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IS 10629 (1983): Methods for determination of Aldicarbresidues in crops, soil and water [FAD 1: Pesticides andPesticides Residue Analysis]

15 : 10629 • 1983

Indian StandardMETHODS FOR

DETERMINATION OF ALDICARB RESIDUESIN CROPS, SOIL AND WATER

J.Si'

@ Copyright 1983

INDIAN STANDARDS INSTITUTIONMANAK BHAVAN. 9 BAHADUR SHAH ZAFAR ~tARG

NEW DELHI 110002

G.. 3 DtClmb,r 1983

IS : 10629 • 1983

Indian StandardMETHODS FOR

DETERMINATION OF ALDICARB RESIDUESIN CROPS, SOIL AND WATER

Pesticides Residue Analysis Sectional Committee, AFDC 56

Chairmann« H. 1.,. BA~IJ

Bungalow No. A, Malkaganj,Dt.·lhi

MembersSHRI E. A. AL~EIJ)A

Snur t'. QUADl\OS ( Alternat« )SIIlU K. D. AMitE

DR]. S. VJo1RMA ( Alternat« )DR K. C. GUHA

Rt/Jrejenting

Hinc.lu~lan CiU.l-Gl'igy Ltd, Bombay

National Organic Chemical Industries Ltd,Bombay

Central Foocl Laboratory, CalC-lIUH: arid Cl~ntral

COHlIlliUee for FOOtl Standards, Nt-w Delhi

C. S. A. University of Agriculture and Technology,Kanpur

Department of Food (~finistry of Agriculture),Ne,Y Dtlhi

DR R. P. CUAwr..A ( Alternat« )DR KAJ..YAN SINOH

n« K. KRISRNAMURTJlY

5111\1 P. K. DII1NGRA (Alternate)DR S. S. GUPTA Bayer India Ltd, ThaneDR R. L. KArJI~A Department of Entomology, Punjab Agricultural

University, Ludhiana

Pesricides Association of India, New Delhi

Rallis A,ro-Cht-mical Research Station, BangaloreC)'ananud India Ltd, Bombay

DR R. C. GUP1'A (Alttrnate)DR). C. MAJUMDAR

DR V. SRI:NIVA8AN ( AII"",d, )DB M. S. MITHYANAT}lAD.aA. L. MOOKlmJBJ:

SaRI G. N. BHARDWAJ ( Altern,",)DR V. LAKSUMINAKAYANA Directorate of Plant Protection, Q,aarantine and

Storage, Faridabad

C c.J1Yri,1a1 1983INDIAN STANDARDS INSTITUTION

Thil publication i. protected under the INli.,. lAfJy,i,'" Ad (XIV of 1957) andreproduction in whole or in pare by any meaDI except with written perm_ion of tbepublisher 'ball be deemed to be aD UatiiapmeDt or copyright under the said Act.

IS I 10629 • 1983

(aSIR ),

Indian Veterinary Research Institute (leAR),Izatnagar

R,prlsentinlIndian Agricultural Research Institute (leAR),

New Delhi

Central Food Technological Research Institute( CSIR), Myaore

Dn ]. R. RANG.SWAIIY (AII,rna',)DB B. L. WATTAL National Institute of COlumunicable Diseases,

Delhi

DR R. C. NAITHANI (.All,rnal,)DB K. V18B••WABAIAB

DB R. K. SETHIDB K. SIVASANKABAH

DB S. Y. PANDB" (.AII,rnt",)DR S. C. SRIVASTAVA

DRS. K. HANDA (Al',rIl41' )DBNAGABHU8HO\N R.o

( Conti,.u,4from /NAIl t )

Mlmb"sDB S. K. MUKBBJ••

Regional Research LaboratoryHyderabad

Public Analyst, Government of Haryana,Chandigarh

DEPUTY PUBLIO ANALY8T ( Aluma« )DB T. D. SETH Industrial Toxicology Research Centre (CSIR).

