am ,: Imgl!)

25 ,
13. 11.7.009
4,00-4,30
pm
!
,,
Bhavani
I,
Pampalayam

Agrag;;tram

(Erode}

. .: I mgll

• : Ot •
BOLIOl : 0.'
"iiN _: 0.0
it' mOl
! mg,
I mg,
,
,i , _: mgll)
26 : 14,,1. 2009 1
iBDL ~i:Ooi501 mgll)
8.00·8.30. ,, Bhavanisagar Bhavani I BOL DL : ,,-:OCOO1 mgll)
am , : 1.00001 m,1Il
LO!!Jll.: ",Sll) •
27 14.11.2009 Kombup,alayam ).0000: mgll) ,
1.30-2.00
pm
Neyyal (Karur)
'Kodumudi
).0000: mgll I
28 : 16.11,2009 :
Pater
1.00-2.00
(Chengatpat)
Dimmavafam
, pm ,,
,

122,11.2.009'
Pe,nnaly8i Thiruvevdipura
, 29 •, 10.3011.00
(Cuddalorej m
am
. I i
~:
4.~~STATE , I
Godavari river 25km from
• 25.10,2009
30 at tapovan Nashik

BOL DL ).00 I mgll) ,

Ahemadnagar,
: PO,st Randha
,) Imv '
25,10.2009 Parvara ~DL: ~m.,
Western
Maharashtra : BDL Ut . ).00001 mgl :

,!

----.SGsL SGS India Pvt Ltd., Environment Division, Chenna;

29
 '-, ',­

Analysis
,
of pesticid", residues
. "
in rjver ,,>;,,!:,"
". "~Y~'"''
"
,cO' . f,um India
,.;. . , ' ....
, • .. .'. ,..: . , •. ,: ... : ..•J . ".':: .
: ,.':, . ;.mg/l I
2,.10,2009 Porv."
. ,
:,'" " . , ~.
. ' . , .'" .
, .'.
..'
. . ,BOl
: SOL ,'~
~ I 4
,: .' 'I . ' . : . I SOL .: . : mg/l)

33

34

.,
\, ­

35

36 '
,i

37

38 '

, mRIll
40 ,i I~ ~m.ill
: 6.00001 mglll
: BOl,Ol I mg
,
! 41 '
~ .: ~~~:
, : .: I mgll
I "O~"lm"
: . : 0.' I mg. :
:. . : 0, . mgll) i
42 : l~:' m,lll,
IBDliDl : O,{)(){)()l mgfl) ,

_S_GSit- SGS indio Pvt Ltd., Environment Division, 'henna;

30
 Analysis ofpe5ticide ,eSidue5i~nverwa~erl~ediTl1erit samphis@nj India

.
..... ... .. ... ..i ..
..... ....' .

·i ... ..• . ,. ..

J~_ ~:~~:~:;
... . in"
mg/l

~'~:;:
, mgll)
45 I mgll :
, ,1.11.<009 Bhogavo River .
:~ I mgll
Im,11
~ .........••....... I mgll
I mgll .
22.11.2.009 Purna River . :' Jm,/I)
46
.: I mgll)
. .: . I mg/l)
47 mg/l)·
<2.11.2009 Tapi River Post Randher ]iii;oL : 0..<J0"21 mgll)
~DL : 0.00001 mg/l)

48 05.12.2009
,
Sabarmati River
Chhotl Chllool25
Kms from
~~.:~::~:;:l : BOl . , mgll)
Gandhi Nagcr)
-: ;.00001 mgll) i
Multani, Betul :'""mmm________________________
, 0.00001 mgll) :,
11.12.1009 Tap' River Near Kamrej (35 : I mgll) :
Km from Surat), I mg/l)
•
49 I mglll

: STATE
I . "1,/1)
27.11.:W:J9 Mus, River Suryapet mgll)
01 mg/l)
mgll) •
51 0000 mgll) ,
1.7.11.2009 Pateru River Suryapet = mgll)
mgll)
•
:

,5, mglt}
: mglt}
I mgll)
:
i
,
27.11.2009 Sabati River Bhadrachalam BDl
BDl , m,/l)
I m,ll)
I m,/l)

53 27.11.2009
Pfanahita River
Adilabad
ti
I
I,
I m,lIl
I mg/l)
" .. ,, . I mg/l)
,,
,,

_sIlsl r
SGS India Pvt Ltd" Environment Division, Chenna;
31
55

27.11.2009·
56

27,1 t .20d9' . M.~i1Jeera River." '

57

Oi.12.2009 Pen'na-r Ri'ver Nellore

58
I

Gund\~kamma
59 03.12.2009
Ri'ver Ong9le

03.12.2009 Krishna River Yijayawa:da

60

61 i .
03.12.2009 krishna River· Nagarjuna Sagar

62
·04.12.2009 Godavari.River Karirtmagar

04.12.2009 Godavari River Rajamun'diy

63

64
05.12.2009 Sileru River ,SrikakUlam

- . ",- .:-
-SGs:- SGS India ~vi: ~td., ~nvjron~ent Djvis"io,~, Ch~linai
32

, " .,
 Ana(ysis of' "
pesticide resi.duesiririVer
.' . " .
water/sediment,
samples
. '
from India
.

10.' RESULTS OF SEPi/.lEi'tT OF RlVERWATER

1
Vaigar
Kachadai
,i (Ma<,luraj) .
p.m•.
I
13.11,2009 I
2 4.00 to 4.30
- Bhavani
. Pal1ipalayam
p.m. ' (Erode)

(Punjab) •
3 08.10.09 I Satluj river downstream,
06.00 AM (punjab)

, (Punjab) .
4 08.10.09 I Satluj river
i, downstream,
04.30 PM (Punjab)
near bridge
.Charnbat,
Etawa Distt,
5 30.10.2C09 Chambal
Near Bhiod
Road Bridge
L
30.10.2009 Mathura,
6 Yamuna r'(ear Rail
02:25pm' Bridge

~H$. SGS Jndia Pvt Ltd" Environment DiYision, Chenna;

33
 ..
'.'
"/

.
". .
"

-'·'.'i·
..... :.' .

.' .

..
-.,'.

' .. :."
.', ':.
\.

'.' ,
.
' .'

, '.'

