I

UNITED STATES ENVIRONMENTAL PROTECTION AGENCY I

ENVIRONMENTAL CHEMISTRY SECT10N , BUILDING 1105-JOHN C. STENNIS SPACE CENTER STENNIS SPACE CENTER. MISSISSIPPI 39529-6000

TELEPHONE (601) 688-3216

November 24, 1993

MEMORANDUM

SUBJECT: Baythro id* (Cyf l u t h r i n ) Method Eva1 u a t i on - Report No. ECM003El FROM: Aubry E. Dupuy, Jr . , Ch ie f w K / i'

BEAD/ACB/Environmental Chemi s t r y Sec t ion k

TO: Henry M. Jacoby EFEDIEnvironmental Fa te and Groundwater Branch (7507C)

THRU: D o n a l d A . M a r l o w , C h i e f BEAD/Analyti ca l Chemistry Branch (7503W)

The EFED/Ecological E f f e c t s Branch has requested an Environmental Chemistry Method Val i d a t i o n on C y f l u t h r i n ( Baythro id*) res idues i n water and sediment. The a n a l y t i c a l methods a r e i nc l uded i n a r e p o r t "Assessment o f t h e P o t e n t i a l Eco log i - c a l l B i o l og i ca l E f f e c t s of Bay th ro id* (Cyf l u t h r i n ) u t i l i z i n g A r t i f i c i a1 Pond Systems", submi t ted by t h e A g r i c u l t u r a l Chemicals D i v i s i o n o f Mobay Corporat ion. Th i s r e p o r t (ECM003El) discusses t h e l a b e v a l u a t i o n da ta we ob ta ined f o r Baythro id* ( C y f l u t h r i n ) i n sediment.

The r e p o r t i n c l u d e s a summary, t h e a n a l y s i s performance r e s u l t s i n terms o f p r e c i s i on, accuracy and exper imental d e t a i 1 s i ncl ud i ng 1 i n e a r i t y curves, repre - s e n t a t i v e chromatograms and example c a l c u l a t ions .

The f o r t i f i c a t i o n l e v e l s , which i nc l ude t h e l i m i t o f q u a n t i t a t i o n (LOQ), were 5.0, 10.0 and 50.0 p a r t s - p e r - b i l l i o n (ppb) . Tr i p1 i c a t e analyses were performed on f o r t i f i ed samples and sampl e b l anks.

I f you have quest ions concern i ng t h e repo r t s , p l ease con tac t Henry Shoemaker a t 601 688-1222 o r Aubry Dupuy a t 601-688-3212.

cc: Danny McDaniel , QA O f f i c e r BEADJACBIECS

Henry Shoemaker, Chemist BEAD/ACB/ECS

Text Searchable File

ECM0003E1 09-30-93

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Environmental Chemistry Method Validation Report Number ECM0003E1 Cyfluthrin (~aythroid") in Sediment

Environmental Chemistry Section Analytical Chemistry Branch

Biological and Economic Analysis Division

September 30, 1993

Prepared by:

Reviewed by:

TABLE OF CONTENTS

Page

. . . . . . . . . . . . . . . Part I Summaryand Conc lus ion 3 . . . . . . . . . . . . . . . . . Part I 1 A n a l y t i c a l R e s u l t s 4

. . . . . . . . . . . . . . . . P a r t I 1 1 Experimental D e t a i l s 5

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Part I Summary and Conclusions

We have completed an Environmental Chemistry Method Validation on Cyfluthrin (BaythroidTn) in sediment. This method submitted by the Agricultural Chemicals Division of Mobay Corporat'ion appears to be suitable to gather residue data for Cyfluthrin from 10 parts per billion (ppb) to at least 50 (ppb) in sediment.

The analytical method involves extraction of the sediment matrix by stirring with acetone and transferring to acetonitrile and then hexane by roto-evaporation. The resultant extract is analyzed by Electron Capture Gas Chromatography. The fortification levels were at 5.0, 10.0, and 50.0 parts per billion (ppb) with triplicate analyses at each level.

