Endosulfan residues not detected in river water samples- Scientific Research by shreeram kannan

REPORT

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

Analysis of pesticide residues in river water/sediment samples from India

CONTEIHS ,

I, S.No

Page No.

Description

,, ,

Declaration

I,,

Quality-Assurance Statement

,, ,

Certificate of Affirmation

i Summary of the Project ----------------~

6 ------,_ ...

....

' Project Details

Introduction

---

'''''

,, ,,

About S<:;S India Pvt Ltd

Identification of Study Areas & Sampling Sites

list of SampLing Locations (Sediments and Water)

Sampling Procedure for River & Surface Water

,, ,,

Quality ControL & QualityAssurance

10 ,

• PartiaL Valid,ation Document for Pesticide Residue AnaLysis

Procedure for Sample AnaLysis

Records Management

12 13

, ,, ,,

~---------

Results of River Water Ii Sediment Samples

-.-....

Conclusion

~naLYSiS ,, ,, ,, ,, ,

,, ,, ...................,,,..

(FAO)

i Chromatograms for result along with the caLcuLations

,, , ,,

26 34 I

GlP certificate

III

ISO certificates

• NA6L certificate

• MoEF certificate

SGS India Pvt Ltd., Environment Divis;on Chennai j

....

Analysis of pesticide residu.â&#x201A;Źsin 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,

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,

, ----

9;~~~Orqf:,'"'''''' > ,--_.-

...• , . :

.,!-

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<,'

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

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in rlver

".''-; ¥iitJ'rlS'¥~iitl!!'rlf~t\mQl~§'ff6inl riara . " . '. """:'_ >", >? ,_,_",< ,:' ',-; -'._ - .' .:,,-.--;"".7 .j.,' ',. ,_ '., -:--_.-' _,'

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)

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; .

,,".'

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

Analysis of pesticide residues in river water I sediment samples from India

PROJECT DETAILS I.

GENERAL INFORMATION

••

Date of Initiation

1410712009

Date of Completion

30{1212009

Name of the sponsorer :

Centre for Environment

a Agrochemlcals

(CENTEGRO) , Mumbai , India

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'

environment Division, ChenoGi

,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 classified into . . pests and, diseases. These pesticides can be broadly . . 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

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

•

Analysis of pesticide residues in river water/sediment samples from India

Analytical Capabilities

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 dr-inking water capacitor and transformer oils.

SGS India Pvt. ltd. personnel are proficient in diverse methodologies, including:

voe, SVOC,

Solid Waste (SW 846) Procedures for Metals, TOC, AVO, HVO,

Pesticide and PCBs, EP Toxicity Et TelP

» »

EPA and Standard Methods for the Examination of Water and Wastewater

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

US EPA Methods for stack emission

NIOSH Methods for Air Testing

PAH s - EPA 8270

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楼:,ijs

,i>i i~iryand~\hi!r sPeCialil'eq par~m et\!rs.. . ,"0--

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' ..' ~ .' 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路 for "\fl,iater contamio.ations by路 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;

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\

'ft.

SGS India Private Limited En.vironmenral S~r\'ke.'i. 101, Signature_ I, 233.35.09. f (91路265) 233"'j::3R;.81~.""""",_ _...."

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UKAS : I

~'_" SGd~ .....'t~'!.1~~ 'f>:;:..J II

e,p.c. Road, Urrni Char RaSia, A1k$.puri. Baroda -

390 007. t 191路2GS}

-.",M"'",~-\''''路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;

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 SI.No River -

__...

Varuna

Ganga

··I•

Varanasi

I,,,

Pilibheet

,, ,, ,

Gomati

Deva

Ganges

!, ,,

Sarayu

,, ,

-,,

6 7

location

Varanasi • • • •

Sampling

,, , ,

Sampling Date

Location

Varanasi

Town

-----_...

Away from 3km from 180 Ghat Near

Total Sample

22.10.2009 2Z.1(tz009

Surajpur

23.10.2009

Village Pilibheet

Near road Bridge

23.10.2009

Daal Mau

28.10.2009

Bahraich District .

Dhasan

Bahraich

Lalitp~r

District

, I

28.10.2009

Near Grash Village

29.10.2009

ehamoal

enambal

Etawa Distt. Near Bhind Road Bridge

30.10.2009

Yamuna

Mathura

Near Rail Bridge

30.10.2009

Bhoipur

Near Hapur Road Bridge

01.11.2009

···-

Total Number of Samples

SGS India P'(l Ltd., Environment Division. Chennai

., ,.

,, ,

.10)0'09

Be~~-j{i\)er

,Rav.j Rjver

,.,, 14: 10:2009'

14,)0:20D9

1 ,, ,,

1 ,10

, "

•

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

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Analysis of pesticide residues in riv~r water !sediment samples from Indla 5.3 ;TAMIL.NADU SlATE

-Thamirab,harani

Kokirakulam

'-: .'

K6kirakulam

:· ··

09.09:200:9

~~--~--~.--~~--~~T.!.~------'·~--~--~

~2---1'~~Va~ig_ai

09.09.2009

Cauveri

Tiruchirapalli

Tiruchirapalli,

. 11.09.2009

Pennaiyar

Villupuram

Th'jrukovilyur

13.11.2009

Bhavani

Erode

Pallipalayam (Agragaram)

13.11.2009

Bhavani sagar

Bhavani

14.11.2009

Noyyal

Karur

Kombupalayam

14.11.2009

Paiar'

Chengalpattu

Dimmavaram

16.11.2009

Thiruvevdipuram 22.11.2009

I :

Kochadai

ir.

··· ·· \ I

Modurai

···

. .. ..

;

8 ·· ··

Srirangam

BhavaniSagar :

· ---~-~""""':""

Pennaiyar

Cuddalore

·· ·

Total Number'of Samples

SGS Indio Pvt Ltd., Erfvit'onment DiviSion! Chennoi

Analysis of pesticide residues in river water/sediment samples from India 5.4 MAHARASHTRASTATE

SI.No. River

Godavari

Parvara

Location .