34 ..
..
: :;: .
..
r. .-' . >:
. f: .'/ ::: .',,' '.
Analysis of Pesticide residues in river
water/sediment samples from India
•

( ANNEXURE I
)

 ... _ - - - - - _... _ ­
1
1 SGS INDIAPRIVATE. LIMITED
1-­
I SGS India l'vt Ud.,l;Iborato!y. lJ509A, Old ~fahabalipumrn Road, lEL: +91 (44) 24963844, 24962=822=------1
I Thordipakkam; Chennai -600 091 _._ _ _ _ _ _ _ _ _..FAX: +91 (44) 24961.0.,,15"'''''_ _ _ _ _ _-1
Issue No & Date: 1,07-06-2010

~~---__---------~-~~~~N~o~:l~----
I METHODVAr,mATION
1_ _ _ _ _ _ _ _ _"D"'E'f¥-RMINAll0N OF PESTICIDE RESIDUES IN WATER BY GC·MS-MS
==___ - - - - I
1.0 Objective

To develop a~ validate Gc-MS-MS p~ocedufe for Ihe eSIi!T1alion of pesticide residues in Waters

2.0 Validation parameters

FolloWing peffonnance parameters will be assessed during valklalion.

System Suilabi[ty

Sledlv'",),

Sensillvlty

Ruggedness

linearity

. Precision & Aoout'ac;I

Recovery

2.1 System Suitability

Perform system wilablli!y by injecting 6 se1s ofknovm concenlralions of aqueous mixture Of 3:'lBly1es. Calculate tr.e CV%

fOf tete:nlion time and areas.

All six Injections should meet !he following criteria

CV of the releotionllrr.e should be S2.%, and CV of the areas shot:ld be !OS%

2..2 Selectivity
The selectivity/speciilcity of the present method is established by' checking the reagenl bl'ank (wilhout spiking

pesticides}. If the roagent blank contains signiOC<lnt inlerference .. t the retention time of pesticides in question, that

wi!! be rejected.

2.3 Serraitlvity

It is e¥Pfe€-Sed as limit of quantifocalion

2.4 RuggednC'Ss

Perform Ihe ruggedness in the (dtowing prameler using: the concentrations equivalent to M.99. ?

P~By Verified By Approved By

I
.. --~----- -~~-i

,
I SGS INDIA PRIVATE LIMITED

Column variation (minimum two.columns with same make and 101. or if possible different jot numbers
Acceptance criteria
• CV % for RT shall be $2 for each COlumn used.

- CV % for area raUo for analyst and column changes shall be 51!)

2.5 Recovery
Recovery of an tll\alyte in an assay is l~ inslrumeni fesponses obtained from an OImour,! of anal'yte added !o and
recovered from sample matrix, compared to deledor response obtained fro:n pUle au'!hentic reference sJaoderd.
The percentage recoveries are determined by measuring the peak area or rer"Overy samp~ at co:;cer.trations of
LOO. Com~;;uing with1he responses of the uMooracied solvent standards. Acceptance criteria
- Recovery sl'.ould be BO 10 120% al 0.Q1 mgIKg level
• CV % of lhe areas of ana!y1e at each concentration level shall be ~ 15 it Ihe ?bove criteria are not met, repeat
the teCOIJery experiment

2.6 Unearlty
Make minimum three (3) caflbralion CtIrves using 5 djfferent concenlrnfion$,
The no. of slandarcis used In constructing a calibration curve will be a function of the anticipated range of
analytical va,ll,;e&. Concenlrations of standards should be chosen on the bases of the concentration range
expected in-the samples.
A calibration curve consists of blank and 5 non·zero slanciarcls covering the expeCled range {coded as CC1
through to eCG). A linear equatiOn will be determlnetl to produce the best f.l fOf the com:enlrntlon !response
relationship, Sel<K:Uon of weighting and use of regression equa\lon should be juslified.
Acceptance criteria
- MID:lmum allowed deviation of the CC1 from actual concenlralltm shall be ±20% and s!andards other than
CC1 from actuat concenlratlon shan be ± 15%
• 'r' shall be ~_99 (or) 'r2' shall be G: 0.98
" At least three oui of five non-zero standards shall meet the <lbove criteria, including the Cet and the
calibration standards at tr.a highest concentratIOn (CC5). Any two consecutive points shall not be excluded.

2,7 Accuracy

Analyze the samples as mentioned under 'Precision 'and calculate (he aroJracy

% Ac(;uracy'" {Mean of obtalned cOncentratiol1$/Actual conccn\r.a:tion of QC'sJ x 100

Acceptance ¢li1eria:

Prepa..red By VcrmedBy Approved By

:~d
I . ~.
SGS INDIA PRIVATE LIMITED

I SGS India J'vt Ltd., Labotatory, 1/509A, Old MahabaJlpuram Rood, TEL: +91 (44) 24963844, 24962822
i Thoraipakkam, Cheimai - 600 097 FAX:+", (44)24963075 ._ _... _ _ _-I
Issue No & Date: l,07..fi6-20Ji)

PageNo:3

DETER..'\1INATION OF PESTICIDE RESIDUES IN WATER BY Gc...MS-MS

. The % accuracy obtained should bewilhin 85-115, expect lor LLOa, where it shoold be within 80-120 .

2,e Precision

Under each calibration curve 8f\jiIly:re 6SEts of each of LQC, MOC and HOC sample1L The precision of the method is
represenled by % Coefficient olvariation and calculated as fonews.

CV %:::: (SDfMean) x 100

Where CV% '" roefficient of wriSton and SO:::: standard de\iotlon

Acccplance crlleria

The precls:iOtl denoted by CV'~!tl n{ each concentration level shaH not exceed 15 expect fQr LLOQ ",here it should oct
dev,ale by more than 20

Resu!1$ of Validation

3,Q Debjil; or GC-MS:

GeMS:, alphn·HCH. belii·HCH, gemma-HCH, della-HCH, Methyl parathion, Aldrin, o,p-DDE, p"p-ODE,
Dieldrin, EndO$l)lfan, Endilsulfon Svlfale, {I,p-,DDD, O.f)-DDT, p,p,-DDO, and P,P-ODT.

- -....•. ~~--

PreparedBy VerifiooSy Approved By

i
I 8G8 INDIA PRIVATE LIMITED
J~-

1 50S -India P.,.tLtd,: Laborntmy. 11509A,. Old Mah~ipuram Road, TEL: +91 (44) 24963844. 24%28'..2
'lboraipakkiun. Ch,nnai 600097 ~_ _ _ _ FAX +91 (44)24%3075
~ r~=oo~N~O~&~Da~~~·TI,~OO~~~6~~"O"IO~------------~
. =c---- _________-'P?J!""- No:'
I-ME'rHOD VALIDATION
LI_ _- - _____~_"D""'E~~.RMINATION OF:.PESTICIDE RESIOVES IN WATER BY GC·MS.MS

3,2 Chroma!.OQrapjii<: Cooditions of Gr'rMS-MS

Insirument : GC-MS Triple aved 7000

Injedo: 7890A Agi!ent Technologies Injector

Solvenl Syringe S!ze lO',Jl

Pte 'injection solvent fluShes 3

Post injectfj)n solvent flushes 3

Injection Mede Spl~ less On 7683 IliadOf'

Injector temp 270"C

Transfer line temp 260'C

Carrier gas Helium

Flow rate 1.0 mUmin.

