ANALYTICAL REPORT ON SEDIMENT SAMPLING AT STAMINA … · Final time 11.5 minutes The gas chromatographs were calibrated usin 6g pesticide standards at 20, 50,100 , 200,400 and 1000

ANALYTICAL REPORT

Prepared by Roy F. Weston, Inc.

Stamina Mills Smithfield, RI

June 15, 1990

EPA Work Assignment No. 1-382 Project No. 3347-11-01-2382

EPA Contract No. 68-03-3482

Submitted to M. Sprenger EPA-ERT

S. Ruhren te Task Leader

/ ' . & A. Section ChiChief

Date

W. S. Butterfield Project Manager

Analysis by REAC Borings, Soils & Testing Labs, Inc.

Prepared by: G. Kanistis J. Tomaszewicz

Reviewed by: Yi-Hua Lin

Table of Contents

Introduction Page 1 Case Narrative Page 1

Section I

Procedure for Pesticides/PCBs in Soil Page 2 Procedures for TOC and Grain Size Page 4 Results of the Pesticide/PCB Analysis Table 1.1 Page 5 Results of the Total Organic Carbon Analysis Table 1.2 Page 6 Results of the Grain Size Analysis Graph 1,1-1.4 Page 7

Section II

QA/QC for Pesticides Page 11 Results of the EMSL Analysis Table 2.1 Page 12 Results of the Surrogate Recovery Table 2.2 Page 13 Results of the MS/MSD Analysis Table 2.3 Page 14 QA/QC for Total Organic Carbon Page 15 Results of the MS/MSD Analyses Table 2.4 Page 16

Section III

Chain of Custody Page 17

Appendix A Data for Pesticides/PCBs Page Al Appendix B Data for TOC, and Grain Size Page Bl

Appendices will be furnished on request.

INTRODUCTION

REAC Laboratory, in response to ERT work assignment 3347-11-01-2382, provided analytical services for samples received from the Stamina Mills site, Smithfield, RI on May 3,1990. These services involved both in-house and subcontracted analyses, a QA/QC data review and a final report summarizing the procedures, results and QA/QC data.

Upon receiving the samples in the laboratory the sample custodian followed standard procedures for inspection of the chain-of-custody and record keeping for sample tracking.

Four soil samples were received from the Stamina Mills site. These samples were analyzed for pesticides/PCBs, total organic carbon (TOC), and grain size. The grain size samples were analyzed by Borings, Soils & Testing Labs, Inc., Harrisburg, PA. The pesticides/PCBs and total organic carbon were analyzed by Weston/REAC, Edison, NJ.

CASE NARRATIVE

During the QA/QC review of the raw data packages for the analyses of sample 6522, result variability was observed in two of the three analyses. There was a wide variation in the raw instrument readings for the TOC analysis. Two of the six readings were above the calibration limit and one of the four remaining readings was approximately three times the reported value (averaged result). In addition, sample 6522 was the matrix spike/matrix spike duplicate (MS/MSD) choice for the pesticide/PCB analysis. Here the variance in the spike recoveries for dieldrin was noticeable, MS-139% and MSD-1450%. However, the percent recoveries were reasonable for the other spike components as was the surrogate recoveries of both the MS and MSD. This observed variation of results suggests the possibility that the sample is nonhomogeneous and that the results for sample 6522 are potentially biased low. Observation of the soil sample jar shows a soil saturated with an unknown liquid layer (oil?). Samples of this nature often have a wide variance of results in duplicate analyses.

OOOC.I

ANALYTICAL PROCEDURE FOR PESTICIDES AND PCBs IN SOIL

Extraction Procedure

The soil samples were extracted by the sonication method. A 10 g aliquot was mixed with the surrogate, and 30 g sodium sulfate and the mixture was sonicated with 100 ml of 1:1 acetone/hexane for about 10 minutes. The extraction was repeated two more times with 100 ml portions of solvent. After extraction, the combined extracts were reduced in volume and solvent exchanged with hexane. The hexane was cleaned by column chromatography through Florisil and reduced in volume to 1 ml prior to analysis.

