PEERConsultants, P.C. ENGINEERS SCIENTISTS MANAGEMENT CONSULTANTS

mOO Twin brook Parkway • Suite 410 • Rockville. MD 20852 • (301) 816-0700: • FAX (301) 816-9291Pollution. Environment, Energy and Resources

July 2 6 , 1990

Mr. Steve VealeRemedial Project ManagerU . S . EPA, Region 61445 Ross AvenueDallas, TX 75202-2733.REFERENCE: Contamination Mapping, Rogers Road and Jacksonville

Landfill Sites (WA Nos. 09-6LB6 and 01-6LD3)Dear Mr. Veale;

PEER is pleased to submit four copies of the Draft TechnicalMemorandum for Contaminant Mapping at the Jacksonville Landfill andRogers Road Landfill.

A final version will be made available after PEER receives thecomplete analytical package from the subcontractors. Soil volumeestimates will not change upon receipt of the complete analyticalpackage.

Please contact Bob Wassmann or me if you have any furtherquestions.

^-—•5incre>rely,

RAL:mfsEnclosures

cc: ^ A p P c ^ e2) & A »>->•»> »^/it >'*• KtiClQ

1\ :U</ec.f2 p-.l<^W.ishirwon, I X ; : Kockville. Ml): Philadelphia. PA; Daytnn. UH: Cambridge. MA: < )ak KidKff. T.N:

Atlanta. dA: St. Charles. MO: Richland. WA: Alken. riC

145578

REM VIRemedial Response Activities at Uncontrolled

Hazardous Waste Facilities

^s

\Environmental Protection AgencyHazardous Site Control Division

Contract No. 68-01-7448

PEER Sheladia Associates, Inc.Advanced Sciences, Inc.

Consultants RC. MEL, Incorporated

Phoenix Safety Associates, LtdResource Applications, Inc.Transviron, Inc.

DRAFTTECHNICAL MEMORANDUM

FORCONTAMINANT MAPPING

AT THEJACKSONVILLE LANDFILL SITEJACKSONVILLE, ARKANSAS

July 27, 1990

DOCUMENT CONTROL NUMBER

09-FS1-TM-243

PREPARED BYPEER CONSULTANTS, P . C .

REM VIU . S . EPA CONTRACT 68-01-7448WORK ASSIGNMENT NO. 12-4RB7

Executive Summary

The Feasibility Study Report for Jacksonville Landfill site(PEER, June 1990) identified four sample locations, and a drumdisposal area (shown in Figure 1) with equivalent 2,3,7,8-TCDD*concentrations exceeding 1.0 ng/g. The Centers for Disease Controltypically recommends a reduction of surface contamination to amaximum of 1.0 ng/g equivalent 2,3,7,8-TCDD and subsurfacecontamination to a maximum of 10 ng/g as a common remedial actionobjective for dioxins and furans in residential areas. This wouldlimit risks from all substances associated with the JacksonvilleLandfill Site to levels approaching a lifetime excess cancer riskof 10'6 (in consonance with the National Contingency Plan) for allpotential routes of exposure combined. •

The Feasibility Study estimated approximately 2406 cubic yardsof soil, debris, and waste ( 1 6 3 6 yd3 from the drum area plus 770 yd3-from the other specified areas) may require remediation. Becauseapplicable treatment methods are extremely costly, the objective ofthis effort was to perform additional sampling to more accuratelydefine contaminant boundaries under this contaminant mapping phaseof the RI/FS. Revised calculations based on more stringent gridsamping now result in an estimated a volume of 438 yd3 (surfacearea = 1309 yd2) of 2,3,7,8-TCDD contaminated soil above 1.0 ng/g,including 130 yd3 (380 yd2) above 10.0 ng/g.

* 2,3,7,8-TCDO equivalence is • method of quantifying the significance of the exposure to each of thecomponents of complex mixtures of chlorinated dibenzo-p-dioxins and chlorinated dibenzo furans using availabletoxicological data and reasoning on the basis of structure activity relations.

Graham Road

N

ContaminatedAreas

TrenchesSite Fence

0 100 200 300 400

Scale (feet)

AREAS OF 2,3,7,8-TCOO CONTAMINATION AT JACKSONVILLE LANDFILL

FIG.1JACKSONVILLE LANDFILL, JACKSONVILLE, AR

Objectives

The objectives of the contaminant mapping phase were to moreaccurately determine the contaminated areas containing 2 , 4 , 5 -trichlorophenoxyacetic acid ( 2 , 4 , 5 - T ) , 2,4-dichlorophenoxyaceticacid ( 2 , 4 - D ) , 2,4,5-trichlorophenonxypropionic acid (2,4,5-TP orSilvex) , 2 , 4-dichlorophenol and 2,3,7,8-tetrachlorodibenzo-p-dioxin( 2 , 3 , 7 , 8 - T C D D ) . Since the chemicals are all co-located and2,3,7,8-TCDD is the principal source of the excess cancer risk, itwas used as the primary indicator of the contaminated area.Surface dioxin contamination was defined to a 1.0 ng/g isopleth andestimated to a 10 ng/g isopleth, and subsurface dioxincontamination was defined to a 10 ng/g isopleth.

Sampling and Mapping

Four separate contaminated areas were sampled independently.Surface soil samples were collected and analyzed for 2,3,7,8-TCDDuntil the 1.0 ng/g isopleth was defined. Subsurface soil sampleswere collected and analyzed until the 10.0 ng/g isopleth wasdefined. To calculate equivalent 2,3,7,8-TCDD, two samples werecollected from each of the four locations to fingerprint thelocation-specific contaminants. The fingerprinting consisted ofcomplete dioxin/furan analysis by isomer and complete method 8270and 8080 for semi-volatile organics and pesticides/PCBs.Individual dioxin/furan concentrations will be used to calculatethe relative proportions of each isomer in relation to 2 , 3 , 7 , 8 -TCDD. 2,3,7,8-TCDD was used as the indicator compound for mappingpurposes. The presence of various chemicals in the soils, as wellas evidence of differing disposal practices made it necessary foreach location to be treated individually. Each of the four areashas an independently calculated location specific 2,3,7,8-TCDDequivalent ratio. (Analytical results for the fingerprint samples

have not been received at this time. This draft report uses actual2,3,7,8-TCDD concentrations rather than equivalents. Theequivalent 2,3,7,8-TCDD ratios will be incorporated into the finalreport.)

Sample locations were recorded by measuring compass direction(based on magnetic north) and distance from a bench markestablished at the center point of each contaminated area. Thecenter point was the estimated point of highest concentration(based on previous sampling) of 2,3,7,8-TCDD equivalents. Samplingbegan at a point beyond any known contamination and progressedtoward the center point (from least contaminated to mostcontaminated). The first round of sampling consisted of foursamples taken from the extremities of the horizontal axes ( N , S , E,W) at the surface. After sample analyses were evaluated at the onsite laboratory, the next round of sampling proceeded toward the.center point if less than 1.0 ng/g of 2,3,7,8-TCDD was detected.If a 2,3,7,8-TCDD concentration of 10.0 ng/g or higher wasencountered at the surface, the next round consisted of surfacesamples taken further from the center point plus samples taken ata depth of greater than one foot. The concentration of 2 , 3 , 7 , 8 -TCDD detected at each sampling location determined the distance anddirection of the next sampling point ( e . g . , the next sampling pointwas established-close to the previous point if results approached1.0 ng/g and a farther distance from the previous sampling point ifresults were significantly above or below 1.0 ug/g).

A bench mark was established at the estimated center point ofcontamination by augering a six inch diameter hole 1.5 feet deepand cementing in a 0.5 inch diameter galvanized pipe leaving threefeet exposed above ground surface (see Figure 2 ) . Reproducibilityis a critical factor in this mapping effort. Assuming the worst

SURFACE GRADE

1 1/2"

SCHEMATIC DIAGRAM OF THE CENTER STAKE

JACKSONVILLE-ROGERS ROAD LANDFILL SITES, JACKSONVILLE, ARKANSAS

case, that is all location stakes being destroyed, exactreproducibility of the sampling sites can be established as long asthe bench mark remains.