Oven temp. Programme InltiaI100'C(hold OJ)lJmin) to 170~C @ 1S"Clmin {hO!d 1.00 min)
10 24Q"C@S"C/min (held 2 00 min) 10 280'C@2O"Cknin {hold
2.0m!n}

Run lime 20.417min.

MS CQNDITIQNS;

Mass spectromeler operated MRMMode

He Quench now 2.25mUmin

N2 Colfision 1Iow 1.5 rnVmin.

Ion Source 23Q"C

EM Vollage 1281V

Filament Bias Vollage 70eV

Total Run lime 20.417 minutes

~edBy Verified By Approved By

I
SGS INDIA PRlVATE LIMITED

I SQS India Pvt Lid., ~boialOl)'. 1/509A, Old Mahabalj~ Road,

I Thoralpakkam, Chennai- 600 097 _ ~__TEL~'
",'~+g",l,",(44?)2"4",,96,:,J~844,,,",2:::-49;-;:6l_'_22_ _ _ _.....---i
FAX4<lq44)24963O'15 ~
Issue No &; Date: l,01-06-20\O
.I
P No:5
I :METIJODVALIDATION
DETER,\1INATION OF PESTICIDE RESIDUES IN WATER BY GC.MS-MS

4.0 Prepal1ltion of Reagents

4:/.1 ~raijpn of fAisUci® standard sip SohJliPQS: T;an~fur 10mg of slaodard inle a 10mL vo:Ume'!ric flask and
alSso),;e in HPLC gtade Methanol Of EthjiI acetale, MOike up lhe volume wilh the S<lffie. Label a.'it! slOfe ihe soivUoo
in a refrigeraror below 4"C. This $ted; is Slable up to the expilY dale mtmlioned in the Certilic;;le of Analysis (eOA).

4.1.2 .E!:m1§~.ij.on of pes!iciC'e worWng slanders! SQl!.rtl9fl: Transfer the 25O<,JL of each Sla'ldard in to the 25 mL
volumetriC flask and made up 10 Ihe mark with Ethyl acetale, labeled as 10 j.!gfrnL and store the ootul.:on in a
refrigerator below 4"C. This stock is slable up 10 three months.

5.0. Preparation of CalIbration Curve (CC) Standards,

5.1.1 Pre!.)arat\c(\ of SjO!;k ~1h11Pns of sl?ndard sotullQns; Prepare the foll(Ill'Ang stock dllI.funs ranging from 500 10
7500nglmL with elhyl acetale "as Shewn beloW' using (l;lulions from workio!j sti!ndalrd solullort These standard
dilutions are slable for 7 days
StOCkCooc{pgfml) i Volume {If StOCk(mL} : Volume of Diluent{mL) Fio<ll Volume Final Cone..
, '

I, I,
(mL) (ng/mL)
10 7.5 2.5' 10 7500
10 . 5.0 5.0 10 5000
10 2.0 8.0 10 2000
!-W... 1.0 9.0 10 1000
..
5 1.0 9.0 10 500

Prepared l}y Verified By Aprf\},,~d By

I
I s~s INDIA PRIVATE LIMITED

I­
I sas Jndja.PVllM., LoJ>orn:01y:"j/5ll9A, O~ Mah'''bcl'";=purnm=''Ro'"""'aaC".----"''TE'''['"'.'"7'9"""'(44=)24"'9(>3844. 24962822 - - - - - ­
j ~oraip~ ChennaJ - 600 097 --+F"AX=,,'+"'9"'I-';44:;:o:24~96,,3"'07:::5==-----'------1
lssueNo & Dale: 1.Q7..QO...2010

I'a eNo:6
MEmOD VALIDATION
DETERMINATlON OF PESllCIDIE RES1DUES IN WATER BY GC-MS-MS
~--------============."--"=====------ ~ .. i

PlllAAratiQf! of pesliCide residues for C<l;librg\ion rurv.elj: Prepare CC1 IDCC5 daily ranging from 50 10 750 J1S!mL willi
Ethyracelale.

Slqck Cene Volume of! Volume 01 Final Volume FinalConc. label

(nglml) Slock(mL} : DlIuenl(mL} (rrI..) {nglml)­
7500
0·100. 0.900 1Jj{)J 75O .CC5
5000
0100 0.900 1.000 500 CC4
2000
{).1~L ..
f--­
1000
. 0.900 •
1.000 200 CC3

0.100 ,0.000 ' 1.000 : 100 eC2

,
500
0.100 0.900 1.000 150 CCI

5.1,2 Quality Control (OC) samples for pesticides

Prepal'ljllloo of stock. difu\lons: Prepare Ihefofov.ing concentrations mngmg from 1,5{) 10 13.50 msfl with n-Hexane.

StocK Cone. Volume of Volu!'f1o of Final Volutni? Final Cor.c.

(!JgfmL) Slocl<;{m Diluent{m (mL) ("",mL)
L) L) .,
10 0.76 325 6750
10 3.75 625 3750
10 1.6 6.5 1500
.... ­

5,1.3 lliparaliQn of quality C9!1lfQl samples: Prepare the rono....ing ooncentmUons da'!y ranging from 30.000 to
4COJ}QOpgiL with mobile phase or Ethyl aootate for aft of Ihem to ;achieve !he fcllc\"Iing quality c:ootroi samples and
labellhem
As lO'JJef qualify oonirol standard (LQC).Medrum quality coolro! slandard(MQC) & Higher qua~!y control
sta!ldard(HQC)

SlOd< Cone. ' I/olurr.e of i Volume of Final Vulume Final Co.,c.

. ,
(nglmL) stoo<;(rn . muen!(m (mL) {l-IgIL)
,i
. L) , L) .,
6750 I 0.1 '0.9 1.0 675
3750 ' 0"1 o.s 1.0 375
1500 "-1°·1 ,0.9 1.0 150

---~By Verified By Approved By

'., ..