Sampling Location TAPOVAN, NEAR PANCHVATI, 25 KM FROM NASIK CITY

Nasik

Western Maharashtra

Sampling Date . 25.10.09

DIST-AHEMADNAGAR, POST RANDHAWESTERN MAHARAS.HTRA

Total Sample 1

25:10.09 1

Western

Parvara

Krishna

Pune

Krishna

Sangli,

Maharashtra

Manjira

Purna

Latur

Amaravati, Akola, Buldhana &

Jalagaon 8

Tapti

Jalgaon

.DIST-AHEMADNAGAR (WESRTERN MAHARASHTRA: 70 KM FROM RANDHA. WAI, NEAR MAHABALESHWAR AUDDUMBER, NEAR SANGLI

26.10.09

POST MHAPUR, TAL-LATUR, DIST-LATUR; 15 KM FROM LATUR CITY

02.11.09

POST CHANGDEO, TAL· MUKTAINAGAR, DIST JALGAON 70 KM FROM JALGAON CITY, 35 KM FROM CHANGDEO

Yavatmal, Nanded,

Penganga

Hingoli,

Washim and

Buldhana districts

Godavari

Nasik

31.10.09 01.11.09

1 1

1 11.11.09 1 12.11.09

16.11.09 POST MAHUR,DHANODA PHATA,75 KM FROM DIST YAWATMAAL

PAITHAN, 56 KM FROM AURANGABAD

Total Number of Samples

29.11.09

SGS India Pvt Ltd., Environment Division, (hennai

Analysis of pesticide resiciuesin river . - ;';il.rer Isedjln~ntsamples from .IDdia "

. ~;5GU~ARAT STATE : . ,

No." RiVer

I -

;

::-., -,.

' , " " ("

AHMEDAMb

, VASADi 25:~ FROM '" VADOOARA '.

Vadocara

Nar:maSia

Narmada·

VadoiWa 6: Bharuch .'

Shetrunj

Bhagad

Bhogavo' , , Surendra

Palita~a

: .,

. Nadi, D~ng?lrpur

Dhupeshwar Malkapur, Navasari

29.10.09

.6AHRUCH.

, : 30.10.09'

15 11M FROM PAlITANA,'G1)JARAT ·2HMFROM

21.11.09

D!.!NGARPU R 15KM FROM

Nagar

Puma

SUREI'iORANAGAR J -

. DHARAGIRI {1011M FROMDIST,NAVSARI, GUJARATj

1)PQST RANDHER, TAL 8

Tapi

Multani,

({11 KM FROM SURAT

Betul

CITY)

Sabaramati. Garidhinagar

Tapi

sal,lPle

'. I ,

Total

I .1) NEAR EUS BRIDGE,

. Sabarama!; Ahmedabad; , Mah;

.. ·

,'"

:', -

. Sampling

!,ocati6n .' .. ,', ,, .

, ',

SarnPli.i!l1,9~~tioh .·o.• w·· .

: ~r.

21..11.2009

21.11.09

22.11.09

CH)-IQTI CHILDD, 25 KM FROM PALITANA, GANDHINAGAR

I 1

5.12.09 Multan;, NEARKMlREJ( 35 KM 1 fROM SURAT 12.12.09 Betul Tot.l.Humber of Samj>l::::e,,-s_ _ _ _ _ _ _ _'-_1"'O'-..J

SGS India Pvt Ltd:, Environment Division, Chenna;

Analysis of pesticide water/sediment samplesfrom India . . - . residue.sinriver . '. ". . . ."

5.6.ANDHRA pRADESH

:. .

! 51. No.

NAME Of RIVER'

~""""MUSi ..

, I' ···

location

··· ·

SAMNN(i . LOGATION

Suryapet.

$ury~pet

I I

21 Paleru

Suryapet

Sabari .

Shadrachalam

..- ....

, 4

Ad,ilabad

. Pranahita

__.

,, ,, SAMPLING ..., DATE .

Swarnamukhi ,,

"! Tungabhadra

iDindi _ _..

.. ..

.... _....

i Pennar River

27.11.09

I .. .. ..

Karnool

,, ,, ,,,

27.11.09

Godavari River

Sileru River

27.11.09

Dindi

27,11,09

.. .. .. .. ..

Sangareddi

27.11.09

Nellore

Near Bridge

02.12.09

1 1

.. .. ..

, , ..

River

""""~

Gundlakamma . Krishna River

I ..

Adilabad Srikalahasthi

I I

Srikalahasthi .

Dindi

27.11.09

........................... 1

Manjeera

27.11.09

"""""~

Bha:dracha,lam

17.11.09

,, ,, N~. ~f ,, ,, Samples ,

,, ,, ,

Ongole

03.12.09

Vijayawadaand NarAgjuna sagar

Vijayawada and Nagarjuna sagar

03.12.09

Karimnagar and Rajamuridry

Kar5m Nagar and Rajamundry

04.12.09

SriKaKulam

Srikakulam

05.12.09

• Total Number of Samples

.~----

SGS India

PVt Ltd., Em'ironment Division! Chennai 11

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O(,:u5,tbdy se.ais

·1'-~_(A~("PJ:as.~),~::Jars', ',_ '. -'

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foW

Alum,in'l.Jm

. 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, '~.q~ipi:n~~~', aU- .the--. safety' p~ocedur,e~ .' " '~a8p.l'.i'ng. ,,'.'.- '. "

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,folloWed a.s~p_er Etqlogy ,Cheniitat:Hyg{ene Pi~an':as_ gi:V,~n below. ,-',

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were

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,"., '-~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_:-.:~:~-:,:.'.,}

.' _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~ ,.,> -'- ,,

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Analysis . of

pesti~ide resio~es i~ - riv,!r~ater /sediment samplesfrom India "., . -

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

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 ~he river.' Samples were collectedfadng upstream, right bank, left bank and center .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

".- ,

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'. pre~a(e~:iRY fii [jOg a.."arpple.路

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to {die~kfor: poSSible ." . .. ' . '

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An~lysls .

of Restitide residues ""att;rlsediment . . ". .in river '. . . . .samp}esJrom India

After路reYlewing,the, n'portit was handed.ovN to the prp)ect l~a<ler for fjrial report pre'pa'ratidn~ . . . 0,.

6.7

Safet~

Field work done in. connectlonwl,h collecting water/sediment samples In surface waters'follow~d the protocols described in the Environmental Assessment Program . '. . 颅 . 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路' 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

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 路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!

- -

'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

1 ml of WS1to 10 mlwith toluene

10 ppm. Wb;king st<lndardZ ----' . . w~smade by diluting , giving路,oncentration of1 p~m: Working standard 3 was made by diluting 0.1 ml of WS2 . to 1 ml, with anOO ppb. . tOluene giYingconcentration ," . '

.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

Analysis of pesticide residues in river wat.erlsediment samples from . . India

7;7.3 SPII(E.aR.E<:;9VERY:.路

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

3 4

50.12

5ulfate : Imidadoprid

48.50

48.25

51.30

49.83

路41.44

43.29

39.44

49.20

49.50

49.20

50.1

100.22

39.25

4.0.3

80.62

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颅 MS.