LucknowIndofil Chemicals Ltd, ThaneUnion Carbide India Ltd, New Delhi

PUBLIO AXALYS'r

SHRI G. C.JOSHI (AII,rna',)SBRIT.PUBNANANDAK,

Director (Agri at Food )Director General, lSI (&-offid. Mmab,,)

S'~'MrySHRI M. L. KUMAR

Senior Deputy Director ( Agri at Food), IS I

2

lJ5t] AMENDMENT NO. 1 MARCH 1~5TO

15:10629-1983 METHODS FOR DETERMINATION OF AlOICARBRESIDUES IN CROPS. SOIL AND WATER

(RIgs b~ olau Btl J. 4, hsading) - Substitute•Clean-Up' fo~ 'C~een-Up'.

(Rzgss ~ am 6, alau ee J .4, tine 20) .. SUbstitute'10 ml t ffM. '100 ml' •

(Rzges ~ awl 6, alau ee 3.4.. line 25) - Substitute'sodium hydrogen carbonate' f()lt 'sodium. carbonate'.

(AFDe 56)Reprography Unit, lSI, New Delhi, India

IS : 10629 - 1983

Indian Standard

METHODS FORDETERMINATION OF ALDICARB RESIDUES

IN CROPS, SOIL AND WATER

o. FOR E W 0 R D

0.1 This Indian Standard was adopted by the Indian StandardsInstitution on 30 August 1983, after the draft finalized by the PesticidesResidue Analysis Sectional Committee had been approved by theAgricultural and Food Products Division Council.

0.2 Aldicarb has a broad spectrum of effectiveness against many speciesof insects, mites and nematodes. It is systemic and applied only in theform of granules and is used as a soil treatment on a range of cropsincluding bananas, coffee, tobacco, cotton, potatoes, sweet potatoesand sugarcane. Frequent and increased use of aldicarb formulations oftenresult in harmful effects due to toxic nature 01 residues. Carefulassessment of residues is, therefore, an important step in safeguardinghuman health and in the establishment of sound regulatory policy.

0.3 This standard will enable the health authorities and others to followuniform test procedure for the estimation of aldicarb residues invarious crops, soil and water.

0•• In reporting the result of a test or analysis made in accordance withthis standard if the final value, observed or calculated, is to be roundedoff, it shall be done in accordance with IS : 2·1960*.

1. SCOPE

1.1 This standard prescribes spectrophotometric and gas chromatographicmethods for the determination of aldicarb [2-Methyl.2-( methyltbio)propionaldehyde 0-( methylcarbamoyl) oxime] residues in crops. soil andwater. The residues determined include aldiearb, its sulfoxide and the,ulfone•.

-Rules Cor rounding off numerical values ( "l';sed).

3

IS I 10629 • 1983

1.1.1 Spectrophotometric method may be adopted as a lirnit test forroutine purposes with the minimum detection limit of 0·1 Iug/g (0-1ppm) whereas gas chromatographic method shall be the referencemethod with the minimum detection limit of O·005/p.g/g ( 0·005 pplll ).

2. SAMPLING

2.1 The representative samples for the purpose of estimating aldicarbresidues in various crops, soil and water shall be in accordance with thesampling procedures as prescribed in the relevant Indian Standards,wherever available.

2.2 Preparatio. of Laboratory Sample

2.2.1 Soil, Coffee, Tobacco, etc - If needed, grind to pass through suitablesieve. Reduce to about 100 g by mixing and quartering.

2.2.2 Vegetables and Fruits

2.2.2.1 Remove visible soil particles by gentle rubbing. Rootvegetables may need scrubbing with a brush and some washing.

2.2.2.2 Remove all inedible portions of vegetables and stems andstones of fruits if any.

2.2.2.3 If a peel or skin is not normally consumed, it should beremoved and if edible it should be included.

2.2.2.f Cut a representative sample into pieces and reduce bymixing and quartering to about 300 g.

2.2.2.5 Blend the 300 g sample in a waring blender to obtainhomogeneous mixture. Mix content with sepatula and reblend toensure homogeniety.

2.2.3 liTflier - This does not need any processing.