The Method Limit of Detection (LOD) was 5.0 ppb and Limit of Quantitation (LOQ) was 10.0 ppb. Recoveries for Cyfluthrin in sediment at the (LOD) ranged from 70% to 118% with a mean of 91.3% and relative standard deviation (RSD) of 26.6%. Recoveries for Cyfluthrin at the (LOQ) and above ranged gram 83% to 93% with a mean of 87.3% and relative standard deviation (RSD) of 4.7%.

Since there is no clean-up and the acetone would extract many other contaminants, the limit bf detection of Cyfluthrin may be compromised in some samples. The (LOD) and (LOQ) may have to be adjusted for certain highly contaminated samples.

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P a r t 11 A n a l y t i c a l Results

E P A Recoveri% of C y f l u t h r i n in Sediment C

Samp 1 e Added(ppb) Found(ppb1 %Recovered Mean SD

Blank 1 0 0

3-24 5 . 0 5 .94 118

5-25 5 . 0 3 .52 7 0 . 4

S-26 5 .0 4 .28 85.6

Blank 2

S- 27

S-28

S-29

Blank 3

5-30

5-3 1

S-32

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Part I 1 1 Experimental Details

Liquid-Solid Extraction

1. Before extraction, the sample is homogenized with a teflon or stainless steel spatula and a sample for dry weight analysis is removed from all samples if the final calculation is to be based on sediment dry weight.

2. 50 grams of sediment sample is weighed into a 225 ml amber glass jar. 50 ml of acetone is added to the sample in the jar and a stir bar is added. The sample is tightly capped and stirred at moderate speed for 15 minutes.

3. The extract is vacuum tiltered into a 250 ml evaporating flask through a Buchnerfunnel lined with a disc of Whatman #41 filter paper and a 5-10 mm bed of Celite 545 which has been previously rinsed 4ith acetone. The sample jar is rinsed with an additional 50ml of acetqne and this fraction is filtered and combined with the first acetone extract. The acetone is allowed to evaporate in the roto-evaporator until water remains. ~

+ 4. 125 ml of acetonitrile is added to the water fraction and

the extracts are evapo ated to dryness by gentle rotary evaporation. was not totally evaporated, an additional 30 ml of acedonitrile is added to complete the evaporation of the watei. d 10 ml of hexane is added to dissolve the residues a d the flask is sonicated for 2-3 minutes.

5 . The hexane extract is carefully removed with a Pasteur pipet. Part of the sadple is transferred directly to an amber autosampler vial tdr gas chromatographic analysis and the remainder is transfeJred to a labeled 8 ml amber storage vial and stored at -15+1deC.

Analysis of Extracts

The extracts and standards aJe analyzed by high resolution gas chromatography using a 5 meter The non-polar methylsilicone Samples are grouped by standards. On-column injection

x 0.53 mm fused silica column. stationary phase is 2.65 um thick.

dose level along with appropriate is used with an injection volume

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of two microliters. The injections are made using the auto injection system on the HP5890 gas chromatograph. In all cases, the injection volume of standards and samples must be identical. The oven is temperature programmed to allow the Cyfluthrin to migrate through the analytical column in a reasonable time. The chromatograms are stored on computer disk and printouts generated at the end of each analysis.

Calculations

Calculation of Cyfluthrin concentration in the sample is by direct comparison to the standards which were injected immediately before and after the sample. The analyte concentration in one milliliter of the sample extract may be calculated as follows:

Conc. of Standard (ng/mlf = Conc. of Extract (nq/ml) Avg . Peak Area Peak Area

The analyte concentration ng/g (ppb) in the original sample may be calculated as follows:

Cyfluthrin Concentration = Extract Conc.(nq/ml) x Extract Vol(m1) in Sample (ng/g) Original $ample Wt. (gram)

NOTE If concentration based on dry weight is needed, replace the original sample weight with its dry weight equivalent.

NOTE While this method of calculation is valid for samples of known fortification levels, it would not be suitable for samples of unknown quantities of Cyfluthrin. Calculations using a standard calibration curve would be more appropriate.