_SGS.-

SGS India

Pvt Ltd" Environm~nt Division, Chennai

':> ;.

, .'....:,,",' ,.,:.;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/;;,.:'<':, :":~' ,:,:,:;.,.: ,:.: \-.: ::~_ :': ..>' Se]'lj!ll~ijt'.s:l!J'1pt~~;(aR8rpx'in)~terY;25g d.t~·i4eight}0;i"e extracted wi'th . a 1 ';':;";'::

.. '

"''':'',''

',',

" , ; ' ' , : ' .'"

' , " . " " .• ,

,',.':\"~,,,';:"'-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, 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 ;Sliil,. ..of .', .,:: ~-::::".-<", "c-, "", ,'~/,•• ,'. ',-" •. '-' .'.', ,,',_'.,"', :.': '; :: ",',"",.,'>". .',:----.',:,:' ,~'.",'.'.,"", 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 ~'_,'1",

< • • , ; '____

•

'._

(>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.

,'"

,:.

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 垄ondensationof pestitides on surfac~s9f within the laboratory . . . '" . , ,. '-_. - .giass vessels ','

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路 detectable residues. (DL :0.00001 mgtl).

",..c_

-----.V.u~

SGS India Pv: Ltd.) Environment Division, Chenna;

.,;. ~

Sarayu足 .' ,:. ,

-';,

-足 ,

Analysis of pesticid!'lre.siplJes in riVeT water /sedimentsaITlJ;>leS from I.~dia ..

.... ..

, ." .

! STATI . ; Satltlj" Riv.er

(~unj~h)

Satlul:River (Punjabj

Satlu{River

(Punj~b) -

,,: ..

..'

'~:~':;'

.~:: ~",g!

:0' '.

~~DL:'

~ :B~L ~~;;:~

19hiaKhas.

; near bridg'e

~c'

Stream, ,Near Joadl~r1dge

Beas River

13.10,2009 18:45pm

Near Road Bridge

:, 14.10.ZC09 ,I

i 11:30am '

, ,i

RaYi Rive:r

mg/l) ;

mg/t)

: Rn!

ri,.:, nrum, mgll) :

: BDL Q!c~ m.111 . I BDL'tJh.:.O.OOOOI mglll

BDLIDL

,.Down

Stream, Near,

BDlfDl JiglDl

Chandlgarb post [Pakistan Border]

, mgll) I mgll)

LQtl2(l'l,m., ).00001 mgll) : 0.COOD1 mgll)

• Rh' m, : 0.00001 mgll

-----

•........

18 ,

~1 ~!;:

Ravt River

,i ,

• mgli) I EDUDl :~ m.1 !BoLiDL.: . I mgl

~~:~:;

, o

: Kanuwat, Down ' ; Stream-, Near ,

Seas.River

·~lDl:.

I ,:

I mgl

I mg,

I Rm m : 0.00001 m.,

~~~:~~;~II

Ha:rike, Down

15.10.2009

mglll

Stream, Near

Beas River

13:QOpm

Dam

: - I '

• .

I mg/l) ~~..m~! n

~~.~

Down Stream,

I Road Bridge

:~m'll

iI 16

'~,""/ll

•~ .

~15T~~r-~~t-~"-~iIHar Har'G051ii1dpi;,:;,-jj~- '. Beas River

.lm.JI):.

~ '~m.111 J" I . m .DL: ... ",gil)

r.,...14-1-----l~~-'-~······--~-+Be-a's·,·"D·'ow-n--'-f~~Z"'·

13.10.2009 ' ; 16:~Opm I

'~.~ .:~m.d)

, ~nstre~m,

6eas River

i .......

Ine~r bridge

. '. . . 1

~. ~:~'~+~:';l)

. . ;".~".~

::.

: '.' .' ..

_S.G~ SGS·Jndia Pvt Ltd., Environment DiYisi~n, Chennai

Analysis of pesticide residues in river water/sediment samples from India .

• 09.09.2009 i 8.30,9.00 I am

Thamin.jbarani ! fThirunetvell)' :

Kokiraku{am

}Qi;t.: Vaigal

4.4;·5.15 pm

(Mad~(ai)

11.09.2009

7.45-S.15

CaWen

am,

_:O~m.

Kochad.i

, i

liruchiJapaUi

(Srtrangam}

Pen(1aiyar

7,45-a.15 am

1hirIJkovilyur

{Villupuram)

(Erode}

Bhavani

,, Bhavanisagar

Kombup,alayam Neyyal

1.00-2.00 , pm

Dimmavafam

122,11.2.009'

(Karur)

Pater (Chengatpat)

, : : :

it'

'Kodumudi

: 16.11,2009 :

•, 10.3011.00

Imgl l : BOL(~1 mgll :BDL~ mgll , : mgl!) : mgll) I m'ill) ,:,Imgll) ,: Imgl!) .: I mgll

• : Ot • mOl BOLIOl : 0.' ! mg, "iiN _: 0.0 I mg, _: mgll) iBDL ~i:Ooi501 mgll) I BOL DL : ,,-:OCOO1 mgll) , : 1.00001 m,1Il LO!!Jll.: ",Sll) • ).0000: mgll) , ).0000: mgll

1.30-2.00 pm

, 29

14.11.2009

Pampalayam

Agrag;;tram

Bhavani

: 14,,1. 2009 8.00·8.30.

.:O~mg

13.11.2009

13. 11.7.009 4,00-4,30

I mgll Img

~:::~::

09.09.2009

:mgll)

Pe,nnaly8i

Thiruvevdipura

(Cuddalorej

Godavari river

25km from Nashik

. I

~: 4.~~STATE 30

• 25.10,2009

25,10.2009

at tapovan

Parvara

, I

Ahemadnagar, : PO,st Randha Western Maharashtra

BOL DL

I mgll) ,

Imv

~DL: ~m.,

: BDL Ut . ).00001 mgl ,!

----.SGsL

).00

SGS India Pvt Ltd., Environment Division, Chenna;

'-,

Analysis of pesticid", residues in rjver ,,>;,,!:," "~Y~'"'' ,cO' . f,um India , . " ". " ,.;. . , ' .... ,

•

: 2,.10,2009

.'.

,..:

. , •. ,:

... :

..•J

".'::

,.':, . ;.mg/l I Porv." :,'" " . , ~. , .'. . . ,BOl ~ I . , . ' . , .'" . ..' : SOL ,'~ ,: .' 'I . ' . : . I SOL .: . : mg/l)

36 ' ,i

38 '

40 ,i

, ! ,

41 '

, mRIll ~m.ill

: 6.00001 mglll : BOl,Ol I mg

I :

:. 42 :

~~~: I mgll

"O~"lm"

. : 0.' . : 0,

l~:'

mg.

mgll) i

m,lll,

IBDliDl : O,{)(){)()l mgfl) ,

_S_GSit-

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

Analysis ofpe5ticide

,eSidue5i~nverwa~erl~ediTl1erit samphis@nj India

..... ... .. ... ..i

..... ....' .