Gas Chromatographic Analysis

The extract was analysed for pesticides and PCBs using simultaneous dual on-column injections. The analysis was done on an HP 5890 GC/ECD system, equipped with an HP 7673A automatic sampler, and controlled with an HP-CHEM STATION. The following conditions were employed:

Primary Column DB-608, 30 meter, 0.53mm fused silica capillary, 0.83 um film thickness

Injector Temperature 275° C Detector Temperature 325° C Temperature Program 180°C for 2 minutes

5°C/min to 225°C Final Time 11.5 min

Secondary Column RTx-5, 30 meter, 0.53mm fused silica capillary, 0.50 um film thickness

Injector Temperature 275° C Detector Temperature 325° C Temperature Program 180° C for 2 minutes

5°C/min to 225°C Final time 11.5 minutes

The gas chromatographs were calibrated using 6 pesticide standards at 20, 50,100, 200,400 and 1000 ug/L. The results from each mixture were fit to a straight line, and the coefficients of this line were used to calculate the concentrations of the pesticides in the sample extracts. Quantification was based on the primary column (signal 1) and the identity of the analyte was confirmed using the secondary column (signal 2). A fingerprint chromatogram was run using each of the seven Aroclors, toxaphene and chlordanes. Calibration curves were run only if any of the preceeding compounds were found in the sample.

oooo;:

The results, listed in Table 1.1, are calculated by using the following formula:

c . (r-F) x K x gf S x W x D

where.

C = concentration of sample (ug/Kg) T = response from the chromatograph Y = intercept of the fitted line V = volume of extract (mL)

DF = dilution factor S = slope of the fitted line

W = weight of the sample (g) D = decimal percent solids

00003

PROCEDURES

1. PROCEDURE FOR TOTAL ORGANIC CARBON IN SOIL

A known weight of sample (1-10 mg) is introduced into the TOC furnace of the Dorhman DC-80 Total Organic Carbon analyser in a platinum dish and converted to carbon dioxide by heating it. A direct reading in ug/ml is printed.

Calculations were performed using the following formula:

TOC(ug/g) = (A-B) x D C x S

Where A = Instrument Reading (ug/ml) B « Blank Value (ug/ml) D - Volume of standard used to calibrate the instrument (mL) C = Weight of Sample (g) S = Decimal percent solids

Results are listed in Table 1.2.

PROCEDURE FOR GRAIN SIZE

Grain size was determined according to procedure ASTM D422-63, "Particle Size Analysis of Soils," 1985 Annual Book of ASTM Standards Vol. 04.08 Soil and Rocks: Building Stones. The results appear in Graphs 1.1 to 1.4.

0000*1

Table 1.1 Result* of Pesticides and

Polychlorinated Biphenyls Analysis in Soil

Project *2382 StMina M i l l s

(Reported concentrations, ug/kg)

SAMPLE ID Soil Blank 6522 6524 6525 6526 SAMPLE SIZE (Q) 10.65 g 10.91 g 10.92 g 10.39 g 10.69 g MATRIX Soil Soil Soil Soil Soil SAMPLE LOCATION Site 1 Site 3 Site 4 Site 5

a-BHC 2.0U 2.0U 2.0U 2.0U 2.0U 8-BHC 2.0U 2.0U 2.0U 2.0U 2.0U b-BHC 2.0U 2.0U 2.0U 2.0U 2.0U

HEPTACHLOR 2.0U 2.0U 2.0U 2.0U 2.0U d-BHC 2.0U 2.0U 2.0U 2.0U 2.0U ALDRIN 2.0U 2.0U 2.0U 2.0U 2.0U

HEPTACHLOR EPOXIDE 2.0U 2.0U 2.0U 2.0U 2.0U ENOOSULFAN (1) 2.0U 2.0U 2.0U 2.0U 2.0U p,p'-D 0 E 2.0U 2.0U 2.0U 2.0U 2.0U DIELORIN 2.0U 2.0U 12.6 2.0U 34.9 ENORIN 2.0U 2.0U 2.0U 2.0U 2.0U