_6,0 sa~pie p'~paration

6.1, ~. Ext~'cliOn
Shake 'sa'rpple well and accu~lely measure- sample in·a one liter gtaduated cylinder. Pour the sample
" , , ' " , ­
into <H'IIO liler sep:ar3\ingfun,neL' Rinl:ie tlie cyjinde~ willi' _SOml of sollfenf(DCM). Pour the'solvenl into
e~r~Ction :device. Sha,ke'lh~ sepa;atin~.fu~nel vig~rousiy, ror 2minufes. Allow the layers'to Separate fur at
!c:ali>110minules. DraIn organic phase lhrough a funnel cor\taining' !he ~ium sulphate Into a turbo viaL
Repeat 1M ex\mction and pass organic' ptllise through sa~e sodium sulphate, Wash sodium sulphate
\'Jilh several portions of OCM and drain '<'IeIL Evoprillte 10 d:yness vnder the nrtr09i!'D stream and
reconstitule wilh 1m! of ethyl- ace~le.
6.1.2 J;?ii.~action performam;q lIerificalion!
Extraction performance is carried out by spiking the O(gancchkuine pesticides inla grape samples' at
O.OOO01mgfltt.
1.8 Valida:lon parameters
1.8.1 Selectivity

The sele~ivily of lhe present II1etho:d was established by checking 1~1e reagen! (wlth01,l1 spiking

pe$IiGidt~s) 'Figures 1. t & 1.2 is represenlalive chr.oma!ograms of reagenl blank samples. The

iv.ethod was found \0 be.$pecifi¥:'and seleClilffl for pesticide residues men!ioned in scope,

1.8.2 Sensitivity

The limit of quanlifitnlion (LOQ) was found to baO.01 mglKg for all pesticide residues,

1,8.3 Ruggadne~s fT!lble: 2.1 to 2.8)

In this ease for an pesticides me,nlioned in 1.1 C?lumn cfw:nge was observed, The obsBNed valves for
column change are within the acceptance criteria. AI! CC's and QC's were wilhin the acceptance
c'rjleti!;l,

1.8.4 Recovery (Table 4.1 to 4.4).

The perCEntage recovery of all peS!i~ides mentioned in 1.1 performed al different levels were wilhin 60
to 120% <It 0:01 mgIKg level and fiOto 120% al 0,025 mg/Kg level
1.&.5 Unearity

Verified By Approved By
 l
SGSJNDlA PRIVATE LOOTED·

J SGS -lndill: Pvt Ltd., LabnratOJ)'> IfS09A: O"Id;;;;;:""""';:;C:;:':;I;;::ptmun~::-R;;Coorl;::;;,----TTEULc"'-:+9""1"(4"4)"'24963844, 24962822

i ThoraipakkarnLChennai·.. 600 097 _ _"FAX=:S+.<.91':i(~44")"2,,,49,,,6,,30,,7,,;
= " , -_ _ _ _~ ...._
Issue No &. Date; I, 07·06·2{)10

Page No:B
I METHOD VALIDATION
DETERMINATION OF PESTICIDE RESIDUES IN WATER BY GC-MS-MS

The method was found to be linear between the ranges of 0,01 mglKg to 0.15 mglKg for pesticides. A
straighlline fit was made furoUSh the dala points by using 1/Affiount weighling method. The observed
correlation coeffl(':ient tr1 was greater than 0:98 and r was greater than O.9i}. Hence Um method Is
linear in Ihe statoo range.

1.8.6 ACCuracjf (Table: 4.1 to 4.4)

The % recovery obseJVed tor spike samples are given In the table,

1.3.7 Precision (Table: 6,1 to 6.3)

The % CV observed for the samples are given in Ihe table.

UU LnjectotoStability

Injecto, stability resulls ~te labulated. The batch size was decided 8S 19 hrs. {251njections}

(it was delerrr.:."1ed at room tempeHlture 20 ± 2~C i

1.9 Conclusion

Based on the resu;ts of validation, it can be: concluded that the present method is suitable for the
estimation of pesticides over concenira1ion range of 0.01 mg/Kg for Organochlorine pesticide and
Pyrelhroids, O.02mg/Kg in gtupe samples. The precision and accuracy are very much wilhin the
prescribed limits in this concentration range,

The method is found 10 be rugged, and vel'f stable.

,,
I
Sr..No. COm::.>OUOO I RUIl·1 I Run·2 I Rur.-3 R,,,. Run·5 Run.6 Mean SO CV .­
1 .~BtoI"l",Q-241ltlfO?her.~!. 50521 I.. 49510 I 46703 45'" 411184 49402 49079 930.535 : HID

Prepared By Verified By Approved By

I i
[
SGS INDIA PRiVATE LIMITED
I
1--.... -' - ­
\sos +ndia P:vtt.~d .• ~ory, 1/509A~ OIdMababalipUram ~om1,
1:.ThorniP#run; Chennai - 600 097 .
TEL +91 (44)24963844,24962822
__~F~AX~:~~1(~44~)~24~9~63~OO~5~~o-____________~1
I
],sue No &lli'''', 07-0",20(0
I
[METHOD VALIDATION
DETERMlNATfON OF.PESTICIDE RESrDUES IN WATER BY GC-MS-MS
j

Prepared By Verified By Appr.oved Uy

1
SGS INDIA PRlVATE LIMITED

=ip=uram="R"oc:,dJ,----"rn;;;,L",-c",=,(;:;44-;;lo;2:;;;496=3844=,c;2::;;49"62"S22=--~
1smj" IndiaPvtLtd., Labor.ltory, i/509A, Old b.i'",habal""
I Thoraipallim,Chennai-600097 FAX: +91 (44)249§~;!;O",7S7o;=_ _
L<:suc No & Date: 1, 07-06·201Q
----'l
Fage ~Q:IO

DETER1\I1INATJON OF PESTICIDE RESIDUES IN WATER BY GC.-MS·MS

I
43 Deltamelhrln
18673 18328
22925 :
17198 '
=" '
16476 :
221'rr­
17094 16949 17453.0 &S5. ~5a 4.00

I iI

,,

Prepared By Verified By

l
 SGS INDIA PRIVATE LIMITED

I SGS lndia Pvt Llrl., Lobo,,'o'1', 1/509~, Old MatrnbaHpru.";:·Roo=d,r----"TE",I",'""'+"91"(cc44"")",."'96=38474,""24"'96"'0""2"'2--­

I Thoraipakkam,Chennai-600097 FAX:+9J 44 24%3075
Issue No & Dal~~ 1, 07-U6·201 a

PageNo:l1 _
I METHODVAlJDATION
DETERMINATION OF PESTICIDE RESIDUES IN WATER BY GC~S..MS
,
I as CyIlultnin-lll . 15040 12653 11545 11046 11831 10957 12295.3 1454.55 11.Il3_
i 3. CvlIlI.hrin-1V 4660 4225 4~s.2 462ll 3933 4271 4339.83 27U73 6?,!_
CvoermeltJM.1 23387 21579 21165 21330
I " I Cv~i~e!hlin-II
38
,
18233 ' 17123
21189
16m '
215!lO
16587 1692. 16107
21691.7
16962.7
546.692
714.833
3,90
4,~~
, 4.07
I 3. !1ypermethrin.JlI 15919 , 14168 ~ 11!312 15165 11~24 1400~.a 00ll.734
,
40 C~_Q1rin-1Y ----­ 12497 .2735 1~361 12056 11997 11751 12232..8 362.61i
..~~
1.........1:!.. Fen>relmale 51378 I 51240 48782 50000 ~98 47832 4~2.1_7 1484.41 ~,"!..
42 Esfenvelerale 42787 ; 4061G 40819.3
I 42100 40184 39725 39870
'~J~ 3.10
, ... _---,

r-.. . . . ~ ...
43 : DeMamethrin i ""'10150,' - 9871
,
0054: ..JfSS9 9123 ... 9171 9493 4511)11 4.75
,
44 ' Famax;;:done BOOB: 71\4B ' 60061 7106 7006 ...,=
666IJ 7238.33 492.47 6.80
-­

I'repm'edBy Verified By Approved By

 SGS INDIA. PRIVATE LIMITED

1.0 Objective

To develop and vaf.date GC·MS·MS procedure for the estimation of peslicide residues in Waters

2.0 Validation parameters

Following performance parameters Will be assessed during validation.