Sample Collection

Surface samples were collected 3 to 5 inches below grade. Thetop three inches of soil were removed using a steel shovel; sampleswere then collected using stainless steel spoons (see Photograph1 ) . The top three inches of soil were not sampled because of thepossibility of dioxin photodegradation caused by sunlight.Subsurface samples were collected by augering to a depth of 12 to18 inches. The bottom of the hole. was then cleaned with astainless steel spoon and the sample collected after all loose soilwas removed. A power auger was used due to the amount ofsubsurface debris associated with the landfill (see Photograph 2) ._

Sample Equipment Decontamination

Stainless steel spoons, steel shovels, and steel auger flightswere decontaminated by washing with a mild detergent solution andthen rinsing with distilled water. Equipment decontamination wasverified through background sampling; non-detectable levels ofcontamination were required for verification.

Analyses

A Subcontractor, Flint Environmental Services, Inc,, Tuisa,OK, supplied an on-site field laboratory (Photographs 3 and 4) thathad demonstrated and proven 2,3,7,8-TCDD analytical methods capableof achieving 0.3 ng/g detection levels with a high degree ofaccuracy and precision. The analytical method used on site was the

Photograph 1Sample Collection

Photograph 2Drilling Soil Boringpower Auger

ooc^-0(N00

Laboratory

Region VII "Rapid Determination of TCDD Using Gas Chromatographyand Tandem Mass Spectroscopy" (Appendix I ) . This method employs atriple quadrupoie mass spectrometer (MS/MS) as the final detector.The Flint laboratory was equipped with a Sciex TAGA 6000Einstrument. The specificity of detection inherent in such a systemsignificantly reduces the need for sample cleanup. This, inturn,improves productivity and cost effectiveness relative to other high 0s'resolution and low resolution GC/MS analytical techniques. ooField Activities

PEER Consultants mobilized field personnel and equipment tothe Jacksonville Landfill Site on May 2 9 , 1990. FlintEnvironmental supplied the on-site laboratory and technicalpersonnel to perform the sample analyses. One hundred and sevensoil samples were collected between June 1 and June 15, 1990.-Ninety nine of these were analyzed on-site for 2,3,7,8-TCDD within26 hours from the time of collection. The remaining eight sampleswere shipped to Flint Environmental, San Diego, CA, forfingerprinting analysis. Site demobilization took place from June16 to June 20, 1990.

Sample collection and analysis was organized as follows:

o Location 1 (JK-LC1) was centered at the midpoint betweenRI sample locations PS-PT-07/08. Twenty-two surface soilsamples, including two duplicates, and five subsurfacesamples were collected and analyzed for 2,3,7,8-TCDD.

o Location 2 (JK-LC2) was centered on RI sampling locationSS-F4-01. Five surface soil samples and two subsurfacesamples were collected and analyzed for 2,3,7,8-TCDD.

o Location 3 (JK-LC3) was centered on RI sampling locationSS-H2-01. Twenty-six surface soil samples, including twoduplicates, and five subsurface samples were collectedand analyzed for 2,3,7,8-TCDD.

o Location 4 (JK-LC4) was centered on the drum disposalarea. Twenty-two surface soil samples,, including oneduplicate, and five subsurface samples were collected andanalyzed for 2,3,7,8-TCDD.

o Two additional surface samples were collected from eachof the four above mentioned locations and analyzed fordioxins/furans by isomer and complete method 8270 and8080 for semi-volatile organics and pesticides/PCBs(fingerprint samples).

o Six background samples were collected and analyzed onsite for 2,3,7,8-TCDD to verify quality control/qualityassurance (QC/QA).

o Two suspect drums identified by the U . S . EPA removalaction contractor and one identified by the PEER sitepersonnel were sampled and analyzed for 2,3,7,8-TCDD.

Findings

Overall, surface and subsurface soil concentrations of2,3,7,8-TCDD were generally below 1.0 ng/g. A breakdown of sampleconcentration ranges, excluding background and fingerprint samples,is shown below. Appendix II contains data sheets for all samplescollected.

10

o 6 9 samples had concentrations from non-detect (ND) to 0.5ng/g

o 15 samples had concentrations from 0.5 to 1.5 ng/go 7 samples had concentration from 1.5 to 5.0 ng/go 0 samples had concentrations from 5.0 to 10.0 ng/go 2 samples had concentrations above 10.0 ng/g

Location JK-LC1 straddles an access road with small piles ofdebris found on both sides of the road. The road and shoulders areslightly overgrown with grass and weeds. Soil borings revealed agravel and dirt road bed at least twelve inches thick, with clayfound on both sides. Construction rubble including bricks andconcrete were either buried in the clay along the sides of the roador used in the construction of the road bed.

This location produced only four surface soil samples between0.5 and 1.5 ng/g 2,3,7,8-TCDD. The highest concentration, being1.43 ng/g, was detected in sample JK-LC1-11, located 40 feet duewest of the center stake. See Figure 3 for surface soil samplelocations and Figure 4 for surface soil concentrations. AppendixIII contains all sample locations by compass direction and depthsof sample collection. Subsurface soil borings had concentrationsranging from 0.17 to 0.32 ng/g. Figure 5 depicts soil boringlocations and contaminant concentrations found at location JK-LCl.Using data gathered during the contaminant mapping phase andpreviously during the RI, approximately 86.5 yd3 (260 yd2) of soiland debris is contaminated above the 1.0 ng/g level. No samplescollected during either sampling event produced concentrationsabove 10.0 ng/g 2,3,7,8-TCDD at location JK-LC1.

Location JK-LC2, previously documented as RI sampling locationSS-F4, is located in a densely wooded area abundant with largetrees and a thick growth of ivy covering the ground surface. Soil

11

MAGNETICNORTH

020

060

140

150

17

200

(PT07)

JK-LC101 05 1 1

0 012 09 070 0 0

030

(FT 08)0

19 180

160

13

10

ROAD (PT06) 080 0

SCALE FEET04

25 50

(• ; APPROXIMATE LOCATION OF PREVIOUS SAMPLESCOLLECTED DURING THERI

SURFACE SOIL SAMPLING LOCATIONS AT JK-LC1FIG. 3

JACKSONVILLE LANDFILL SITE, JACKSONVILLE, ARKANSAS

12

MAGNETICNORTH

Qi

.370

.37 .2 .320 0 0

(.02)0

SCALE (FEET)

0 25 50

ALL CONCENTRATIONS IN ng/g TCDD

( ) APPROXIMATE LOCATION OF PREVIOUS SAMPLSSCOLLECTED DURING THE fit

SURFACE SOIL CONCENTRATIONS AT JK-LC1FIG. 4

JACKSONVILLE LANDFILL SITE, JACKSONVILLE, ARKANSAS

13

,MAGNETIC

NORTH

SB-04 Y0 ^S,

.17 "

LOCATIONS AND

JACKSONVILLE LANDFILL SITE, JACKSONVILLE, ARKANSAS

1 LEGEND: SAMPLE NUMBERSAMPLE CONCENTRATIONS (ng/g TCDD)

SB-0?0

.26

JK-LC1

SB-030

.18

0

CONCENTRATIONS OF SOIL BORINGS AT JK-LC1

SB-020

.32

SB-05.17

SCALE (FEE

•25

-

T)

50

FIG. 5

14

borings unearthed a wheel hub possibly from a rail car. The soilin this immediate area is loose and granular and littered withglass and metal. The glass has been melted and is covered withcarbon indicating burning activities.

Figure 6 indicates surface soil sample locations, Figure 7surface soil concentrations, and Figure 8 subsurface soil boringsand concentrations for location JK-LC2. Two surface soil samplesand two subsurface soil borings were above 0.5 ng/g. The highestconcentration detected at this location was 2.04 ng/g found atsurface soil sample LC2-02 situated only five feet from the centerpoint. Some interferences were present during analysis that werecharacteristic of PCBs. This confirms the presence of pCBsdocumented at this location during the RI. A total volume of 4.74yd3 (14 yd2) is above the 1.0 ng/g isopleth. No samples at locationJK-LC2 collected during the contaminant mapping phase or the RIwere contaminated above 10.0 ng/g 2,3,7,8-TCDD.