Source of Analytical Reference Standard

A standard of 1 gram of Cyfluthrin (Baythroidr"I was received from The Agriculture Division of Miles, Inc., Kansas City, Missouri. In its neat state, Cyfluthrin is extremely difficult to routinely homogenize and manipulate because of its extremely thick syrupy nature. Therefore, the standard was supplied as a 50.2% Cyfluthrin solution in Cyclohexanone.

$

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Source of Sample Matrix

Sediment was collected locally from the Pearl River near Stennis Space Center. Sediment was collected in wide mouth jars which had been previously rinsed with acetone and hexane then allowed to air dry. Sediment was refrigerated and brought to room temperature before use in the method trial.

Instrumentation for Quantitation

1. Gas Chromatograph - Hewlett-Packard Model 5890 with on- column capillary inlet, electron capture detector, and automatic injection system.

2. GC Column - 5 meter x 0.53 mm I.D. fused silica megabore capillary column with a 2.65 mm film of methylsilicone stationary phase (HP-1) and a 1 meter x .53 mm un-coated gap attached with a glass connector.

3. Carrier Gas - Hydrogen, make-up gas, methane/argon 4. GC Parameters

Oven Program Starting Temp - 170" for .5 minutes Ramp - 15" per minute Final Temp - 240" C for 1 minute

Detector Temp - 32Sa C Electrometer - Range 2, fittenuation 7 Inlet Head Pressure - 7 psi Injection Volume - 2 microliters Cyfluthrin Retention Time - (3.665 .02) minutes

Modification of Method

We made a slight chanqe in the oven program. The registrant used a ramping rate of 40'C per minute to a final temperature of 290" C. A ramping rate of 1 3 C per minute to a final temperature of 24UC gave us good results with a much more stable base line o n our particular instrument.

Chromatograms and Linearity Check

Chromatoqram #1 - Method Blank, Unfortified Sediment S-22

Chromatoqram #2 - Method Blank, Unfortified Sediment S-23 Chromatoqram #3 - Cyfluthrin Standard, 2 5 ng/ml

Chromatogram #4 - Sediment S-24, Fortified at 5 ppb.

Chromatoqram #5 - Cyfluthrin Standard, 50 nq/ml. Chromatoqram #6 - Sediment 5-27, Fortified at 10 ppb. Chromatoqram #7 - Cyfluthrin Standard, 2 5 0 ng/ml.

Injection Time: May 27, 12:12 p.m.

Chromatogram #8 - Sediment S-32, Fortified at 50 ppb. Injection Time: May 27, 11:51 a.m.

Chromatoqram #9 - Cyfluthrin Standard, 250 ng/ml Injection Time: May 27, 11:40 a.m.

#10 - Example Calculation for Sample 5-32 , #11 - Linearity Check for Cyf luthrin (Baythroid"))'

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Gtitleation CoMtdON NA116E: fxwuin. OTHER NAMES: BAY FCF. 1212, Baythmid* H, So&*. CODE NUMBERS: CBS 14816-18-8; SHB 698800.

FAMILY: synthetic pyrethoid- p ~ ~ ~ ~ ~ . C o M e a s e n n J r ~ g r x d e p d ~ ~ t i s m i . D r r d 4 &.~stemieomeric ermtiomer pairs (I-IV).

~nmeat8 lGuide i inw SOLUBILITY: Pmctidy i n m W in mbr. Budly dub& in n-hex-

m-m N-. - - - - .- F I R S T A I D : ~ ~ ~ ~ I X I S ~ M ~ . G ~ ~ O ~ ~ ~ ~ ~ . ~ ~ U . P hold lida ooen a d fhsb with a ate&, gentle etrsrm dmbr or 15 month-to-month. I n ~ t i o n , & - m a iarge qiuntftpdadik. white. gelatin soiumn, or rf them am not amilabk -6 water. Avoid alcohol. =RGENCY TELEPHONE: 81644&2582 (Mobay).

BP: Baver AG

- - -I"# ..+.--- - -- --. .- - - -- 09-30-93

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