System Suitability

Sleclivl1y

Scnsitivr.y

Ruggedness

Linearity

Prer;l$icn & Accuracy

Re"""'Y

2.1 System Suitability

Perform syslem t;l,;ilubllity by injecting 6 sets of known concentralions of ac,ueous mixture of 3M!ytes. Galcula!4! lhe GV"'J..

for rele1i1iOO (me and areas,

All six il'ljedions should meellhe following criteria

CV of the retention tin'Ie should be 52%, and CV of the areas should be .s5%

2,2 Selectivity

The seleclivflyls~ecificl1'i of the presenl method is established by checking the reagent blank (without spiking

pesticides). If the reagenl blank contains significant interference allhe retention time of pesticides in question, !hat

wi!! be rejected.

2.3 Sensitivity

It is expressed as limit of quanlif~

2.4 Ruggedness

Perform the ruggedness in lhc followlng prameter using the ccncenirallons equivalent 10 MOe

Prepared By VerilledBy AppmvcdBy

 Analysis of Pesticide residues in river

water/sediment samples from India

( ANNEXURE II
)

--~---------~~--
;=

I. Quantitative Analysis Calibration Report

.
Batch Info
8at£h Data Path D:\MassHunter-oJd\GCMS\l \data\?O100517\QuantRe$tl!ts\Uncority.bat:ch,bin
Analysis lime }0-1-:;!010 3:19 PM AnaTyst Name Adrnin
Reportlime 1O+20tO S:.qS PM Reporter-Name Admin
Last CaUb Update 10+20Hi ];19 PM Batch State Proc.essed

Target Comp()lJnd EndosfJlfan~I .~~~~~~~~

'Ennoswlfan-l· 5 LIWOls', 5 LC"'Cl~ PalMIS. SPOiOiSUsed. 0 ci~' .~-~~~-~~.
~ x10 4" -'i~T7':4i:i3OC5; it '·-~4.7;{!f3Al

1! 'R~;Z "-0.0051111'0

t ~~
U

. - . .' ~~

1
',' ~.
0,9 ~ .
9,'
o.i
0,6
0.5 •
OA
o.:r
0.2
0.1
o .. ---".

.().t~-:5o-·O·--~·100~150- ~'QO~'200'35O"'400---4'So ;&, s~6-soo-n.t1 7Oo~'75e sOo·_j

.~_.~~_ _ _ _ .~_. _ _. ~_.~_. .~~.~~.. ~_.~~".CC'~l!alion{~l1

CallbratiQII srI) cal TYPI! Level Enabled Response RSO

'...;0,"
'"
CC_l.O
=,0
calibration
Ca"btaOO'l ,
1 El

'"
12J3700
14.092.1
''"' COO<

50.C-OOO
100.0000
n:o.oooo

CC•.3.D
0:.....0
C,ailbmtion
C'tIrobr.lticn
3
•5
El
~ ,,<,
3125 1$,62€{)
15.0020 5oo.o00!l

0:_5,0 CallYati:1II 13709 1&,2789 750.0000

"

.'

,
;,
Batch Info
Batch Data Path
Quantitative Analysis Calibration Report

O:\!'1assHullter-016\GCMS\1\t!ata\2010C{517\QuantResults\llnearity.batch,bin
Analysis Time 10-1-2010 3:19 PM Analyst Name Admin

Report Time 10-1-201fl5:'15 PM Reporter Name Adnin

~
last Qllib Update 10+2010 3:19 PM Batch State, Processed
:)

:>
:)

;> ,.S ,
:> 3 "., ,

2.5
:> 2

:> 1,5

, 0,5
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,:> :'-r---'-r-~:c'~-:-r:-"",:-""c:--:+-
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..---+.-~-.4--.-~-~.-"---,-.-~,--,,,~
~_'. ..~~ ______ _
) C;!libratlo!l STD Ca(l'vpe I.e,., Enabled ResportS(! OF RSO up Cone

)
CC_J.O
CC_2.0
CaPbtlllioo
C;imtjon ,
1
"8 '81
m
3,G36ll
'1.nS7.
SQ.OOGO
1OO.COOO
"_3.0 eal,tratiCn 3 e
) CC_'to
C~S.O
ClWtion
O1I:brnt.!cn
•
5
8 '"
,,%
.ns
4.6785
$.5926
200.0000
500.0000

~ " 6.1713 750..0000

)
)

I
)

l
)

Patte 2 of 3 Ponte<! at 17:45 on: OHO-ZOIC I

 Quantitative Analysis Calibration Report

Batch Info
Batch nata Path O:\1-1assHunter-OId\G04S\1 \data \20 l{)0617\QuantResults\Unear!ty .batch.bin
Analysis Tlme 10+2010 3:19 PM Analyst Name Admin
RepcrtTime 10+201(15:45 PM Reporter ""me Adrffin
tast CaHb Updtlte 10·1-;Wl.O 3:19 PM Batch State. Processed

2.5
2
"
1.5

0·'o
1 -.-/0
• ­
J > ·
•••
- - , - - - ~l- -,~ -r -
'00~_'. _ _ 'OO _ _ _ _ _ 700_a
~--y~--, ~----r ~-~r---'-~ ~~;""~-,-------,,-""-----·---T-----~-,..-----~t----~

._ _ _ _ .~_. _ _ .~ __ .~_~~_. ___. ___. _ _ ._~_._~.~_.~_.~enIrQ~ (pfIb)

Ci)jibratian sro tat Type levcl Enabl'ed Response .F RS!) ~Cont

CC_l.O
C<=-2.D
Callbratio1
(a!itra{ion ,•
,
0 Ul
m
2.2267
2.729J
SO.OOOO

J(Ju._
CC_3.0 calibration '"
~ 7" 3.66111 200.0000
CC_4,1)
OC_S.D
Caijbration
CilJbraO.m
•5 0
0
2'180
4llS
~.96(H