Location JK-LC3, RI sample location SS-H2, is centeredapproximated ninety feet directly east of the drum pile (JK-LC4) ina heavily wooded area. Young trees were so dense that manybranches and limbs had to be removed so that line of sight could bemaintained between the center point and sampling locations. Thefoliage blocked- sunlight to the extent that a flash bulb was neededwhen taking photographs in this area (see Photograph 5) . Soilconditions were mostly granular with clay approaching to withinfifty feet south of the center point. Strong indications ofburning were apparent starting at the center point and throughoutthe area to the south and west.

Location JK-LC3 provided the most challenging mapping due tothe high concentration of TCDD, the wide area over which it was

15

MAGNETICNORTH

05

03

02

JK-LC2

(SS F4) 010

SCALE (FEET)

04

0 5 10 15

( ) APPROXtMAlE LOCATION OF PREVIOUS SAMPLE COLL£CTEO DURING WE Rl

MAGNETIC °3NORTH

020

04JK-LC205 J

( S S F 4 ) ^0

SCALE (FEET)

0 5 10 15

( ) APPROXtMAlE LOCATION OF PREVIOUS SAMPLE COLLECTEO DURING WE fit

SURFACE SOIL SAMPLING LOCATIONS AT JK-LC2

JACKSONVILLE LANDFILL SITE, JACKSONVILLE, ARKANSASFIG. 6

002086

MAGNETICNORTH

.22

.37

SCALE (FEET)

5 10

ALL CONCENTRATIONS IN ng/g TCDD

( ) APPROXIMAJE LOCATION OF PHEWOUS SAMPLECOLLECTED DUHINCI THE HI

15

1 .

MAGNETIC -37

NORTH ^——-—^^^

/ 204 ^^

/ 111 \.22 ( JK"LC2 a 1

^-———•—^^ o0

SCALE (FEET)

0 5 10 15

ALL CONCENTRATIONS IN ng/g TCDD

( ) APPROXIMAJE LOCATION OF PHEWOUS SAMPLECOLLECTED DUHINCI THE HI

SURFACE SOIL CONCENTRATIONS AT JK-LC2

JACKSONVILLE LANDFILL SITE, JACKSONVILLE, ARKANSASFIG. 7

002087

MAGNETICNORTH

LEGEND: SAMPLE NUMBERSAMPLE CONCENTRATION (ng/g TCDD)

SB-010

.55

JK-LC2SB-02

0

.7

SCALE(FEET)

10 15

LEGEND: SAMPLE NUMBERMAGNETIC SAMPLE CONCENTRATION (ng/g TCDD)

NORTH

SB-010

.55

SB-02JK-LC2 °

-4-

SCALE(FEET)

0 , 5 10 15

LOCATIONS AND CONCENTRATIONS OF SOIL BORINGS AT JK-LC2

JACKSONVILLE LANDFILL SITE, JACKSONVILLE, ARKANSASFIG. 8

002088

spread and the interferences imposed on the analytical equipment.Flint Environmental chemists indicated that the interferences whicharose during the analytical procedures were similar tointerferences produced by PCBs. After surveying the sampling areamore closely a porcelain connector from a transformer was found inthe immediate area (see Photograph 6 ) . Four surface soil sampleshad TCDD concentrations from 0.5 to 1.5 ng/g, five from 1.5 to 5.0ng/g, and one above 10.0 ng/g. In addition, one subsurface soilboring sample had a concentration above 10.0 ng/g. Sample LC3-16,located forty-one feet south of the center point, had the highestconcentration of all samples collected ( 3 9 . 7 1 ng/g TCDD). Asubsurface soil boring sample collected at the center point yielded26.03 ng/g TCDD in comparison to RI sample SS-H2 taken three inchesfrom the surface at the same location which produced 2 6 . 6 ng/gequivalent 2 , 3 , 1 , 8-TCDD. The sampling and analyticalreproducability at this location indicate extensive, homogenouscontamination. Approximately 127 yd3 (375 yd2) of 2 , 3 , 1 , 8-TCDDcontaminated soil above 1.0 ng/g including 50 yd3 (140 yd2) above10.0 ng/g are present at location JK-LC3.

Because of the close proximity of locations JK-LC3 and JK-LC4both locations appear on a single series of maps. Figure 9 showssurface soil locations. Figure 10 indicates surface soilconcentrations, and Figure 11 plots subsurface soil boring samplepoints and concentrations for locations JK-LC3 and JK-LC4.

Location JK-LC4 is the drum disposal area located at thesouthern end of the landfill. Tall grass is growing intermittentlywith bare patches where drums and debris are visible. No trees arefound in this area with the exception of a few saplings. Denseclay is the prevalent soil type.

19

5ation JK-LC3

:aph 6

„, ^OtX°" ^-Lc3

20

MAGNETIC

NORTH

0 21

05 15° 25l4 ° 0 00

(DS 01)13 -"0

100

oa —I— ° o o04 08 09 08 020 0 0 ., 0 0

.^ 23 19

.^^ o 24 °(SS H2) ^ 12 °

'.\0

" 07 1«0 0 19

0030

(SS12) 1a0 0

H-X-X-X-X.-X.-X-X-X-X-X-X-X-X-X-X-X-X-X-X-X-X-X-X X-X X X-X-X-X-X-X-X X X X X-X-X-^X^-X-X-X-X-X-X--X-X-X-X-X-X-X-X--X--j<-)<-X-X-X-X-X-X--X-X-X-X-X X-XrX X-X-X-X-X-X-X-X-X-X-X-X-)

SURFACE SOIL SAMPLING

JACKSONVILLE LANDFILL SITE. JACKSONVILLE, ARKANSAS

07 JK-LC4 SAMPLES

-j- CENTER STAKE

C J APPROXIMATE LOCATION OF PREVIOUS SAMPLES

05 COLLECTED WRINQ THE W

01

LEGEND: JK-LC3

0

0

(DS 02)0

09„ (DS 03) 20

(PT02) " „ <> ^0

0

0

18 (Ds0^)o JK-LC4 °

1 70 06 02

JK-LC3 o •(D305)0 (DS06)

77 o(DS09) o

6 (DS 08)(DS 07)

(PTOI)^0 0

1 10

16 070 0

*

mL/J

0fwce

LOCATIONS AT JK-LC3.4

SAMPLES

SCALE (FEET)

HKBBBB[KJ B^ HD25 50

FIG. 9

75

002091

MAGNETIC

NORTH

0 .440 0

(26.6)

(2.51)

( -X-X-X-X-X-X X-X-X -X-X-X-K-X-X-X X- X-X-X-X X-X-X-X-X-X-X-X-X-X-X-X-X-X-X-X-X-X-X X X-X-X-X-X-X-X-X-X-ii-X-X X - X - X - X - X X X X-X-X-X-X-X-X-X-X-X-X-X-K-X X-X-X-X X - X - X - X - X - X - K - >

SURFACE SOIL CONCENTRATIONS AT JK-LC3.4FIG. 10

JACKSONVILLE LANDFILL SITE, JACKSONVILLE, ARKANSAS

002092

MAGNETIC

NORTH LEGEND: SAMPLE NUMBERSAMPLE CONCENTRATION (ng/g)

LC3-SB-040

.35

LC3-SB-03 M'\C3 LC3-SB-01

LC3-SB-0526.03

LC4-SB-040

.33

LC4-SB-03 JK'\C4 LC4-SB-01

.29

i.C4-Sfl-051.48

SCALE (FEET)

FENCEALL CONCENTRATIONS IN ng/g TCDD

K-X-K-X-M-X X X X K K X X X X K-X K. K X X X ' X X X X X X -X M-X X-X X X X X-^-X-X K-X-X-X-X X X X X-^-M-X-M-»(-)(-X-X-K-X-i(-X-»-X-X-»t-K-)f-X-X-)(-X-X--X-K-X-4«-i(- X-X-X -X- )(-)(• -X-X-X-l

LOCATIONS AND CONCENTRATIONS OF SOIL BORINGS JK-LC3.4FIG. 1 1

JACKSONVILLE LANDFILL SITE, JACKSONVILLE, ARKANSAS

002093

When reducing the radius of the 1.0 ng/g perimeter, samplelocations would be advanced until a detection approaching 1.0 ng/gwas reached or a drum on the surface was encountered. At locationJK-LC4 surface soil and subsurface soil boring samples were takenwithin two feet of drums and the sample produced a TCDDconcentration below 0.5 ng/g. This has been attributed to the soiladhesion of 2,3,7,8-TCDD.