3. EXTRACTION AND CLEAN-UP

3.1 Apparatu.

3.1.1 Rota,y FlmA EfJaporatoT

3.1.2 WaTing Bl,ndl, or Equivalent - Leakproof and explosion proof.

3.1.3 Chromatol'aphie Column - 30 em length and 1·3 em inner diameter.

3.1.4 Wate, BillA

4

IS : 10629 • 1983

3.1.5 Ai, Condenser - Snyder type

3.1.6 Mll ..~nttic Stirrer (11m Hot Plate

3.2 Reagent.

3.2.1 Aceto ie - Analytical reagent grade/glass redistilled.

3.2.2 Acetonitrile - Analytical reagent grade/glass redistilled.

3.2.3 (4'hloro!or,n - Analytical reagent grade/glass redistilled.

3.2.4 Ilyjlo Super-Ce!

3.2.5 Mftlultzol- Analytical reagent grade/glass redistilled.

3.2.6 Benrene - Analytical reagent grade/glass redistilled.

3.2.7 Sodium Sulfate - Anhydrous, analytical reagent grade.

3.2.8 Glacial Acetic Acid - analytical reagent grade.

3.2.9 H)tdro.~en Peroxide - 30 Percent.

3.2.10 Coagulating Solution - Prepared by dissolving 0·5 g ofammonium chloride in 400 ml of water containing 1 ml of orthophos­phoric acid.

3.2.11 Florisil- 150 -250 p.m ( 60 -100 mesh ).

3.3 Extraction - Transfer 50 g of sample to a blender. Add 150 1111

of an 80: 20 mixture of acetone-chloroform and 100 g of anhydrouspowdered sodium sulfate. Blend for two minutes at low speed andallow to settle for one minute. Decant the solvent into a Buchner funnelcontaining Whatman No. 1 filter paper covered with a thin coat ofhyflo-supercel attached to a 500 ml filter flask. Apply vacuum cautiouslyuntil all the solvent has filtered into the filter flask. Re-extract the cakealongwith the filter paper with two 100 ml portions of acetone-chloroformand filter the extracts. \Vash the blender and cake with 50 ml of mixedsolvent.

3.~ eleen-Up - Transfer the filtrate (sr, 3.3 ) to a 500 ml round bottomflask and add one drop of diethylene glycol. Connect the flask to arotary vacuum flash evaporator and place in a water bath at 30°-40°0.Apply vacuum and reduce the pressure carefully to about 50 mrn Hg,After the solvent has evaporated, disconnect the flask immediately. Add5 ml of acetone, swirl and warm the flask under hot tap water for 30seconds. Add 50 ml of coagulating solution and swirl the flask. Allowmixture to stand for 30 minutes with occasional swirling, Filter using

5

1811.. • 19S3

vacuum, through 3 mm layer of hyfto-supercel on Whatman No. 1 filterpaper in a Buchner funnel into a receiving flask. Wash the flask and preci­pitate with 2 X 25 ml portions of methanol-water ( 1 : 9), allowing eachwashing to remain in contact with precipitate about 20 seconds beforeapplying vacuum. Transfer the filtrate to a 250 ml separatory funnel andadd SO ml of chloroform, shake weU and allow the layers to separatecompletely. Drain the lower layer through a bed of anhydrous sodiumsulfate into a 250-ml round bottom flask. Repeat extraction of aqueouslayer with 2 X 30 ml portions of chloroform and collect the extractsin the same 250-ml flask. Wash the sodium sulfate bed with 2 X 20 mlportions of chloroform. Add one drop of diethylene glycol andevaporate to dryness under vacuum as before. Add 100 ml of hydrogenperoxide-glacial acetic acid (2 : 1 ) to the residue flask, attach an aircondenser (snyder type) and oxidize the residues with continuous stirringat 70 ± 2·0 for 30 minutes on a magnetic stirrer-cum-hot plate. Removethe flask and cool in an ice bath for 5 minutes. Add 60 ml of 10 percentaqueous sodium carbonate to neutralize the mixture. Transfer theneutralized mixture to a 250-ml separatory funnel and extract withchloroform as before. Add one drop of diethylene glycol and evaEorateto dryness under vacuum as before. The residue is dissolved in 100 mlof 10 percent acetone in benzene poured on to a 1~·5 em column of florisilcontained in a IS-mm i.d. glass chromatograph tube, the florisil beingprewet with benzene. The column is allowed to elute and the eluate isdiscarded. This discard is necessary to remove the nitrile and oximemetabolitiel of aldicarb, which would interfere in the aldicarbdetermination. Finally, the aldicarb residues now oxidized to aldiearbsulfone, are eluted from the column in 150 ml of acetone-benzene(40: 60).