·i

... ..•

. ,.

J~_ ~:~~:~:;

...

in"

mg/l

~'~:;: 45

, ,1.11.<009

Bhogavo River

~ .........••....... 46

22.11.2.009

Purna River

<2.11.2009

Tapi River

Post Randher

05.12.2009

Chhotl Chllool25

Sabarmati River

Kms from

: BOl

Gandhi Nagcr)

Tap' River

, mgll)

Near Kamrej (35

I mgll) : I mg/l) I mglll

Km from Surat), •

-: ;.00001 mgll) :'""mmm________________________ , 0.00001 mgll) :,

Multani, Betul 11.12.1009

I mgll I mgll . . :' Jm,/I) .: I mgll) .: . I mg/l) mg/l)· ]iii;oL : 0..<J0"21 mgll) ~DL : 0.00001 mg/l)

~~.:~::~:;:l

, 48

, mgll) I mgll : I mgll Im,11

: STATE

27.11.:W:J9

Mus, River

mgll) 01 mg/l)

Suryapet

mgll) 0000 mgll) mgll) mgll) mglt} : mglt} I mgll) , m,/l) I m,ll) I m,/l)

51 1.7.11.2009

Pateru River

Suryapet

27.11.2009

Sabati River

Bhadrachalam

,5,

27.11.2009

Pfanahita River

BDl BDl

Adilabad

" ..

_sIlsl

"1,/1)

I m,lIl

I I,

I mg/l) I mg/l)

,, . ,, ,,

SGS India Pvt Ltd" Environment Division, Chenna;

• ,

• : : i ,

27.11.2009路

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

Pen'na-r Ri'ver

Oi.12.2009

Nellore

Gund\~kamma

Ri'ver

Ong9le

03.12.2009

Krishna River

Yijayawa:da

03.12.2009

krishna River路

Nagarjuna Sagar

路04.12.2009

Godavari.River

Karirtmagar

04.12.2009

Godavari River

Rajamun'diy

05.12.2009

Sileru River

,SrikakUlam

03.12.2009

63 64

-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

p.m•.

Kachadai

Vaigar

(Ma<,luraj) .

I 2

13.11,2009 I 4.00 to 4.30 p.m.

- Bhavani

. Pal1ipalayam ' (Erode)

(Punjab) •

river

08.10.09 I 06.00 AM

Satluj

08.10.09 I 04.30 PM

Satluj river

downstream,

(punjab)

(Punjab)

(Punjab) . i, downstream,

near bridge .Charnbat,

30.10.2C09

Chambal

Etawa Distt, Near Bhiod Road Bridge

L 30.10.2009

Mathura, Yamuna

02:25pm'

r'(ear Rail Bridge

. ~H$.

SGS Jndia Pvt Ltd" Environment DiYision, Chenna;

". . "

'.'

-'路'.'i路

.....

:.'

.. -.,'.

' .. :."

.',

':.

'.'

, '.'

34 ..

.. : :;: .

.. r.

.-'

. >: .

.'/ ::: .',,' '.

Analysis of Pesticide residues in river water/sediment samples from India â&#x20AC;˘

(

ANNEXURE I

)

...

_ - - - - - _... _

SGS INDIAPRIVATE. LIMITED

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

I Thordipakkam; Chennai -600 091

~~---__---------~-~~~~N~o~:l~----

==___ - - - - I

I METHODVAr,mATION

1_ _ _ _ _ _ _ _ _"D"'E'f¥-RMINAll0N OF PESTICIDE RESIDUES IN WATER BY GC·MS-MS 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

--~-----

-~~-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, i Thoraipakkam, Cheimai - 600 097

TEL: +91 (44) 24963844, 24962822 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,

'lboraipakkiun. Ch,nnai 600097

TEL: +91 (44) 24963844. 24%28'..2 +91 (44)24%3075

~_ _ _ _ FAX

r~=oo~N~O~&~Da~~~路TI,~OO~~~6~~"O"IO~------------~

. =c---- _________-'P?J!""- No:' I-ME'rHOD VALIDATION LI_ _- - _____~_"D""'E~~.RMINATION OF:.PESTICIDE RESIOVES IN WATER BY GC路MS.MS 3,2

Chroma!.OQrapjii<: Cooditions of Gr'rMS-MS Insirument

Injedo: Solvenl Syringe S!ze

: GC-MS Triple aved 7000

7890A Agi!ent Technologies Injector lO',Jl

Pte 'injection solvent fluShes

Post injectfj)n solvent flushes

Injection Mede

Spl~

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.

less On 7683 IliadOf'

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

SGS INDIA PRlVATE LIMITED I SQS India Pvt Lid., ~boialOl)'. 1/509A, Old Mahabalj~ Road, I Thoralpakkam, Chennai- 600 097

",'~+g",l,",(44?)2"4",,96,:,J~844,,,",2:::-49;-;:6l_'_22_ _ _ _.....---i ~ _ ~__TEL~' FAX4<lq44)24963O'15 Issue No &; Date: l,01-06-20\O

I :METIJODVALIDATION

No:5

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) , '

I, I,

Fio<ll Volume

Final Cone..

(mL)

(ng/mL)

7.5

2.5'

7500

10 .

5.0

5000

2.0

8.0

2000

1.0

9.0

1000

1.0

9.0

500

!-W... 5

Prepared l}y

Verified By

Aprf\},,~d

I I I

s~s

INDIA PRIVATE LIMITED

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

~--------============."--"=====------ ~

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

of! Volume

Volume

(nglml)

Slock(mL}

7500 5000 2000

f--

1000

500

DlIuenl(mL}

Final Volume

FinalConc.