Two surface soil samples and two subsurface soil boringsamples were between 0.5 and 1.5 ng/g TCDD. The only sample thathad a concentration above this was surface soil sample LC4-15having a concentration of 1.9 0 ng/g. This sample was very close toan isolated drum. Approximately 220 yd3 ( 6 6 0 yd2) of 2 , 3 , 1 , 8-TCDDcontaminated soil is above 1.0 ng/g including 80 yd3 (240 yd2) whichis above 10.0 ng/g at location JK-LC4. See Figures 9 , 10, and 11for surface soil sample locations, surface soil sampleconcentrations, and subsurface soil boring sample locations andconcentrations, respectively.

General Observations

The first round of samples from each location was collectedoutside the "hot" areas, beyond any contaminants. The second roundof samples moved closer toward the hot spots to locate the 1.0 ng/gperimeter. This sampling strategy employed a gradual progressiontoward the known hot spots. This method allowed for accuratedistance measurements between sources of contamination and soilsamples to better understand the dioxin migration through the soil.

Samples were collected in native soil (not backfill), only twofeet away from drums at several surface soil and soil boringlocations. All of the samples were below 0.5 ng/g, indicating howstrongly the dioxin adheres to the soil. If the soil was backfill,

24

contaminated with glass and other debris, the occurrence of asignificant (S 0.5 ng/g) dioxin concentration greatly increased.

Conclusions

Soil samples collected during the contaminant mapping phaseindicate that the dioxin present on-site is primarily located inthe residual material in the drums and in back-filled soils where §(NPCBs are present. Open burning has been documented at the landfill §and could have contributed to the dioxin contamination throughincomplete combustion of PCBs producing TCDD at locations JK-LC2and LC3. TCDD trace contamination from herbicides is the morelikely source at locations JK-LC1 and LC4. Drum samples collectedand analyzed during the RI normally have concentrationsapproximately one order of magnitude greater than theconcentrations detected in adjacent soil samples. Soil samples,collected during the RI and during the contaminant mapping arecomparable, and within the same order of magnitude.

Locations JK-LC2 and JK-LC3 were the only two locations thatproduced surface sample concentrations above 2 . 0 ng/g TCDD duringthis mapping study. These two locations were also very shaded fromdirect sunlight. Although not enough samples were collected tosubstantiate this, it is possible that photodegradation of TCDD isoccurring at some of the more exposed locations at the JacksonvilleLandfill.

In very general terms, native clay samples were relativelyclean (less than 0.5 ng/g TCDD) while littered, granular, backfillwas more likely to be contaminated. Soil conditions' at LocationsJK-LC2 and JK-LC3 were very similar, both composed of dark, loose,granular soil littered with broken glass. Locations JK-LC1 and JK-LC4 looked like surface dumping occurred while native clay soil

25

remained relatively undisturbed with the exception of the road bedconstruction at JK-LCl.

Calculated TCDD contaminated soil volumes for two TCDDconcentrations are as follows:

SOIL VOLUMES_____Location____ > 1 nq/cr > 10 no/aJK-LCl 86.5 yd3

JK-LC2 • 4.74 yd3

JK-LC3-JK-LC4

127 yd3 50 yd3

220 yd3 80 yd3

Total 438 yd3 130 yd3

26

APPENDIX I

Region VIZ Rapid Determination of TCDD Using Gas Chromatography andTandem Mass Spectroscopy.

REGION VII

RAPID DETERMINATION OF TCDD

USING GAS CHROMATOGRAPHY

AND TANDEM MASS SPECTROSCOPY

I Page

APPENDIX C-I - RAPID DETERMINATION OF TCOO USING GAS CHROMATOGPAPHYAND TANDEM MASS SPECTROSCOPY

1.0 ANALYTICAL METHODS1.1 SCOPE AND APPLICATION1.2 SUMMARY OF METHOD1.3 INTERFERENCES1.4 'SAFETY1.5 APPARATUS AND MATERIALS1 . 6 REAGENTS1.7 CALIBRATION AND LIMIT OF DETECTION DETERMINATIONS1.8 QUALITY CONTROL REQUIREMENTS1 . 9 SAMPLE COLLECTION, PRESERVATION, AND HANDLING1.10 SAMPLE EXTRACTION1.1 1 CLEANUP1.12 GC/MS/MS ANALYSIS1.13 METHOD PERFORMANCE1.14 DATA REPORTING

2.0 DATA VALIDATION PROCEDURE2.1 DELIVERA8LES2.2 CALIBRATION2.3 SAMPLE DATA2.4 QUALITY CONTROL2.5 HOLDING TIMES2.6 CONCLUSIONS

LIST OF TABLES

C-I-lC-I-1C-I-2C-I-2C-I-3C-I-7

C-I-10C-I-15C-I-20C-I-22C-I-23C-I-24C-I-28C-I-33C-I-33C-I-35C-I-35C-I-36C-I-40C-I-43C-I-45C-I-46

TABLE C-I-1-1 - OPERATING CONDITIONS FOR D8-5 GAS CHROMATOGRAPHYCOLUMN C-I-31TABLE C-I-1-2 - MS/MS OPERATING CONDITIONS C-I-32

LIST OF FIGURES

FIGURE C-I-1-1 - IDENTIFICATION CRITERIA AND LIMIT OF DETECTIONCALCULATION , C-I-19

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1.0ANALYTICAL METHODS

1 .1 SCOPE AND APPLICATION

This method is for use in the rapid determination of 2,3,7,8-Tetrachloro-dibenzo-p-dioxin (2,3,7,8-TCOO) in water, when 2,3,7,8-TCDO is known to bethe principal or the only tetrachlorodibenzodioxin isomer present. Themethod is intended to be used when analytical results are required rapidly,such as when site cleanup operations are in progress.

The method employs a triple quadrupole mass spectrometer (MS/MS) as thef'.-al detector. The description of the method here has been written forthe conditions of the Sciex TASA 6000E instrument. However, other MS/MSinstruments are also acceptable, as long as the quality controlrequirements are met. The specificity of detection inherent in such asystem significantly reduces the need for sample cleanup. This, in turn,improves productivity and cost-effectiveness relative to other highresolution and Tow resolution GC/MS analysis techniques (described inAppendices C-II and C-III). The apparatus and methods described are alsodesigned for use in a mobile laboratory, which allows for rapid on-slteanalyses.

The method described here is not specific to the 2,3,7,8-TCDO isomer.Since the method is not isotner specific, false positives, including isomersother than 2,3,7,8-TCOO, may occur. But errors in this regard would be onthe side of safety. Emphasis in the aethod is placed on avoiding falsenegatives, as this is a more critical consideration when public health isto be protected.

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This method is restricted to use only by or under the supervision ofanalys ts experienced in the use of gas chromatography/trlple quadruplemass spectrometers.

Because of the possible toxiclty or cardnogeniclty of 2,3,7,8-TCDO, theanalyst must prevent exposure to himself /herself or to others, by mater ia lknown or believed to contain 2,3,7.8-TCOO. Section 1.4 of this methodcontains guidel ines and protocols that serve as minimum safety standards ina l imi ted access laboratory.