5,5O'Il
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iUAnt Time: Dec 24 09:12:01 2009

,<.:.ant, Het.hod
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hiaWt: Tit"le' Grapes and Pomegranate
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'-espouse via Initial Calibration

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211 £ndosultan-II o N.D. d

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apee200B.N Fri Oct; 01 lO:Oti;S2 2010

 Instrument; I!l
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Quant Method D 1 \msdaheru\l \ME:THO!')S\Grdpes20IHl.l.'
Quant T~tle Grapes and Po~egrar.ate

QLar..t t:pdate l'hu Dec 24 09,)0:22 :::OQ9

ResponSe via Initial Calibra~ion

- - - -.. ~~----

. - R.-:'i':~Qfon RespOriSe'- Cone Units Devil1ini

Target compounds Qvalue

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21) Endosulfan-!I 0.000 N.D. d

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----~-.»~~--------~----.------~--~~--~---~~--~.-~-------------------------

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t: Met-hod D, \madchem\ 1 \MET;-{OOS\PES'f-',fG .H
t Title : Pesticides
t- update i Wed Dec 02 1~,t.5;29 2009
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,ast update Wed Dec ;Z:) J.7:42:37 2009
!spO,~$e via Initial Calibration

Compound R.T. Qlort IiespOnse Cone Units Dev(Hin)

-------------------------~--------------¥~~~~*-------.----.----.--~~~.~-

arget CO!lIpounds Qvalue

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.~-------------------------------.-~-~-----------------~--~~.--~~ ------~

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Is2000.M Fri Oct 01 1.0:09:30 2010

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! • I
'T P AcqulsWon Pate Jam;: d, untis Area \coocmntratlon! (%) Y
am. ype. I . i {~gIKg} Time (min) I (~gIKg)
(counts)
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2 2~ppb ~~~~~!:rd T~I23120091;38:29 PM rmj~~c:~~~~ci-! _ i~~/K~= }240_0'_ _ -l~~"~ __j5.e~_______ "I~O,1 ~.~.=~_ll~oo_._~~.~·l
3 . 5OppI:J
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4 100 ppb
Standard 12f2312p09 2;23;54 PM Imidacloprid-I flg('<g . 51300. j 100. 5.60 '05.9 105.9-l

@'--2oo'PPb Stal1d"rd 1212312009 246:37 PM ImidaclopnC:'.J~gIK9 111000. i200. 5.60 121.2: J1GIl. 1

o _ Blank Unknmvn 12/2312009 3:09;20 PM Imidacloprid:I_I~lKg _ 0.00 ._INIA- __..JO.oo iNo Peak TNtA ­
'r 9110058169 Unknown 1212412009 12:57;00 AM Imldaclopric-I l~glKg 432. iNIA ~~... I~J.:::~==I
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COCCfJo!r;l,ti.QJl...u9L1Sg, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __
150 170 180 190
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Sample Analytc peakt Analyte Analyte j AnalytC" 'I Analyte \ Ca~iCufa!e~ \ Accurac .
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Nama TYpe Name I Units
(counts) I (~g/KQ) Time (min) j (UQ/Kg) 1 ~

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,t.\cqulsltfon Date
,, In,
Peak Area jCQi'lce,ntration
,(counls). i
(IJ!lIKg) j Time (min) i (~gIKg) I ' I
rr-ho +5:iiT'-'''ima ,~- ~Fi6[--''"'-'-:
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ppb .
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20.0 ""'_ '5,62
1'0,0 -
117,6.
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11fu,-:
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3 50 ppl>
100 ppb
Standard
Standard
1212312009 2:01:12 PM Imidacloprid-II jl'lllK9 25400, 50,0 . 5,58 151,2
12123/2009 2:23:54 PM~' !mfdactoprld·U -, ~!K~ --';- 51600. - '--~--1100, --- -. --- ._,. S~[j9-"--'-- 103~--- ~, - - ~j1ci3.-' -"~-I i
;'5 200 ppb Standard 1212312009 2:46;37 PM Imidac]oprid-II Ii9/Kg 100000, j200, ,,_,
5,59 ___":",1196: ;98,8, J
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1 9110058170 Unknown 12124/20091:19:44AM Imlda~:oprid-lr I19tKg", 2170. NtA .=5.63 _ 15.68 h--l~A ~

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. I Analyte j
Peak Area I' Concentration
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Name Type ame: m (counts) 1 (!1g1Kg) rIme (min) 1 (V9fKg) , -
I .­ --... -.... -+-­ _ ...__L .._ .......

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n ••

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~-----
-- -- - -- ...... ..,..

IS:~~1e sf~p'I-:Cqulsiti::a:'F:~;:~.]I-A;~;~:·:-p~i~~~~-i~:~~~i~:~:'~' :~~~~~:-l~i~~~~'i;~i~:r~~~~~t~:-l'

, amP, yp€' I I ame m (counts) (pgIKg)
'"

Time {mIn) (pglKg} 0,

=:twpr-
, - 20ppb
~g/Kg- "·-}~i70. ---'-h'bll---= ~ ~_~-"--Imr-----'bOtt-'-'-~
fsrandard
Standard
12123120091-15:47PM
120.Q~ tS24Q.
12/23120091:38:29 PM
Imidacloprid-Il
.. ____ 5,62 _
!midacloprld-U fl9/Kg11.6 ____ 188.0 "
50ppb Standard 1212312009 2;01:12 ~
125400. ___150.0 •__ ._~ 5.58 _._ _151.2_ _.__ 4~02._~
Imidaclcprid-!1 tJglKg -j
151600. ~
Imid3clOpn~~ugIK9 :=J9~ ~
100 ppb Standard 12123/20092:23:54 PM fmidaclopnd-I! !Jg!Kg
100.· -,5.59 103, '.103.
_, 200 ppb Standard
121231200Q 2:<6:37 PM . 1100000. 1200, rS9 ---'98. - -. _=____
Un~!1OWn 12123120093:09:20 PM Imidacloprid-II §'K9
Blank 10,00 !NIA
-::::--- 911QOS8173 Unknown 12/24/20092:27:55 AM fmidacloprid~lr yglKg"-' -l~250.~-- _J~:-=_~i~
0.00 No Pa.k INIA
j~.~1 -- -. ----lNJA - --=
_. __....
=~
i;.'...,.i._~ __
_oot ....."'>U__ ~
-~
.....-:ti!F,...
___
--
....~"" ..~'''... ~ f~-,,."'~
.......~tw,..iI1""i'n""'"ef....
-~
......... _
--
... iIi '" ~.. o'
~'"'''''''''''''''U re;ct""<"'iii>"~"'ik-
- - -""-
1.!'."'ih...,r= 1~_'f'~-;;;t"'i:.,--;'"a;;:>r..""tifi':R"""I·I~
_ _ " " , _ ........ ,,""'''''u......
"""""",,," - " <-- - - ­
I
_'"""''''I>J......