p,p'-0 D D 2.0U 2.0U 2.0U 2.0U 2.0U ENOOSULFAN (II) 2.0U 2.0U 2.0U 2.0U 2.0U

p,p'-0 D T 2.0U 2.0U 2.0U 2.0U 2.0U ENORIN ALDEHYDE 2.0U 2.0U 2.0U 2.0U 2.0U ENDOSULFAN SDL FATE 2.0U 2.0U 2.0U 2.0U 2.0U

METHOXYCHLOR 2.0U 2.0U 2.0U 2.0U 2.0U TOXAPHENE 20. OU 20. OU 20. OU 20. OU 20. OU CHLOROANE 20. OU 20. OU 20. OU 20. OU 20. OU AROCLOR 1016 20. OU 20. OU 20. OU 20. OU 20. OU AROCLOR 1221 20. OU 20. OU 20. OU 20. OU 20. OU AROCLOR 1232 20. OU 20. OU 20. OU 20. OU 20. OU AROCLOR 1242 20. OU 20. OU 20. OU 20. OU 20. OU AROCLOR 1248 20. OU 20. OU 20. OU 20. OU 20. OU AROCLOR 12S4 20. OU 20. OU 20. OU 20. OU 20. OU AROCLOR 1260 20. OU 20. OU 20. OU 20. OU 20. OU

U denotes detection Unit.

oooc:

Table 1.2 Results of the Total Organic Carbon Analysis in Soil

Project # 2362 Stamina Mills

(Concentrations reported in ing/Kg)

Sample No. Location Concentration

6522 Site 1 8200 6524 Site 3 20000 6525 Site 4 5200 6526 Site 5 29000

OOOCG

Graph 1.1 Grain Size Analysis Plot Project # 2382 Stamina Mills Sample # 6522

'i V

1 O >

pf

§

3 1 I

< 4

ft

t

»ce NT

5

TUN £9

J 0

ir v

3

;HT

1 5 s § m

f ?

f !

f Ii/ \ \ *t

o Jt)

n >-I 0 """

l?\

^ * *

V* >

— V

T^

,v-'­

• X.

r>! ei ', &\

2! §"* !

? |

55

1 1

O c7) £j

—

-, 6 -f-/­/ ff

1 '2 I kj

3 9 IN

NO. 4 F

m0) r­

•o

•o

m ^ > 33

r3

*f i

i'i

o

^ z » H m 5xr r S

m m

­°

/* S*'\

^

-"' _^^ ]r~*~

.—• ^^ r~~

X x

•/l SO

NO

1 0 o a o

m c/t

40 «

^ K1 1 /

o 7 -,

J"

n ~ _ v

X s—

n

a.

r~ o a

5 3

•o

1

•4­

^ •s

— v*

Z >

5

0 c »

i T) m 1.i(/> r < >z

•n 0 C l

0" > H

A m z 52 z rn m 73 \s>

DO O5n

z

l/>o

?0

mi/->

z o

%

f\

! 4

|

J

O

o o

/ •/—

—1 -=­ NO. 200

> n 0 o

Graph 1.2 Grain Size Analysis Plot Project # 2382 Stamina Mills Sample # 6524

r\

tf 1 ^> 0 j

0 go 3 5

• <4

Ptf

5

»cc NT

5

TIN

i

:* «

5

if »•.e:c

§

;HT

g • 5 S 8

3 ?3 4

^ ' a-j

§I11* t

o Jt)> -

-

TV

^

— Oi t> ;

8 " k-=*-i 3 1 N

>H

•<­

-^

$ i

2! 3

rI *

-t IN

3, 4 1 N.