1.2 SUMMARY OF METHOD

A one (1) liter sample of water Is taken and spiked with Internal standardsof Isotopically labeled 2,3,7,8-TCOO. The sample Is extracted wi th 3-60 mi.portions of methylene chloride. The methylene chloride is exchanged toisooctane during concentration of the extract to approximately 1 mL. Anoptional column chromatography cleanup may be performed. However, It w i l lusual ly be possible to analyze the concentrated Isooctane extract directlyusing capil lary column GC/MS/MS. Capil lary column GC/MS/MS conditions aredescribed later In this Appendix, which a l low for separation of TCOO fromthe b u l k sample matrix and measurement of TCDO 1n the extract.Quant i f icat ion 1s based on the response of native TCDO relative to theIsotoplcal ly labeled TCOO Internal standard. Performance Is assessed basedon the results of ERA performance evaluation samples, spike recovery tests,and method and field blanks.

1.3 INTERFERENCES

Method Interferences say be caused by contaminants In solvents, reagents,glassware and other sample processing hardware that lead to discreteartifacts and/or elevated backgrounds at the Ions monitored. All of these

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materials must be routinely demonstrated to be free from interferencesunder the conditions of the analysis by running laboratory method blanks asdescribed in Section 1.8. The use of high purity reagents and solvents andnew glassware helps to minimize such interference problems. Purificationof solvents by distillation in all-glass systems may be required, prior totheir use.

Pure water samples are not expected to exhibit significant interference ormatrix effects. However, the analyst should be alert to the possibility ofinterference by chlorinated compounds giving the same or similar massspectra as TCOO, or by the matrix of ground water from the site. The useof a triple quadrupole mass spectrometer as the detector serves to minimizethe influence of interferences from chlorinated compounds.

1.4 SAFETY

2,3,7,8-TCOO has been identified as a suspected human or mammaliancarcinogen. The toxicity or carcinogenicity of each reagent used in thismethod has not been precisely defined; therefore, each chemical compoundshould be treated as a potential health hazard. From this viewpoint,exposure to these chemicals must be reduced to the lowest possible level bywhatever means available. The laboratory is responsible for maintaining afile of current OSHA regulations regarding the safe handling of thechemicals specified in this method. A reference file of material datahandling sheets should also be made available to an personnel involved inthe chemical analysis.

1.4.1 J?econnended Safety Practices

Cach laboratory must develop a strict safety program for handling 2,3,7,8-TCOO. The following laboratory practices are recommended:

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Contamination of the laboratory wm be minimized by conductingall manipulations in a hood.

The effluents of sample splitters for the gas chromatograpn androughing pumps on the GC/HS should pass through either a columnof activated charcoal or a trap containing oil or high boilingalcohols.

1.4.2 Guidelines for Safe Handling

The following precautions for safe handling of 2,3,7.8-TCDD in thelaboratory are presented as guidelines only, and are based on safe handlingpractices included in U.S. EPA Method 613. The precautions for safe .handling and use are necessarily general in nature because detailed,specific recommendations can be made only for the particular exposure andcircumstances of each individual usage. Assistance In evaluating thehealth hazards of particular laboratory conditions may be obtained fromcertain consulting laboratories and from State Departments of Health or ofLabor, many of which have an Industrial health service. Although 2,3,7,8-TCOO Is extremely toxic to laboratory animals, it has been handled foryears without Injury In analytical and biological laboratories. Techniquescommonly used In handling radioactive and infectious materials are alsoapplicable to handling of 2,3,7,8-TCOO.

1.4.2.1 Protective Equipment: Throw-away plastic gloves, apron or labcoat, safety glasses and lab hood which are adequate for radio-active work.

1.4.2.2 Training: Workers must be trained In the proper method ofremoving contaminated gloves and clothing without contacting theexterior surfaces.

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1 . 4 . 2 . 3 Personal Hygiene: Thorough wash-ing of hands and forearms aftereach manipulation and before breaks (coffee, lunch and shift)with any mild soap and plenty of scrubbing action.

1 . 4 . 2 . 4 Confinement: Isolated work: area, posted with signs; segregatedglassware and tools; and plastic-backed absorbent paper onbenchtops.

1 . 4 . 2 . 5 Waste: Good technique includes minimizing contaminated waste.Plastic bag liners should be used in waste cans. Janitors shouldnot handle wastes.

1 . 4 . 2 . 6 Disposal of Wastes: 2,3,7,3-TCDO decomposes at temperaturesabove 800'C. Low level waste, such as the absorbent paper andplastic gloves, may be burned in a good incinerator. Waste con-taining high quantities (milligrams) of 2,3,7,8-TCOO should bepackaged securely and disposed through coinnercial or governmentalchannels that are capable of handling high-level or extremelytoxic wastes. Liquids should be allowed to evaporate in a goodhood and in a disposable container; residues may then be handled

, as above.

1 . 4 . 2 . 7 Glassware, Tools and Surfaces: Satisfactory cleaning may beaccomplished by rinsing with 1,1,1-trlchloroethane, then washingwith any detergent and water. Dishwater may be disposed to thesewer.

1.4.2.8 Laundry: Clothing known to be contaminated should be disposedwith the precautions described under Section 1 . 4 . 2 . 6 . Lab coatsor other clothing worn in 2,3,7,8-TCOO work may be laundered.

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Clothing should be collected In plastic bags. Persons who conveythe bags and launder the clothing should be advised of the hazardand trained 1n proper handling. The clothing may be put into a. •washer without contact if the launderer knows the problem. Thewasher should be run through a cycle before being used again for

other clothing. Disposable garments may be used to avoid a ilaundry problem, but they must be properly disposed or 2

(Nincinerated. §

1.4.2.9 Wipe Tests: A useful method to determine cleanliness of worksurfaces and tools is to wipe the surface with a piece of filterpaper, which is extracted and analyzed by gas chromatography(limit of sensitivity of approximately 0.1 ug per wipe). Lessthan 4 pg/crr2 2,3,7,8-TCDO indicates acceptable cleanliness;anything higher warrants further cleaning. More than 400 pg/on2

indicates an acute hazard that requires prompt cleaning beforefurther use of the equipment or work space and indicates that

. unacceptable work practices have been employed in the past.

1.4.2.10 Inhalation: Any procedure that may produce airborne contami-nation should be performed with good ventilation. Gross lossesto a ventilation system should not be allowed. Handling of thedilute solutions normally used in analytical and animal workpresents no inhalation hazards except in case of an accident.Finely divided soils contaminated with 2,3,7,8-TCOO are hazardousbecause of the potential for inhalation. Such samples should behandled in a confined environment, such as a hood or glove box,or laboratory personnel should wear masks fitted with a particu-late filter and charcoal sorbent.

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1.4.2.11 Accidents: Semove contaminated c lo th ing immediate ly , t ak ingprecautions not to contaminate sk in or other articles. Washexposed s k i n v igorous ly and repeatedly un t i l medical attention isobta ined.

1 . 5 APPARATUS AND MATERIALS

1 . 5 . 1 Samp ling Equipment

Grab sample bottle 1-L or 1 qt, amber glass, fitted with a screw cap linedwith Teflon. Foil may be substituted for 'Teflon if the sample is notcorrosive. If amber bottles are not available, protect samples fromlight. The bottle and cap liner must be washed, rinsed with acetone ormethylene chloride, and dried before use to minimize contamination.

Automatic sampler (optional) may also be used. However, the sampler mustincorporate glass sample containers for the coHectton of a minimum of 250mL of sample. Sample containers must be kept refrigerated at 4°C andprotected from light during compositing. If the sampler uses a peristalticpump, a minimum length of compressible silicone rubber tubing may beused. Before use, however, the compressible tubing should be thoroughlyrinsed with methanol, followed by repeated rinsings with distilled water to(Binimize the potential for contamination of the sample. An integratingflow meter is required to collect flow proportional composites.

Kote: Clearly label an samples as "POISON" and ship according to U . S .Department of Transportation regulations.