(rrI..)

{nglml)

label

0·100.

0.900

1Jj{)J

75O

.CC5

0100

0.900

1.000

500

CC4

{).1~L ..

. 0.900

1.000

200

CC3

0.100

,0.000

' 1.000

: 100

eC2

0.100

0.900

•

, 150

1.000

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.

Cone. Volume

StocK

(!JgfmL)

5,1.3

Volu!'f1o

Slocl<;{m

Diluent{m

Final Volutni? (mL)

Final Cor.c.

("",mL)

0.76

325

6750

3.75

625

3750

1.6

6.5

1500

....

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 sta!ldard(HQC)

Cone. ' I/olurr.e

SlOd<

(nglmL)

---~By

,i .

of i Volume

, stoo<;(rn .

muen!(m

Final Vulume

Final Co.,c.

(mL)

{l-IgIL)

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

Verified By

Approved By

control

'.,

sa~pie p'~paration 6.1, ~. Ext~'cliOn

_6,0

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

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

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

i ThoraipakkarnLChennai·.. 600 097

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,

Precision (Table: 6,1 to 6.3)

1.3.7

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. 1

COm::.>OUOO

.~BtoI"l",Q-241ltlfO?her.~!.

Prepared By

I RUIl·1 50521

I Run·2

I Rur.-3

I..

49510

Verified By

46703

R,,,. 45'"

Run·5

411184

Run.6

49402

Approved By

Mean

49079

CV . 930.535 : HID

[

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 ],sue No &lli'''', 07-0",20(0

[METHOD VALIDATION DETERMlNATfON OF.PESTICIDE RESrDUES IN WATER BY GC-MS-MS

Prepared By

Verified By

Appr.oved Uy

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

----'l

Fage ~Q:IO DETER1\I1INATJON OF PESTICIDE RESIDUES IN WATER BY GC.-MS路MS 43

22925 :

Deltamelhrln

18673

18328

17198 '

=" ' 16476 :

221'rr颅 17094

16949

17453.0

&S5. ~5a

4.00

Prepared By

Verified By

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 I

CyIlultnin-lll CvlIlI.hrin-1V CvoermeltJM.1

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3. 40

C~_Q1rin-1Y

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r-.. . . .

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11!312

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362.61i 1484.41

1~361

12056

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39725

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42787 ;

21189

11046 462ll 215!lO

11545

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60061

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666IJ ...,=

Approved By

'~J~

3,90

4,~~ , 4.07 ..~~ ~,"!.. 3.10 , ... _---,

4.75 6.80 -

SGS INDIA. PRIVATE LIMITED

1.0 Objective

To develop and vaf.date GC路MS路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

)

Quantitative Analysis Calibration Report

Batch Info 8at£h Data Path

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

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iUAnt Time: Dec 24 09:12:01 2009 0: \msdche;n\l \METHODS\Grapes200S.H hiaWt: Tit"le' Grapes and Pomegranate }LasC Upoate wed Dec 23 17,42.37 2009 Initial Calibration '-espouse via

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t Title

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Wed Dec 02

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2009

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-------------------------~--------------짜~~~~*-------.----.----.--~~~.~-

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j -

arne

11-

Acquisition Date

'Oi:12i"wr

1100 ppb

IPM

I:ZOO ppb

ISlanK

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- ...........

"....., ,--.

....... _ool''It<l\mU_ , , - - _~'

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__________.--___

2..~4 ~--~-__:=."r-- ~_._.

1---·-

__·I~~8pe8k-'"--t~~: - .-

15.134- ~·---·~!6.45

..... "'" fl_ .... .-.-.-. . . , ""~ ..,,;rkT~I-r...-·.. ;a ~"" $,-, TIE~-...~':',g:;,:;-rlf·~ ..... ....... ,n>,.,.. , ........_ _'I''''''''''''''''''''''' hol....,.... _.....,.. .. •..

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: (l1g/Kg)

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Ii,

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............ ~

JI~tJ9IK9 ~-12550, -

]1212412009 12:o7:ooAMI

!Concentration

Time {mm}!

(119tK9j

~~-!;~~:~~::l~L~:~:-=-tE"~:--l~~~:~~~-::=-i:~~O--~ . .

-;38:29 PM

"-~ 50ppb ,

ItJ~fKg '., -tam ~=j10~(r-~'---'---'-' -~-"-.-. _-.~_~j10~8~~~_~~~~ji~w""- ..

11:15:<] PM

20pp~

(cpunts)

10ppb .

Peak Area !Concentration

e _ _ '~'·..c~·.-

__ .,____ , . GO

------.---

C!1n~~1KQ

120

______ -

.' _,

130

1t.O

160

';sp

",,---,-

170

160

190

Sam Ie I

''"-_-.....' C;;;:::i>"""""j:

'=~_t,.,.,..

12123/20092;01:12 PM Imidacloprid·1 ~glKg __ 12f2312p09 2;23;54 PM Imidacloprid-I flg('<g . 1212312009 246:37 PM 12/2312009 3:09;20 PM Imidacloprid:I_I~lKg _ 1212412009 12:57;00 AM Imldaclopric-I

ImidaclopnC:'.J~gIK9

l~glKg

____ ". ,. "......

.,'iJ;w't;;;~iliY)"';'",,;;W

• •

•

........... "'" """

_~J_'"

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L........ "0,.1 ~l T.._'* _ _ ..... _ ..__r_,.,..".........

i J n

__ _

•

••

n _

->--..

•

23000:--.J50.0 51300. j 100. 111000. i200. 0.00 ._INIA432. iNIA

---

._...._~5.60 ___ .--:40.7 _ _. 81.5 .1

5.60 '05.9 105.9-l

5.60 121.2: J1GIl. __..JO.oo iNo Peak TNtA

~~...

........... _ _",j","<t:"'4.",........... ~ ...."""L-, ... <>: . .~~ tl~'_""5;;;;"'" ~i&"'·i.. '.... _"

..,."'