....... _-......_ ""0[<4')""''"''1_0' .." .._~.. I

~Ll ' ', 00 *~:~ ~I ~~~~~,>;"7t"7;;~11'-I

I ~:~;:I,~ ,;';; ~" r, -I.]
.....
1 00 l~,
-: ._,~.~.~~,. ' -Ll )"'U J
..• ~~ r_~I_,_,_' ~A ,,~~.
I

_...---­,.
> • • • ~ ,. ,. • ••
"'''--'''''"i''''~ 'i:::$.?.,.. 1... ·..,__
_ ...... _..- .._"""V,,,,,...,, ,

':L.._ 1... ~
R' " .......,'
"""",.,
-.-'"-----­
(I'!'

-_. I
I 23-1:2-200S.lmidtlclcprld.rdb (lmidac/oprkHI): ·UI'lt'af' Regression ("1.1 x" .,..eighl1ng): 'f '" 509 x'" ·730 (r '" 0.9900)

1.00eSj
-­ _._~-.-I)-
a.OOe4

6. 00c4
4.00~4
1
_.------­ --.­- •.---~------ -- ______- - - - -

2..00eAk~
.~ ~ 70
__~-~---r--~
_________________________________________
'0 • • • 00 .,
---y-_h~
iwm~~ 100
_--,-,

,.. ,m ,m MO .~
, _ , "

____________________________________
,. .70 ,,0 100 _
,

~
..,.

,
,...,. "~-"""""'-

Sample
An I tc Puk! A I tt! ' Analyte i Analyte. Analyw' j Ca!c:u{a{ed
Sllmple Acquisltfon Date a.y I na X ! Pe<.'lk Area Iconccntration Retention
-Name Type Name VOlts i (counts) [(~g!Kg) Time (rnrn) j (~gIKg) {',I)
.. ~ __ , ,_t
,"_.!'~ _ _­ '_'_ _ J., _ _ ••• ___•• __