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1.5.2 Glassware

AH glassware is initially cleaned with aqueous detergent and then rinsedwith tap water, deionized water, acetone, toluene and methylene chloride.Other cleaning procedures may be used as long as acceptable method blanksare obtained. Commonly used glassware are:

• Separatory funnels, 2 L with Teflon stopcock.

Erienmeyer flasks, 250 mi

Roto Evaporators (optional)

• Concentrator tube, Kuderna-Oanish, 500 mL. Attached toconcentrator tube with springs.

Snyder column, ^uderna-Oanish three baTI macro, with ground-glassconnection to the evaporative flask.

1 mL serum vials with Teflon faced septa and aluminum caps

2 mi serum vials with Teflon faced septa and aluminum caps

1.5.3 SC/HS/H5 System

Gas chroraatograpn - an analytical system with all required accessoriesincluding syringes and analytical columns. The injection port must bedesigned for capillary columns and splitless injection. On-columninjection is also acceptable.

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Triple quadruple mass spectrometer with GC transfer line (Sci'ax 7AGA 6000E(or equivalent), Thornhill, Ontario, Canada)

Compressed Gases: Zero Grade Air (from destination,not water hydrolysis)Ultra High Purity NitrogenUltra High Purity Argon

Column: 15 m long, standard bore fusedsilica capillary ( e . g . , 0.32 imi1 . 0 . )08-5, 1.0 micron film thickness.

1.5^4 Miscellaneous

Miscellaneous laboratory equipment include:

Soiling chips - approximately 10/40 mesh. Heat to 400'C for 30minutes or Soxhiet extract with methylene chloride.

• Water bath - Heated, with concentric ring cover, capable oftemperature control ( 2 ' C ) . The bath should be used in a hood.

• SHanized glass wool• Purified Nitrogen gas• Nitrogen blowdown apparatus

Crimpers for 1 ml serum vial• Crimpers for 2 ml serum vial

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1.6 REAGENTS

1.6.1 Stock Standard Solutions

Stock standard solutions correspond to three isooctane solutions containingunlabeled 2.3,7,8-TCOO at varying concentrations, and ^C^-2,2,7,8-TCOO

- (internal standard, CASRN 80494-19-5) at a constant concentration. Thesesolutions optionally contain ^Cl 2,3^7,3-7000 (surrogate compound, CASRN85508-50-5) at varying concentrations. These stock solutions are to beused in preparing the calibration standard solutions, and are to beobtained from the Quality Assurance Division, USEPA, EnvironmentalMonitoring Systems Laboratory, Las Vegas, Nevada (EMSL-LV). If notavailable from EMSL-LV, stock standard solutions may be prepared fromcoffinercially available standards. However, the accuracy of these solutions.must be checked against EPA supplied solutions.

The three stock solutions will have the following concentrations ofunlabeled. internal and optional surrogate standards.

(Note: At the present time stock standard solutions are prepared usingisooctane. Toluene has been used in the past and may be used in thefuture. However, this should not have any significant effect on thepreparation of diluted calibration since toluene and isooctane aremiscible).

1.6.1.1 Stock Solution /I (CC1)

Unlabeled 2,3.7.8-TCDO - 0.2 ng/uL"C^-Z^^^-TCDO - 1.0 ng/uL^C^-Z^.Z^-TCOD - 0.06 ng/uL (optional)

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1 .6 .1 .2 Stock Solution f2 (CC2)

Unlabeled 2,3,7,8-TCDO - 1.0 ng/uL'^^^J^-TCDD - 1.0 ng/uL^CI^^^^.S-TCDO - 0.12 ng/uL (optional)

1 .6 .1 .3 Stock Solution 43 (CC3)

Unlabeled 2,3.7,8-TCDO - 5.0 ng/uL^C^^J^-TCDD 1.0 ng/uL^CI^^J^-TCDO 0.2 ng/uL (optional)

NOTE: Store stock solutions in 1 mi. amber mini-vials under.refrigeration.

1.6.2 Calibration Standard Solutions

Calibration standard solutions are prepared to simulate the conditions ofsample analysis as nearly as possible. Three calibration standard solu-tions are prepared from the stock standard solutions so as to containconstant amounts of internal standard (25 ng/L equivalent) with variableamounts of unlabeled standard (5, 25 and 125 ng/L) and optional surrogatestandard (1.5, 3 and 5 ng/L equivalent). The equivalent concentrations arebased on the use of 1-liter samples, and a final extract volume of 1 mL ofIsooctane as called for In the procedure.

1.6.2.1 For low level solutions, add 125 uL of stock solution fl to a 5ml. volumetric f7ask and bring to volume with Isooctane. Mixwell. This solution contains an equivalent concentration inwater of 5 ng/L of 2.3,7.8-TCDO, 25 ng/L of '^^^J^-TCDO,and optionally 1.5 ng/L of ^C^^^.S-TCDO.

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L-6.2.2 For medium level solutions, add 125 uL of stock solution f2 to a5 ml volumetric flask and bring to volume with isooctane. Mixwell. This solutions contains an equivalent concentration inwater of 25 ng/L of 2,3.7,8-TCOD, 25 ng/L of ^C^-2,2,7,8-TCDO.and optionally 3 ng/L of ^Cl^^.Z.S-TCDO.

1.6.2.3 For high level solutions, add 125 uL of stock solution /3 to a 5mL volumetric flask and bring to volume with isooctane. Mixwell. This solution contains an equivalent concentration inwater of 125 ng/L of 2,3,7.8-TCDO, 25 ng/L of ^C^-2,3,7,S-KQQ,and optionally 5 ng/L of "Cl^^.Z.S-TCDO.

Mote 1: The equivalent concentrations in water are based on anassumption of 100% extraction efficiency and concentration of theextract to 1 mL. The accuracy of the calibration does not dependon the validity of these assumptions, however. In calibration,the relative response factor is determined and an averagerelative response factor is used to determine the concentrationin samples over the entire calibration range.

Note 2: All calibration standard solutions must be stored in anisolated refrigerator and protected from light. Check thesestandard solutions frequently for signs of evaporation.

1.6.3 Sample Spiking Solution

The sample spiking solution can also be obtained from the Quality AssuranceDivision, U.S. EPA Environmental Monitoring Systems Laboratory, Las Vegas,Nevada (EMSL-LV). The spiking solution will have the followingconcentrations of internal standards.

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'^-Z.S^.S-TCDO - 2.5 ng/ul.'•^-Z^J.a-TCDF - 2.5 ng/uL (optional)

Two uL of spiking solution is used per sample. When 2 uL of this solutionis spiked in 1 liter of water, the resulting concentrations in the waterare 5.0 ng/L of each internal standard.

It is recommended that 0.5-1.0 mL of the spiking solution be transferred toa I mi serum vial and sealed with a septum and cap prior to each day's workfor use in spiking samples that day.

Note: It is very important that no evaporation of sample sp.iking solutionbe allowed to occur, since the accuracy of the results is directly de-pendent on the addition of a known amount of internal standard. Thus, thedead volume over the solution should be minimized to prevent evaporation.

1.6.4 Fortified Field STank Spiking Solution

A fortified field blank spiking solution will not be used. If native TCOOspiked samples are required, they will be prepared using commerciallyavailable native TCDO and the above sample spiking solution.

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I.g.5 MisceHaneous Reaoents

1 . 6 . 5 . 1 All solvents should be pesticide grade or equivalent. Thefollowing solvents will be needed:

Benzene AcetoneOichloromethane (Methylene Chloride) CyclohexaneToluene MethanolIsooctane

1 . 6 . 5 . 2 Silica Gel: High purity grade, 100/120 mesh silica gel win beused.

1 . 6 . 5 . 3 Acid Alumina: AG4, 100-200 mesh. Before use, activate overnightat 190'C in a foil covered glass container.

1 . 6 . 5 . 4 Reagent Water: Reagent water is defined as a water in which aninterferent is not ooserved at the Method Detection Limit (MDL)of 2.3.7,8-TCDO.

1 . 6 . 5 . 5 Celite 545: Celite 545. not acid washed, will be used. This isavailable, for example, from Fisher Scientific Co, Pittsburgh,PA.