C 71

^. -•; •t, —

j — c -—

! '2 1 N

3 3 IN.

NO. 4 F

rn CO

r­

^ '"

•o

m

> ;c </i

p1

* fi

i

ii

A

^ Z » H m

2 ­C ° r CI H m 2

-" •*" f ^* . '

-^—• L=>­ • •-• •i — -^ ^"s

1(/_ NO 4O

J"

^

a 0

pi<

«

o a r

r~ o a

J

o X­

Ss*

NO. 2CO

~

• >

0 3

„

~

^

~

X >

3 •n 0

m o

Z

i

^v ^_

N­-

VS —

*'i

~^«

.

f1

09 C. 7) O

T) m z z ! >

r < >

0" > H

Z. m Z 2 z m m 33 f*

l/»o

?0

mi >

z n

\

ir : 4

|

J

o o

> n o o

Graph 1.3 Grain Size Analysis Plot Project # 2382 Stamina Mills Sample # 6525

i5 ^6 »cc HT F IS E* .' ir v

^

- 1

1

3P 3 5

i<a t

<$ 5 5 5 g 1 <5 5 §

Q i

{

?

f i

I

§1

$ 1 «

•

"" Ci 73 >

;

S

hj

_^

L4

f * * -V o!

&i ;

8

n >H

^

>~

^ >

*•"

,L

^^

" $ \

s\ ? 1

1 IN

0~" ^ ^

£

jT

1

3 ff

3

— S/

7^ S

1 '2 1 N

C 7}

^

/

2., '* \ &

9 o •—­ m^^.

s /

j

'

L—4 *—

9- 3

NO.

IN.

4 , c

m m

r-i~\

^ '~

•o

y3

fi

o J z

*N

2C .­°

/ 4-—

/ X

/ /

-1

i 0

£ 8

r X -« m

1L N 3

m i/)

4*O ^J

m •f^ $

x f i

/

/

O

O I- T3 1— — -=H i rf= SO. 20O

o > a

r»

"-"

—•

§"' _

i

X

5 •n 0

en O yi

z

• ,-.

*••.

^

-»»

03 c X

TJ m z z <s>

zo"> H

JL m z C

tX» O

?o

•n

s

r i

Ii

ij

O o

-t z u« r (- m

0.

< > 2

m » r^

Z 71

> n o o

(Kl 0^?>

Graph 1.4 Grain Size Analysis Plot Project # 2382 Stamina Mills Sample # 6526

| G

RA

DA

TIO

N

CU

RV

ES

f

v> tf *e»ceNr fist* ar weifiHt ' \ 1 2o 3 S ^ S ^ S 5 S S 8

S" p

/•" f ? I?,a' c

X

t\ L*> iA \ .

^ i

Classification

r - 1 IN.

S

/ 1/2 IN. /

Oi J— 3 3 IN. z /»• !

^ -\ * CSi /

SO. 4 .

r-r- 0a

/ y H >

r /

/

z /•o NOJ 1 O ^ ui~ - o• N / > n a

3

F / o r ° ILLIM

CT

7*­

i / J m

en

_^^ NO 40 Ul RC

MA

RK

S:

tf B

OR

ING

S, S

OIL

S &

TE

ST

ING

CO

. F

OU

ND

AT

ION

EN

GIN

EE

RS

H

AR

RIS

BU

RG

. PE

NN

SY

LV

AN

IA

m ^***^2

s*^ SO. 60 s*

si / -- NO. 100

o //

NO. ZOO

5 0 o8

§ I

<- •o o 3 a

r* 3 1 a "i

i 3 3

I "(

*

n^>>.-

A

1 —

S3'"1

X? o.

_a

io

0

QA/QC FOR PESTICIDES

EMSL WP 385, containing heptachlor, p,p'-DDE, aldrin, dieldrin, p,p'-DDT and p,p'-DDD was analysed to check the accuracy of the standard calibration. The percent recoveries, ranging from 81 to 123, are all within accepted QC limits except for the heptachlor recovery which was 123% and just above the upper limit of 122%. Results are listed in Table 2.1.