~"
M ____ ,_. _ _ _ •• _____._ •••

3,
i'Oppb
15:47 PM
, PM -,"­
IgIKg
~~~~. -::J;~~-=~= ~.:~~~:=:_~l_~-::::==j}~~:
?Go.
- 150.0 ' 5.60
.. _--_. _.+-­ .--~- .--.~---.~
140.7. 181.5
-- _ .,
4. 1100 ppb 4 PM ll""irl!i,..lnnrirlJ­ 1i--9iKg ­ i100. . 15.GO 195-9 195,9
7 PM Ilmiam:::aopno­ 111'000, "
j2oo; -­ ~5_SO- 1212. , ----'-­
i Me
I~ 1200ppb ,",v_

_~.=,i~fank- oPM Imidaeloprid·! Ivg/Kg

1 AM !.lmlda~J0f?1"id~1 "1r-" _ ~~c;-'-l~-' '--I~'::-::::t~~p_ea~:f~;~-
'"t~ - '':'~"",",,'..-,":...c -~,. ~~9'[~""'~·'''''''-''''''''''''-'''''·''·"'''·lr
-...'. ....ot<.. _ _,....... l ...... -,.':«--_..
~.m''''''''''lf''''''''"'''
I
L..._..:..'
I =:.,~~ ... -...,-
...... ..=:;.~
-, . . . .,..,""Ol_...
_­.!"iOPI....... [ ......-~-
_. ~-', ..,.-~---
"""""1""""""'-" •_- """"'--"
- _~ ",,~,,~_"'nu:_...
" ­ "'....--- l ._~
....."""...""-""~
"

~.
I~
~L,- ..
,

.
''.''l·J!'\~·
f, :
•
I I ,~~,~.r-1i""7"-~~.
I.j
."

... L
i) '~L I' =1 -L
i·
•.,
I
'r~~_I __ ~'--->., '"
I I_

It -,
....

'J::';:''''' " ...

I'r.­
1
·-t 1
I

• I' .""1',,'G .. ,.....-n

{ "I,
'11. ~!I , R'
'~fL.ir . ,~
I,
I

~~,

"I
"I
,. ""'~
I I L I r'l
'~ I: . y '" 51>: x'" 2.04e"'OO3 «( '" C,S94j,)
I'"

I'~
~'~;j
~OOe4
----­
_.----,~------
----­
I
6.00c4 ________. - - - ­
4,00e4~ .---_.-.-­

2-00e-!1.~_----:-~-
" • • • •
, •
,'~_'ro 00
"",
00 I. 11. 1m ,. ,.. I. 100
I
1M
_..., , i
,W _
r-"-"'--'­

________________________________________ ___
~
r
~
~
~
~
~
------------------~~
 , 1-='''-''- .- .,--,.. - ->I

Sampf,e S~mp.le I Acquisition"Date

- Analytc pad::1 Analyte
Anatyte 1
PttakAreu Concentration
Anafyte I Retention
I
Analytc
1
~ Calculated 1A •
-
lconc'cntr~tjon! c{~~ac:.y
Type',
Narri~ Name Units
(counts) I (ug/Kg) I Time (min) I (IlS/Kg) ; ,

,11 1 PM h -" pg/Kg ___14770. 110.0 --i5-61 pO.8 1108_

i2
",.
lPM
- -"
8240. 120.':.______j~~_____ 117.6 _. ___ .-188.0 ___ _
,3 .,,_ ,2 PM 150.0 15.58 )51.2 ]102.
i4 -[tooppb fPM ""
:JfKg
- --­ -T------------C---­
0_ i iOO. ,5-59 1103.
----.~--~--
li03_
­
~ 1200 ppb -"?PM 1200_ ____ 559­ - -l1'9!l'---'j98Jl
16
191
) PM--..........
-rAM ug/Kg I~:~ __~F~--~~--·. ____ ~:::~ -~-i[~. __ -_~-I
"'_"'iiIi'i44il>:~'
II=~......,"
-....
..........
,
...,~
~_V1""_...
- __
-­ -­
-.:;;;=.....z'~~~'1r.':7"..;:-yl~=fi,Z;W
~ ""..--1",..","'"'' _ _"' _";;;;ziii"""
_ ,_"'tU-t'
"'-"-
~""'-~
-" I .........,...._
. .,
............ ~
,....-o:o.;_~~
-~
.... -t-F_W'<-1~'"
I ..., _.' _...........
-~ -~-.
_ ~r~,""'~
~-=,~,.

:1
_I. ''oi''
'-"i-',..,. .....
I'
·,:::-~rin~li ~l. _""_~-UiO-~I'~
-I I i, -U
, ..... " .. u,i"
! -I
f,~~._ .. ,.",~_~r
'L"lL ! I
': ,', .!:,A~~~
li= .......
':lnihr Tr1
I" . l.Jnear Regre!!;~ioo n IX' weighting); Y"' S09 x + ·730 (r"' 0.00(0)
1.ODeS., ____ w
1 _____ . _ . _ -
~00e41 -------­
I, '--"""1
~
I . 4·00e4J
(
_---~
- -_.-­ ------­
2-"""11 - - _..- - ­
;,.,----­
1Q 2'0 ----;O-c,"o--~so'"--~'~b:---~'3o:---~,30:-----.7'o:----,:160:--~'~,~o--,"i~o-'11Q
I
'400
.-
150
,
160 170
--~--r--

180 190
,'''''

:W=:::." h' _ .... _-- -- ­

,
• I
Analysis of Pesticide residues in river

water/sediment samples from India

( ANNEXURE III
)

 .- ,

·l'I'''''l'1(}N~;9~fr ~Ql1f'1,j~~lJj;M~ffi~p~~qAtrTHQ~h
. .(j(j'tji5i£Jt1iUiIATaii¥ftRA,i5ti&·
, - '-"'. _" '."-:-', ,'. __ '.-00-' ,;.~~.-",' '-'" . -" ,,' '.' .' - .

-GriP' l.i~~c:n'i)h" ,\vas., -<:~n:led_ 'our·..·ut "SOS', in4!~ :~i!y-~~¢, 'L!llij.(~d~;_ LiJc ~ct~f(cCi:,._&,CD;j,~~Si
"', SCC,O_ll~ 'irlo m::-, 'TI G~~,: jJ.i,()'-_P;f~k J.~t_d •.~-:.i:~ra:rn:;{ri.l *o'~'~;'l\(r~ 'C~;cnTi'ii-'6'ti'(rn3 in_ the-'
ni'ani;
follO'~\;t~(#~~.~~: .117~E~n:riC:: .
• Ttixiifti',--::ilt'u_c.iici,
• ~!u-~~'g,~',iji~~j,~t~:tu,~~~: ,
• t\n.air'tic:t'Land dinlcal"6hc~I,sfry'-'t.~~,t(~,g

B·as.<i,d -,011_, ih~-' inspeatiol1 ;;~p0!:1 <Iil,~ :,ttj'p ,,(~r((!\y,~YP ,~c;t,i.ml,~ ,t,~~k~~ b.y, 'th~'::'-gS.kr~Gjln~!,_ it ;is.
-~_Q'Ll,firnl~i.1 !!iaJ :Jp~ .!'e~{ f4~IJ-i(y :i~, ~Wp-a~J~:'·qr·'t:9rkl.4cthtg ,(he ,aoo\'e.:.meJllii)ned: ~tu4ic~; in
,¢q-rn:pj"~nce \~iih:'·"(~EC,D.\P._r1ndples, of·'O'-?9{1. tg~:".t;~t,~ry·- p-r:a;Cli~'c:-(G~.~r:Ah:G :t"!o;r'n,l~, ~J;,
'adbPle(f-by::t!I~;;Na('~li~lo ',y:.r:,~- C9fiiRU§r~~:c"tvf9~i[Qfi.~kABtb~oriL)< - -
'Illl-s;Ot:p' :.t:~rJifica~~:'iS, va,iid fdi':',a;:p'crki-u_ o['-tlfr~<! n':! r~ hOlll ,Ih,e,:da\c.-,o(is,:{(!I!" StlRjcC.t' 10 the
:~qh,d~,(W.n)\~a.t' l.~¢_'·~~~t tii~Uj,ty:;p'brripfie'$_.-_w.iih _the Tcr.ms & 'C-~ndi.t'ioll~'-tlJ t~~'N,'~ti:o:_~_:il GLi"
.C9n\p',I(an:Ce'M~nttoring-A~tli_Q:rlit~~:Q;Q;~Ymg.~~1'f.~m_~~rgJ,..r~-@J.
,._­ .. ""'­ .. - -
..-' -, '-," -.', ,
-."'-' '-. ' , ,
,

':" '

,--,'.- '.-'­ '--,'

(,

---\
~-:; . .,
Analysis of Pesticide residues in river

water/sediment samples from India

ANNEXURE IV }
(
'----~
 •
ISO CERTIFICATE 8G8 INDIA PVT.LID
Analysis of Pesticide residues in river

water/sediment samples from India

L
ANNEXURE 'Ii

)
Analysis of Pesticide residues in river

water/sediment samples from India

(~___A__N_N_E_X_U_R_E_V_l_ ___~)

 t>itf,Q;15QUllW20'Ql,CPW
'Governmentoflndia
'Mirii!Wi.of-'Eiivff<i'rirn'snt &: Forests.
p,~ryp~~?Jll3:_hawani, ~<?o c.:o'mp.t~,*,
lOdhlRoad, New Delhl-lfo 003

DatOd 25,1.2008

To

M.r" ~, Part1jlban(
LBbo.cato[y MaMger,
Mis, SGS India PVt. ltd.,
1/S09J\,Oldr,lahalialiputram Road; t.'
(Opp. Govt'~h""ll,
-fharaipakkam,;dehnai·600 097
Subjed::-For recognltion as:Env!ronmen~ai laboratory under' the EnVlronrnen~
(P(Q~on)Act, 1986. '
, Sir,

Pleas,e refer t_o your ap'pHc;Ulpn' seekili9' renewal oT i'i:!:G:o'gI',lJtlO'n of your

Eiwiror'lme'ntal Laboratory >under ,EiwlrQrlment (p'rote_dion), A'q:, ~ga6. It has
been dedded -to, ac:corp 'rE1iiognttigff :to -Mis,; SGS India' 'p\'t. ltd., C:hennal. The
terms and conditlQns s:? given-In ~he An.n~ure;... 1 a.n
have fJlreaQY 'been agreed
by yeu.

,2. You are reques):ed f<j partldpate In the analYtical quality COntrol (AQC)
exercise con~ucted IlvtheC~ptral Poll~tipn {',qntr.oleoard.and·provide "'9ul~r
monitoring r,epbrtS,bf your 'lab, '
3, It m'ay also: be 'n~ted, '-that perlddlt surveillance 9{ r~q}gnized
envkonmc0tq! I~bo:rato!y u.nd¢r ~be:_~nlJ,r(1)rt1,ent·.(PrQ~¢t;tiqhLf\Ctll~89 Will be
Linderti:d<en'by,'CeiWra( GOvt.(tPCa"ttr:asses~:'tn~ pro'pef functjonlngi'~YS:~!'l1atic .
operat!orl'and'rl;:!!,ab.lIiW'of 9,a~'g!fn~r~,t~,,~~:tnt!tla~'9~~tQry., ' - ,