1 . 6 . 5 . 6 Sodium Sulfate: Granular, anhydrous (ACS) sodi'.-n sulfate will beused.

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1 . 7 CALIBRATION AND LIMIT OF DETECTION DETERMINATIONS

1 . 7 : 1 Internal Standard Technique

Calibration must be done using the Internal standard technique. In thiscase, the internal standard is an isotope of the compound-of-interest, and <

i—itherefore, the technique is also referred to as isotope-dilution-mass ^spectrometry. The three calibration standard solutions described in §Section 1 . 6 . 2 are required.

Inject 1-2 uL of each of the calibration standard solutions and acquireselected reaction monitoring data for the following parent-daughtertransitions:

m/z " 320 —> 257m/z " 322 —> 259m/z « 332 —> 268

For simplicity in subsequent sections, only the daughter ions will bereferred to, since quantitation is based on daughter ion response.

Relative response factors for unlabeled 2,3,7,3-TCDO vs. the internalstandard for triplicate determinations of each of the three calibrationstandard solutions are calculated.

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Cauatlon I: Relative Response Factor for the standard (RRF ) for 2,3,7,8-TCOD

^s s (^s)/^;^)

where A^ - the sum of the area responses for the ions,m/z 257 and 259, corresponding to the un labe l edstandard. 2,3,7,8-TCDO.

A;^ " the area response of the Ion m/z 268,corresponding to the Internal standard,'•'C^.S^S-TCDO.

C * the concentration of the unlabeled standard,2,3,7.8-TCDD

C. • the concentration of the internal standard,^q^.SJ.S-TCOO.

Each of the calibration standard solutions must be analyzed in triplicate.and the variation of the RRF values at each concentration level must notexceed 10< RSO. If the three mean RRF values do not differ by more than10X, the RRF can be considered to be independent of analyte quantity forthe calibration concentration range, and the mean of the three mean RRFg(RRF^) shall be used for concentration calculations. The overall mean(RRF^) Is termed a calibration factor.

The calibration factor for the unlabeled 2,3,7,8-TCOO must be verified oneach work shift of 8 hours or less by the analysis of a low level calibra-tion standard. If the RRF for the low level calibration standard differsfrom the calibration factor by more than 10X, the entire calibration must

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- be repeated and a new calibration factor determined. The most recentlyverified calibration factor must be used -in all calculations. Thisverification Is only required for the unlabeled standards.

The theoretical ratio of the m/z 257 to 259 Ions for native 2,3,7,8-TCOO Is1.02. However, 1n practice this ratio will differ from the theoretical due ^oto the very low resolution used In both analyzing quadrupoles for this type '•""'of analysts. The ratio must therefore, be determined empirically as §follows:

Equation II; Isotopic ratio of native TCDD daughter ions

Ratio « A257^259

where A257 » Area response for ion m/z 257A259 « Area response for ion m/z 259

The mean of the ratios calculated for each of the nine calibration solu-tions is used for comparison purposes for qualitative identification of2.3.7,8-TCDO.

1.7.2 Limit of Oetection

Detection limits for each sample wm be calculated based on the maximumion current (peak height) of the internal standard and the level of randomnoise present in the native (320 —> 257) Ion current.

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Equation III: Limit of Detection (LOO)

2.5 X N,, , M.LOO - „ , ,.57 X ——s———

"IS A " - ' 2 S 7 V

Where

^257 Width of the envelope enclosing the random fluctuationIn native (320 —> 257) ion current.The internal standard peak height (332 —> 268 ion)"Single ion" relative response factor (Equation IV)The mass of internal standard '^-TCDO added to thesample.The sample volume

Equation III is used when no peak (no response greater than 2.5 X N—) isobserved on the chromatogram for the (320 —> 257} ion currents. The limitof detection is calculated as shown by the flow chart. Figure C-I-l-i.

Equation IV: Single Ion Native Relative Response Factor (RRF^)

RRF « "111 x -257 " i s rtWhereH^y « The peak height of the [2571 ionH ; , « The peak height of the (258} ionC^ « Concentration of ^C^-TCDO in the calibration check solution.C^ * Concentration of non-isotopicaUy TabeUed TCOO (native in

the calibration check solution).

Equation IV is calculated from the dally calibration check. Peak areas maybe used in place of the peak heights in Equation IV.

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Oafrmination of*ingl< ion RRF

Iram dailycalibration ch»ek

D»(«rminat)on o( IntarnalSlandard p«ak h«ight and nativ

ion (320 "> 2S7] p«ak haight. orwidth of nativ ion nois* »nvlop<

R»port rasuS as NO andcateuiaf dafction fimit

by •sing(» ion RRF' m»ihod

no

no

Report r«suAx *s NO and calcuiafd«t»ct)on (imtt as in normalcalculation of concentration

FIgur» C-I-1-1Identfflcatfon Criteria and Limit of D»(»ct!on Calculation

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1.8. QUALITY CONTROL REQUIREMENTS

The following quality control (QC) requirements are listed in the orderthat they must be run. Requirement I . S . I is to be done prior to theanalysis of any samples. Requirement 1.8.2 is to be included with eachbatch of real samples that is run in one 8-hour time period or on eachshift. Requirements 1.8.3 and 1.8.5 are to be met for each set of samplesanalyzed.

1. 8 . 1 Initial Calibration

An initial calibration must be performed using calibration standardsolutions with varied concentrations of native TCDO ( 5 , 25, and 125 ng/Lequivalent) and 25 ng/L equivalent internal standard. The criteria given inSection 1.7 must be met or the calibration must be repeated.

1.8.2 Calibration Check

A I-point calibration check using the 5 ng/L equivalent native TCOO and 25ng/L equivalent internal standard must be run once every 8 hours or onevery shift. If the RRFg values from this calibration check differ by morethan 10% from the previously determined mean RRF-, the 3-point calibrationmust be repeated.

1.8.3 Method 8 Tank

A laboratory "method blank" on pure water must be run along with each batchof 20 or fewer samples. In addition, a method blank on the 8ackgroundMatrix must be run for every sample analyzed. A method blank is performedby executing all of the specified extraction steps, using 1 liter of puredeionized water or surrogate matrix as appropriate. The method blank is

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also dosed with the internal standard. Results for the method blank mustbe calculated the same way as samples. A positive response >1.0 ng/L forthe method blank on pure water must be followed by re-injection. If stillpositive, the problem must be corrected and all associated samples re-extracted and reanalyzed.

1.8.4 Performances Evalua t ion Sample

The laboratory may be given performance evaluation (PE) samples to run witheach sample delivery group. The results from these performance evaluationsamples wi l t be evaluated. If a result is not within the acceptancecriteria set by EPA, all samples in the batch associated with that PEsample must be reanalyzed.

1.8.5 Internal Standard

Each sample must be dosed with 2 uL of the sample spiking solutioncontaining internal standard (equivalent to 5 ng/L of ^C^-TCOO).

1.8.6 Qualitative Requirements

The following qualitative requirements must be met in order to confirm thepresence of native 2,3,7,8-TCOD:

a. The retention time must equal (within 3 seconds) the retention timefor the internal standard.

b. The 257/259 ratio must be within the range 10< of the .value of theratio determined in Section 1.7 (Equation II).

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c. The ion responses at 257 and 259 must be present and maximize within ±I second of each other. The signal to mean noise ratio must be 2.5 toI or better for both daughter Ions. [Determine the noise level bymeasuring the random peak to valley signal present on either side(within 20 scans) of the 2,3,7,8-TCyO retention window. The 2,3.7.8-TCOO signal must be at least 2.5 times larger than this.i

(Ni—i0-1d. The LOO for each sample is calculated according to the flow chart, §

Figure C-I-1-1.

e. For each sample, the internal standard must be present with at least a10 to 1 signal to noise ratio based on the m/z 268 ion response.