4. SPEOTROPHOTOMETRIC METHOD

••1 Pdaciple - The determination of total aldicarb residue is basedon the carbamoyl-oxime group of the molecule. The carbamoyl oximeis hydrolyzed with base to 2-methyl-2-( methyJth\p) propionaldehydeoxime. Hydrolysis of the oxime in acidic medium forms the aldehyde 2­methyl-2-methylthio propionaldehyde and hydroxylamine. Thehydroxylamine i. oxidized with iodine to nitrous acid, which is determinedcolorimetrically at 530 nm,

~2 App_ratq.

f~2.1 IpectropJaotolllete.. - Capable of measuring at 530 nm,

u a_l_t.~,.l StJdium Hr!tlfollitll - 0·1 N aqueous aolUtion.

6

IS I 10629 - 1.83

4.3.2 Hydrochloric Acid - 1 N solution.

4.3.3 Sulfanilic Acid- Dissolve 1'0 g in 75 ml of water and add 25 mlof acetic acid.

4.3.4 Iodine - 1 percent in acetic acid (tn/v).

4.3.5 Sodium Thiosulfate - 2 percent in water.

4.3.6 Potassium Ace/ale - Dissolve 100 g in 100 rnl of water.

ot.S.' I-Naptuhylamin« - Dissolve 0'5 g in 50 ml of acetic acid,.add 115 JIll of water and 25 mg of activated charcoal, mix well andfilter. Prepare fresh daily just befor use.

4.~ EstimatioD of Aldicarb Re.idues - Place an appropriate aliquot( see 3.4 ) in a 250-ml flask, add one drop of diethylene glycol and evaporateto dryness as before. Add S'O ml of 0'1 N sodium hydroxide and placethe flask in a water bath at 40GC for exactly 40 minutes. Add 1'0 ml ofIN hydrochloric acid. Place the flask in a boiling water bath (80.85°0)and allow to digest for 20 minutes. Allow the solution to cool in an ieebath for 10 minutes and add 0·5 ml of sulfanilic acid solution. Mix welland add 0'2 rnl of iodine solution, mix and let stand for 3 minutes. Add 0'2ml of potassium acetate solution, mix and add 0'2 ml of sodiumthiosulfate solution. Immediately add 0'3 ml of l-naphthylamine solutionand mix well. Let stand 1 minute and dilute to 10 ml with ( I + 1)acetic acid-water solution. Mix and let stand 5 minutes. Transfer thesolution to a 125-ml separatory funnel and extract with 5 ml ofchloroform. Let the layer separate completely and determine theabsorbance of the top layer ( aqueous) in a I-em cell at 530 1Uh, using areagent blank processed along with the sample. Determine theconcentration of aldicarb sulfone from a curve obtained by plotting ",g ofthe standard in ml against absorbance.

4.4.1 Pr,paration of Standard Curve - Weigh 50 mg of aldicarb sulfone,transfer to a lOO-ml volumetric flask and dilute to volume with acetone.Take an aliquot of 10 ml and transfer to lOO-ml volumetric ftask anddilute to volume with acetone. Dilute the second solution the same wayand this gives a concentration of 5-0 JAg per ml, Pipette aliquot of 0, 1.0,2'0, 4'0, 6-0, 8'0 and 10-0 ml into a series of 20-ml test tubes and makethe volume to 10 ml with chloroform. Follow the same procedure asdescribed under 3.4 and 4.4. Plot the absorbance of the standard101utions againlt ug of aldicarb sulfone to obtain a standard curve.