Conc~ntration

@'--

~~-'_\_··-·---l

Analyte=ll Retentlo,!, Analyre i Calculated j Accurac 'j \coocmntratlon! (%) Y

Anatyte.. !!i Peak Area (counts)

Slandani Standard 2oo'PPb Stal1d"rd o _ Blank Unknmvn 9110058169 Unknown

untis

~~~~~!:rd

An.al te

2~ppb

. 5OppI:J 100 ppb

Jam;:

Standard

Pe~ k

Anal fa

~1'--: RrpptJ -- ~-

.-",.•'".' . -

,~~;;;;:~ '·--1~-::..l..~"-":"f''''=L..,'''''~~:'''''''''''''~~'~''",\''\''''''''''"=,,,,--.,-,

I . i {~gIKg} Time (min) I (~gIKg) ! • I 1212312009 1:15:47 f'1~rllmidEclcprt~:r ~f~giKg ----TsosiO:'·--··!10-:O-,5;60 .------111.5 ----~~-·t 1 -. T~I23120091;38:29 PM rmj~~c:~~~~ci-! _ i~~/K~= }240_0'_ _ -l~~"~ __j5.e~_______ "I~O,1 ~.~.=~_ll~oo_._~~.~·l

AcqulsWon Pate ype.

'T P

am.

2 3 4

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. S:rmpIG

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~~-~~~~~~"'---

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1 ·;:t,:'~;;;"~ii~"""imiiI""''' n»

I :LH\¥lA,Y~)

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•i "1." ,...... ';U.II'r'~ j ! l ... • • • • .:. ... "

I .....................

"'10

-~--

po(

23-12·2009.lmidaeJoprid.rdb (Im;d;lcioprid.i): "l.iru::m,!"" Regression i'1 I x" w!Ojghllng): y '" 514 X" 2,O~~"OO3!r;;: 05)943) 1.15c5 !

;:::L'

~ b 00e4

---'____ _--------~-- - -

4.00e<:: :'!.00(,.1

-.-.-

--e------------

• ______- - '4lIi 10

-"-,.---

010

,--. "-"---r------------ - - .-

100

110

120

130

140

150

170

180

190

COCCfJo!r;l,ti.QJl...u9L1Sg, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __

W,',

.,-r",-.,.... 'ILl'

.......

"""".""'''-"''''''' Sample

Sample

Nama

TYpe

,.o:>'"..-,,=".-"'=:-"

"";e

",'

Analytc peakt Analyte

,Acquis'ition DatE

Name

'fJg/Kg

"1:15:47P'\1 2

:29PM '5:::I~i~ PM-l~'

120 ppb

3' ·-tSOPPb4

, Pr,I

5 6

7. PM

heio.$

Analyte j AnalytC" 'I Analyte \ Ca~iCufa!e~ \ Accurac . Peak Area ~Concentrahon Retention !CQncentrabonl r',q Y (counts) I (~g/KQ) Time (min) j (UQ/Kg) 1 ~ 18030_

110.0 ". ---..

-J5.GO--" ,_._-,

, ,

[100:---

. L . - -_ _ _ ..

_..... ~glKg-~l()~ __ JNIA-~=-~-]~-=---:"IINO 857.

IN/A

15.6~ ___

• ''''

~eak

IN/A

C 0:

NfA.

, ,

=&",~..... 'ii"T..::xu.::\iF'" 11~"'1It:7':$;';:;W":=i~h<ilt:;;'>--·~I~~q"".,..-,*... -,~,:;:£' 1"""''9.''~~".'-.!f'i;;¢:~''''''11T-'::;_T_''"a#~'lJ:!¥ ,,,, _ _ ,,-,",_''''''' .:-.-~ -~ -~ -~ -', ,,_~

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,......_ -'~l~""'"-.r _"l::'' ' ' ',,,,,,;

-'-r2'3000:"- '\50.0' -.-- -15:66-- ... -14if7 --·-j81.s--"" l~glK~" -Wi30o. -1'00~ .. -'[5:60 - 1950:--'95:9" . 91K9 11000. \200. ..~ 1212.. ! '~. ~g!Kg

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(lmldrldoprid.j}: 'lJI'lear" Regres$\cf') (',1'1.' welght,ng): y '" 514 X

•

1.15e5 I

1.00i:!S.j

i~ :::1

---------------------_._- ~

( 4.0r:ie4 ZOCle;4

L_c_

- .-,

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

, .......

~~_==;;:==;_ '~-' , , , --...,-' 10 lO 30 40 50

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"90;--~,~o=o-11O -·-1io~13-0-Oncen!rutiflrLU(JI~ . . _ . . ~_ . . ~ __.. _ .....

1<0

150

~OO

1'70

180

190

._ U"""___,_.. ,

..",' =~"

s~m,pJe

s,~mp[e

,arne

rr-ho i80 B-:-

IAm~;ra~:e,akj Ag,a~~e In,

ppb

50 ppl> 100 ppb

;'5

200 ppb

Standard Standard Standard

-~..

'mid.cIoprid'1I1~g/Kg '~.240~--=-

I,-LL'" ,.....

-" •

•••

., -

""--.

_~_

~. . . . . . til

.. " .." ..... "

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.... _ _ .._,.,.,....ru_.".

. - ..

I '

(~gIKg)

+5:iiT'-'''ima ,~- ~Fi6[--''"'-'-:

11fu,-: ;98,8, J

0:00 2170.

,... ,.

,I " " ,. ,.

............

<>.

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r '~

5,59 ___":",1196: ~oo iNO Peak IN!A .=5.63 _ 15.68 h--l~A

NtA

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•••

.... ......._

/. '" "

>Ii

_w . . ._w

....- . . . . .. ""U.... ......... ""_'__'"

>:7"

~I'ii#"'lZ:~iii;; f~:;:;'''''-~""'F-,-12'it' .......

.........

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1~L_

.__ ~ ~.f'"I, 'lil i

, . . . . . . . " " " ,..

~'>oie

I'"

I!I 2;"::t2~:'!lX)g;:imldadoprid"rdb {lmidactoprid..f{j: "L!nMt'" Regre~slon C'1 I X' welah:lng}: y '" 509 X + -7~O (r "" O.U9~O) t.OQe5

,J .I -<\.

'00e'1 <.00e4

2.00e4

------~

----<'-

----------'--'

..----------

---

i 1 0 - - ; - 30 4b 50 eO 7'0 00- e'o lI_________________________________________________________________

100

110

-"C.nn."20nl~~~"_

~oo

.,_ ,

-""<~--

S.OOe4

_.,Jsao_-='j

j200, I'NIA

100000,

--I

~.,...,,,;

~ ••

I . I t :lb',.- ~ ~rlt" .. :~I ,

1'0,0 -

CalcLllated

""""-._ _

".!!-'!,!L.f

Retentl~n' lcanamtr~tfon!Acc;(~~acy I

~ .. ___ '..,.....,'·1_" ... _ ..... _,, __,.- .. ....' ~~ _ ..... . "'''~"''W'''''''''Ii'Jlc~'''''''''--1 ~"J'

,...

_ _w __ ... _ _ _ -1<..... "'"......

•

I '

Analyte 'Analyte Analyte" Peak Area jCQi'lce,ntration ,(counls). (IJ!lIKg) j Time (min)

12123120Q9 1:38:29 PM' 20.0 ""'_ '5,62 117,6. 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

Standard 1212312009 2:46;37 PM Imidac]oprid-II Ii9/Kg Blank Unknown 1212312009 3:09:2Q PM !rnlda¢!opr[d~lI jJQ/Kg 9110058170 Unknown 12124/20091:19:44AM Imlda~:oprid-lr I19tKg",

6 1

- Standard' 1212312009 1:1S:47·P;;rllmidaCioPrid'if-jiJglI<9',·j;;-iiii:-"-

ppb

,t.\cqulsltfon Date

ype

'....'''....'''''' ... ''.-'=,''''~.

='-='""-'-"""'="'''''''''','''''''''''''''''"'''''<'''r'''"='~'l'''

120 do . 140 150 110 1ea _______________________________________________

" I"'''' ..

~=...;-.o

-Sampie

Sample

Name

Type

ame:

16030.

4"PrJ""

1200 ppb

7PM

-1 100.

EiJ5t:r

·l'1!'lo#i.=.n""" ...... ;o:c'... ~' ~ _ , . _ _ "'"'.

I 1 ~".;':~,~~.":"'"

11::!

~-'

_ _ "'~ ..._...,..,""". . . ~

,"-"--

.., .

[4"900.

/1 -