Each sample was spiked with 100 uL of a 2 ug/mL solution of dibutyl chlorendate; percent recoveries ranged from 88 to 142. Results of the surrogate recoveries are listed in Table 2.2.

Sample 6522 was chosen for the matrix spike/matrix spike duplicate (MS/MSD) analyses. A mixture of heptachlor, dieldrin, endrin, and p,p'-DDT was added to give a concentration of 0.1 ug/L for each analyte in the sample. The percent recoveries are listed in Table 2.3. They range from 76 to 154 when the recovery for the dieldrin MSD (1450%) is deleted. The relative percent differences (RPDs) range from 11 to 28 when the dieldrin RPD (165) is deleted. A blank sample was also spiked and analyzed in duplicate. Blank # 3 had percent recoveries ranging from 58 to 70 and RPDs from 3 to 10. These results are also listed in Table 2.3.

00011

Table 2.1 Results of tht EMSL Sample Analysis

Project * 2382 Stamina Mills

(Concentration reported as ug/L)

EMSL mix «85 (1:50 dilution) Date Analyzed: S-U-90

Parameter EMSL Recovered XRecovery Recomnended Cone. Cone. X Range

Heptachlor 40 49 123 42-122 Aldrin 40 40 100 34-111 p,p'-0 D E 40 47 118 30-145 Oieldrin 40 48 120 30-146 p,p'-0 0 0 200 161 81 31-141 p.p'-D D T 200 161 81 25-160

0001;:

Table 2.2 Results of the Surrogate Recoveries for Pesticides/PCBs

Project * 2382 Stamina Mills

DBC Sample ID X Recovery

Blank 93 6522 Matrix Spike 108 6522 Matrix Spike Duplicate 116 6522 133 6524 142 6525 68 6526 113

DBC denotes dibutylchlorendate.

00013

Table 2.3 Results of the Matrix Spike/Matrix Spike Duplicate Analysis

Soil Samples Project * 2382 Stamina Mills

(Extract Concentrations reported as ug/kg)

Sample ID : 050390-403 (6522) Sample Location : Site 1

Analyte Spike

Added Sample Cone.

MS Cone.

MS

XRec. MSO Cone.

MSO

XRec. RPO

HEPTACHLOR

DIELDRIN

ENDRIN

p,p'-D D T

100 100 100 100

0.00 0.00 0.00 0.00

76 139 104

154

76 139 104 154

85

1450

138

131

85 1450

138 131

11

165 28 16

Sample ID : Blank 3

Analyte Spike Added

Sample Cone.

MS Cone.

MS XRec.

MSD Cone.

MSD

XRec. RPD

HEPTACHLOR

DIELDRIN ENDRIN

p,p'-D D T

100 100 100 100

0.00 0.00 0.00 0.00

62 64 62 70

62

64

62 70

60

58

59

67

60 58 59 67

3 10 5 4

0001-1

QA/QC FOR TOTAL ORGANIC CARBON

The lab blank was chosen for the matrix spike/matrix spike duplicate analyses. The percent recoveries were 106 and 111 and the relative percent difference was 4. Results are listed in Table 2.4.

OGOI:

Table 2.4 Results of the Matrix Spike/Matrix Spike Duplicate Analysis

Soil Samples Project * 2382 Stamina Hills

Sample ID : Blank (Concentrations reported as rag/Kg)

Analyte MS SpikeAdded

MSD Spike Added

Sample Cone.

MS Cone.

MS XRec.

MSD Cone.

MSD XRec. RPD

TOC Standard 4082 5405 72.09 4414 106 6083 111

oooie

I I

\A

I I CO I

ro I I

0=

II 35 111 555

Q Q X

1 S

00017

f

0001!