·4.5 C.I..latl.a

Aldiearb residues 'Jill ( ppm)- ~I aldicarb sulfone X dilution factor. mass of sample (g)

. 7

IS : M629· 1983

4.6 Espre••ioD of Result - Report total toxic aldicarb residues asaldicarb sulfone in the sample as p.g/g ( ppm ).

5. GAS CHROMATOGRAPHIC METHOD

5.1 PriDciple -l'he toxic residue of aldicarb in biological substrates iscomposed of aldicarb and its sulfoxide and sulfone metabolites. All threeof these components are determined as a total residue by first oxidizingaldicarb and aldicarb sulfoxide to aldicarb sulfone with hydrogenperoxide-gla cial acetic acid (2: 1 ) and then determining total aldicarbsulfone by gas chromatography, The aldicarb sulfone is determinedutilizing a Harne photometric detector incorporating a 394-fiIter specificfor sulfur-containing compounds, and it is quantitated by reference of thepeak area to a previously prepared calibration curve.

5.2 Apparatus

5.2.1 G4J Cllromatograph - Equipped with flame photometer detectorincorporating a 394 filter specific for sulphur, The gal chromatographis operated under the following suggested parameters. These parametersmay be varied al per available facilities provided standardization isdone.

~0130 ~ ml per minute30j

Column

Column oven temperature

Injection port temperature

Detecter temperature

Carrier gas

Recorder chart speed

A stainless steel, glass column of 2·4 mlength and 3-13 mm ID packed withchromosorb P coated with 5 percentcarbowax 20 M.

1800(~

300°C

200°C

NitrogenHydrogenAir

1 em/minute

5.3 Procedare

5.3.1 Transfer suitable aliquot (s" 3.4) to a 100 rnl flask andevaporate to dryness. Dissolve the concentrated residues in 1 ml ofacetone and inject 8 ,,1 into the column using a microlitre syringe.Identify the aldicarb sulfone peak by itl retention time and measure thepeak area.

8

IS : 10629 • 1.83

5.4 CalcalatioD

. k M VAldicarb sulfone p,g{g ( ppm) = Astd X M-; X V-; X f

where

As = area sample;

Astd =- area standard;

M = p.g of standard injected;

1.\-11 = mass, in g, of the sample;

V = volume of final extract in ml;

~"1 = Jll of the sample injected; and

100f = recovery factor = --------­percent mean recovery

9

IN D I A' N S TAN DAR D S

ON

PESTICIDES RESIDUE ANALYSIS

IS:

5863 ( Part I ) - 1970 Method {or determination of malathion residues: Part I Cerealsand Oilseeds

5864·1983 _Method Cor deter mination of DDT residues in food commodities (first"IllS"'" )

5952-1970 Method Cordeterrn ination of parathion residues in foodgrainl and vegetabl••6169-1983 Methods Cordetermination of BHC ( HCH ) residues in food commodities

(first "Disio,. J10168-1982 Methods Cordetermination of fenitrothion residues in foods10169-1982 Methods for dererrn ination of carbaryl residues in fruita and vegetables

INTERNATIONAL SYSTEM OF UNITS (81 UNITS)

Ba.e UnIt.

QUANTI'rY UNIT SYMBOL

Length metre mMu. kilogram kgTime second sElectric current ampere AThermodynamic kelvia K

temperatureLuminous intensity candela cdAmount of substance mole mol

SapplelDeotar)' Unit-

QUANTITY UMIT SYMUUL

Plane angle radian radSolid angle steradian ar

Derived UDita

QUANTITY UNIT SYMBOL DBI'JNITIOK

Force newton N IN - 1 kg.m/.1

Energy joule J I J - 1 N.mPower watt W lW - t J/aFlux weber Wb 1 Wb =a 1 V••Flux density tE'.la T 1 T - 1 Wb/m-Frequency hertz Hz 1 Hz leI. (._I)Electric conductance .iemens S I S - I A/VElectromotive force volt V tV - 1 W/APressure, stress pascal Pa 1 Pa .. I N/ml

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