~~~~, . " _ " " , _ , , ... J

....

,,"'"

.,i'!!

.... ....... T........ . . . . . . . .",-_...... ---~

". , • ,':""",,, '"

.L,-.

[N/A

l'.-;-;;-;<;';'T.........-i , '~"'"'''''' I .• .,

1.:..;;: -;::-. ---::;::;.--.,;---- _. (212.

••

:::.l""-,,,-eak ... :.. l':'IA"" __'-1 I

"~L~' : ,.,., , '."

IN/A

' .... _

ff -I ""'!

-rfoo.

15;7':;..

I "

Jo""""___

_-+-iJO.:... .....

·-:.;..,--;'iIZ';;.. ~~ ...·.s-,.~~r!' ..._~ ~o<o(~I_""'_" c -... ............ ,

.... . . . . . , _ .... ""._..,..~....

_ _

,,,,

-.~~.-.~--

5.61

""'"

......... ~ ...........~"

'_",- _

'L~'~ -I ""'1

•

'-," _.. ---I;:: ;;;-.;:

T2oo.---- 5.60 jNlA -:::~~ __-:~ 0.00

[0.00

SAM'

Ana!yle I--calculated Retention. 1 concentra~lonl Ac~aCY_ rIme (min) 1 (V9fKg) , I . --... -.... -+- _ ...__L .._ ....... ,10.0 (60 1",6 1116. 20 1 -~_ _ •___ 5:61 ~..::_ . . _.... 150.05.60 40.7 ,81.5 Analyte

--~-

1100 ppb

~--'

Analyte

r'lI

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

Peak Area I' Concentration (counts) 1 (!1g1Kg)

12 PM

~--.r •

.' '1' .••.U_..

9P1f

50 ppb

[4~

71'M

'lOppb

,20"iiPb

IAna~te peak!IA~~!~e .

Acqulsltion Da.te

T'''' =

• • ,

!if

-T~;'<~-~

'1 '"

, "" I .....

"..",-.""

,,,,j

"" ;1·1): "LInear' Regression ("11 k" VJ{!ign!inJ): Y '" 514 X" 2.04>::+003 (r = 0.9943)

I ~:~;ll i

e,00e4 6,O\)e4

41lOc4

_~.-

__-

~ 10~-: 20 --,

-r , oliO

e'a

, L

, _ _ ,---

•

110

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

,.-.....,..-

--~---.~~'=~-==.-=~--~ ..

100

~-----

- --

-- --

......

..,..

IS:~~1e sf~p'I-:Cqulsiti::a:'F:~;:~.]I-A;~;~:·:-p~i~~~~-i~:~~~i~:~:'~' :~~~~~:-l~i~~~~'i;~i~:r~~~~~t~:-l' I I =:twpr~g/Kg- "·-}~i70. ---'-h'bll---= ~ ~_~-"--Imr-----'bOtt-'-'-~ 120.Q~ , amP,

ame

yp€'

fsrandard Standard Standard Standard Standard

12123120091-15:47PM 12/23120091:38:29 PM 1212312009 2;01:12 ~ 12123/20092:23:54 PM

(counts)

(pgIKg)

Imidacloprid-Il !midacloprld-U fl9/Kg Imidaclcprid-!1 tJglKg fmidaclopnd-I! !Jg!Kg

Time {mIn)

(pglKg}

tS24Q. .. ____ 5,62 _ 11.6 ____ 188.0 " 125400. ___150.0 •__ ._~ 5.58 _._ _151.2_ _.__ 4~02._~ 151600. 100.· -,5.59 103, '.103. ~ 121231200Q 2:<6:37 PM . 1100000. 1200, rS9 ---'98. -. Blank Un~!1OWn 12123120093:09:20 PM Imidacloprid-II §'K9 10,00 !NIA 0.00 No Pa.k INIA -::::--- 911QOS8173 Unknown 12/24/20092:27:55 AM fmidacloprid~lr yglKg"-' -l~250.~-- _J~:-=_~i~ j~.~1 -- -. ----lNJA , - 20ppb 50ppb 100 ppb _, 200 ppb

_. __....

i;.'...,.i._~

_oot ....."'>U__

Imid3clOpn~~ugIK9

~ .....-:ti!F,... ___ .......~tw,..iI1""i'n""'"ef.... ....~"" ..~'''... ~ f~-,,."'~ ......... _ -~

-j

...

~.. o'

iIi '" ~'"'''''''''''''''U

_=____

:=J9~ ~

--=

re;ct""<"'iii>"~"'ik1.!'."'ih...,r= 1~_'f'~-;;;t"'i:.,--;'"a;;:>r..""tifi':R"""I·I~ _ _ " " , _ ........ ,,""'''''u...... ....... _-......_ ""0[<4')""''"''1_0' .." .._~.. I

- - -""-

"""""",,," - "

<-- - -

_'"""''''I>J......

I ~:~;:I,~ ,;';; ~" r, -I.] 1 00 l~, ' -Ll )"'U J ~Ll ' ' , *~:~ ~I ~~~~~,>;"7t"7;;~11'-I -: ._,~.~.~~,. ..• ~~ r_~I_,_,_' ~A ,,~~. 00 _ ...... _..- .._"""V,,,,,...,, , I

_...---,. ':L.._ 1... > • • • "'''--'''''"i''''~

,. ,. • •• 'i:::$.?.,.. 1... ·..,__ ~

R' " .......,'

.....

-_.

(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

a.OOe4 6. 00c4 4.00~4

2..00eAk~

_._~-.-I)-

______- - - - -

_.------

__~-~---r--~

--.- •.---~--------y-_h~

'0 • .~ • ~ • 70 00 ., _________________________________________

100

_--,-,

,..

iwm~~

, _ , "

..,.

,m ,m MO .~ ,. .70 ,,0 100 _ ____________________________________

,...,.

"~-"""""'-

Sllmple

Sample

-Name

Type

An I tc Puk! A

a.y

Acquisltfon Date

Name

i'Oppb

, PM

4 PM ll""irl!i,..lnnrirlJ

1100 ppb

,"_.!'~

_~.=,i~fank-

!.lmlda~J0f?1"id~1

1 AM L..._..:..' '"t~

...

=:.,~~

- '':'~"",",,'..-,":...c

~. I~

~L,-

-, . . . .,..,""Ol_... -~,. ...... ..=:;.~ -...,_.!"iOPI.... ...

f, :

''.''l·J!'\~·

[

____

?Go. -

150.0

111'000,

" j2oo;

1i--9iKg

i100.

•

,_.

_ _ _ ••

' 5.60 .. _--_. _.+-

_____._ •••

(~gIKg)

J.,

{',I)

_ _ ••• ___•• __

_ ~~c;-'-l~-'

"1r-"

140.7. 181.5 -- _ ., 195-9 195,9 1212. , ----'- i Me ,",v_

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

15.GO

~5_SO-

'--I~'::-::::t~~p_ea~:f~;~-

-,.':«--_..

~~9'[~""'~·'''''''-''''''''''''-'''''·''·"'''·lr ~.m''''''''''lf''''''''"''' ......-~"""""1""""""'-" •_..,.-~--" "'....--l ._~ ....."""...""-""~ " _. ~-', -...'. ....ot<.. _ _,....... l ...... """"'--" _~ ",,~,,~_"'nu:_... •., I I_ .... I

I I ,~~,~.r-1i""7"-~~. I' =1 -L I i) '~L ... L 'r~~_I __ ~'--->., ."

Time (rnrn)

~~~~. -::J;~~-=~= ~.:~~~:=:_~l_~-::::==j}~~:

7 PM Ilmiam:::aopno oPM Imidaeloprid·! Ivg/Kg

I~ 1200ppb

__ ,

Analyw' j Ca!c:u{a{ed Retention

Analyte.

i (counts) [(~g!Kg) ,_t _ _ '_'_ _

IgIKg

-,"

15:47 PM

Analyte

! Pe<.'lk Area Iconccntration

VOlts ..

I tt! '

na X

i·

·-t 1

It -,

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

I.j

I'r. 1

•

"I, { '11. ~!I , R' .""1',,'G .. ,.....-n '~fL.ir . ,~ I,

~~,

"I "I

r'l

,. ""'~ I I L I

I'"

~'~;j ~OOe4

----

,'~_'ro

"",

11.

•

2-00e-!1.~_----:-~, " • • • •

.---_.-.-

4,00e4~

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

----

________. - - -

6.00c4

I'~ I

. y '" 51>: x'" 2.04e"'OO3 «( '" C,S94j,)

_...,

r-"-"'--'

1m ,. ,.. I. 100 1M ________________________________________ ___

------------------~~

S~mp.le

Sampf,e

Type',

Narri~

I Acquisition"Date -

Analytc pad::1 Analyte Name Units

1 PM lPM -" .,,_ ,2 PM

,11

i2 ",. ,3

-[tooppb

fPM

1200 ppb

-"?PM

-.... .......... ,

"'_"'iiIi'i44il>:~'

''oi'' '-"i-',..,.

(counts)

___14770. 8240.

(ug/Kg)

- -

i iOO.

(IlS/Kg)

,5-59

1108_

.-188.0 ___ _ ]102. li03_

____ 559 - -l1'9!l'---'j98Jl

__~F~--~~--·. ____ ~:::~ -"

i, -U , ..... " ..

----.~--~--

I~:~

"'-"-

;

pO.8 117.6 _. ___ )51.2 1103.

- -- -T------------C---

-I

lconc'cntr~tjon! c{~~ac:.y

I Time (min) I 15.58

-.:;;;=.....z'~~~'1r.':7"..;:-yl~=fi,Z;W ~""'-~ ""..--1",..","'"'' _ _"' _";;;;ziii""" _ ,_"'tU-t'

~_V1""_...

->I

120.':.______j~~_____ 1200_

ug/Kg

I Retention Analytc

, 1-='''-''- .- .,--,.. 1 ~ Calculated 1A •

--i5-61

110.0

·,:::-~rin~li ~l. _""_~-UiO-~I'~

.....

Anafyte

150.0

- __

...,~

PttakAreu Concentration

:JfKg

-rAM

II=~......," _I.

pg/Kg

) PM--..........

191

Anatyte

I .........,...._ . ., ............ ~

-I

-t-F_W'<-1~'"

I ..., _.' _........... _

~r~,""'~

~-=,~,.

-~ -~-.

'L"lL ! I ': ,', .!:,A~~~

f,~~._ .. ,.",~_~r !

u,i"

,....-o:o.;_~~ ....

-~-i[~. __ -_~-I

li= .......

':lnihr Tr1 . l.Jnear Regre!!;~ioo

n IX' weighting); Y"' S09 x + ·730 (r"' 0.00(0)

1.ODeS.,

~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

:W=:::." h'

,'''''

'400

150

.... _-- --

, •

--~--r--

160

170

180

190

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-'

follO'~\;t~(#~~.~~: .117~E~n:riC::

ni'ani;

• 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

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 have fJlreaQY 'been agreed by yeu.

a.n

,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., ' - ,