1.9 SAMPLE COLLECTION. PRESERVATION AND HANDLING

1.9.1 Sample Collection

Srab samples must be collected in glass containers. Conventional samplingpractices (ASTM Annual Book of Standards, Part 31, 03370-76, "StandardPractices for Sampling l/atar," American Society for Testing and Materials,Philadelphia.) should be followed, except that the bottle must not be pre-rinsed with sample before collection. Composite samples should becollected in glass containers in accordance with the requirements of theprogram. Automatic sampling equipment must be as free as possible of Tygontubing and other potential sources of contamination.

1.9.2 Sample Preservation and Handling

All samples must be iced or refrigerated at 4*C and protected from lightsubsequent to spiking with TCDD in the STUDY.

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1.10 SAMPLE EXTRACTION

Caution: When using this method to analyze for 2,3,7,S-TCDO, all of thefollowing operations must be performed in a limited access laboratory withthe analyst wearing full protective coverings for all exposed skinsurfaces. See Section 1 . 4 .

Mark the water meniscus on the side of the sample bottle for laterdetermination of sample volume. Pour the entire sample into a 2-Lseparatory funnel. Alternatively, a top loader balance may be usedand the amount of sample poured out may be determined by the weightdifference.

Dilute 50 uL of internal standard spiking solution in 1 mi. ofacetone. Then Quantitatively transfer the dilute internal standard to -the sample in the separatory funnel.

Add 60 mL of methylene chloride to the sample bottle, seal, and shakefor a minimum of 30 seconds to rinse the inner surface. Transfer thesolvent to the separatory funnel and extract the sample by shaking thefunnel for 2 min with periodic venting to release excess pressure.Allow the organic layer to separate from the water phase for a minimumof 10 min. Collect the methylene chloride extract in a 250-mLErienmeyer flask.

Add a second 60-nL volume of methylene chloride to the sample bottleand repeat the extraction procedure a second time, combining theextracts in the Erienroeyer flask. Perform a third extraction in thesame manner.

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Assemble a. Kuderna-Oanish (K-0) concentrator by attaching a 10-mLconcentrator tube to a 500-mL evaporative flask. Other c&ncentrationdevices (such as a Roto evaporator) or techniques may be used in placeof the K-0 concentrator if the quality control requirements are met.

Dry the extract by passing it through a funnel containing sodiumsulfate on top of glass wool. Collect the dry extract in the K-0concentrator. Rinse the Erienmeyer flask: with three 10 mL portions ofmethylene chloride to assure quantitative transfer.

Add one or two clean boiling chips to the evaporative flask and attacha three-ball Snyder column. Prewet the Snyder column by adding about1 mL of isooctane to the top. Place the K-0 apparatus on a hot waterbath (60 to 65'C) so that the concentrator tube is partially immersedin the hot water. Adjust the vertical position of the apparatus andthe water temperature as required to complete the concentration in 15to 20 min. At the proper rate of distillation the bails of the columnwill actively chatter but the chambers win not flood with condensedsolvent.

When the apparent volume of liquid reaches 10 mL or less, add 1 mL ofisooctane to the condensed solvent. Continue distillation until nofurther volume reduction is apparent. The final condensate should beapproximately I fflL of Isooctane.

1.11 CLEANUP

The need for cleanup is indicated when a particular extract does not meetthe QC criteria for the coelution of all three monitored ions or the ratioA^/A259. Two cleanup procedures are described below.

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I .11.1 Modified Opti-on A Cleanup (Step by Steo)

1. Plug the tip of a. disposable pipet (5 3/4 Inches x 7 am 0.0) witha small amount of silanized glass wool.

2. Place approximately a 1 on layer of silica get over the glasswool.

3. Place approximately a one-half cm layer of anhydrous sodiumsulfate over the silica gel.

4. P " ; g the tip of a second disposable ptpet with a small amount ofsllanlzed glass wool.

5. Place approximately 0.5 on acidic alumina over the sllam'zedglass wool.

6. PTace approximately 0.5 on anhydrous sodium sulfate over thealumina.

7. Arrange the two columns so that the silica gel column will eluteonto the alumina column, and the alumina column drippings will becollected In a vial.

8. Rinse the two columns with 0.5 mL cyclohexane and discard theeluate. Drain until the cyclohexane reaches top of silica gel.Do not allow the columns to reach dryness.

9 . Transfer entire contents of the extract vial onto the silicacolumn, arranged as specified In step 7.

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10. When the solut ion just reaches the surface of the sodium s u l f a t alayer in the s i l i ca get column, add 0.5 nil cyclohexane.

1 1 . Repeat step 10 a second time. Allow the solution to dripcompletely after the second addition of cyclohexane.

12. Discard the silica gel column.

13. Rinse the alumina column with an additional 1 mL cyclohexane.Discard the accumulated elutes in the vial beneath the column.

14. Place a clean 2 ml serum vial under the alumina column.

15. ETute the alumina column with three successive portions of 0.5 mLeach of 15X by volume dichloromethane in cyclohexane, collectingthe eluate in the clean vial. '

1 6. With gentle heating and under a stream of nitrogen, evaporate thesolvent until the volume in the via1 is approximately 1 ml. Ifproceeding directly to GC/MS/MS analysis, solvent exchange to 1mL of isooctane at this time.

17. Seal the serum vial with a Teflon lined septum and cap. label thevial appropriately. Proceed to Option 0 cleanup or store forGC/MS/MS analysis (Section 1 . 1 2 ) .

1.11.2 Option D CTeanup fSteo by Step)

1. In advance, prepare a mixture of 3 . 6 g Carbopacx; with 16. 4 gCelite 545. Activate the mixture at 130*C for 6 hours.

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2. Plug the tip of a disposable pipet with a small amount ofsilam'zed glass wool.

3. PTace a 2 on layer of the carbopack-Celite mixture over the glasswool plug, using vacuum to pack the column.

4. Rinse the column sequentially with 2 mL toluene, 1 niL dichloro-methane-methanol-benzene (75:20:5 by volume), 1 mL cyclohexane-dichloromethane (1:1 by volume), and finally 2 mL cyclohexane.Collect the eluate 1n a vial and discard the eluate.

5. Maintaining a discard vial under the column, transfer the extractwhich has been cleaned up by the Modified Option A procedure,onto the column.

6. After the solvent has drained, rinse the column successively with2 mL cyclohexane, 1 mL cyclonexane-dichloromethane mixture (1 :1by volume) and 1 mL dichloromethane-methanol-benzene mixture(75:20:5 by volume).

7. Allow the column to drain completely and discard the accumulatedelutes. .

8. Place a clean serum v-fal under the column.

9. E7ute the dioxin from the charcoal with 2 mL toluene.

10. With gentle heating and under a stream of nitrogen, concentratethe extract to a volume of approximately 1 mL.

C-I-2723S3*e-22QS9 (2233«r2Cl t2-06-fl9) C2-KAX)

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1 1 . Seal the serum vial with a Teflon lined septum and cap. Labelappropriately.

1.12 GC/MS/MS ANALYSIS

1.12.1 Summary of Operating Conditions

1. Table C-I-1-1 summarizes the 15 m DB-5 gas chromatographiccapillary column and operating conditions. The 15 m OS-5 columnhas been used for chromatograpny which is not isomer specific (novalley is observed between the 1,2,3,4-TCOO and 2.3,7,8-TCDDisomers).

2. Standards and samples must be analyzed under identical MS/MS"conditions. Selected Reaction Monitoring (SRM) scans are used.using a scan time to give at least five points perchromatographic peak. Recommended MS/MS conditions are given inTable C-I-1-2.

1.12.2 Summary of Analysis

1.12.2.1 Verify the Calibration of the system daily as described inSection 1.7. The volume of calibration standard injectedshould be approximately the same as all sample injectionvolumes. The requirements described in Section 1.8.6,Parts b and c nwst be met for all calibration standards.

1.12.2.2 If lower detection limits are required, the 1 inL extractmay be carefully evaporated under a gentle stream ofnitrogen with the concentrator tube in a water bath atabout 40*C. Concentration is recommended for all samples

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which have required column cleanup. Conduct this operationinmediately before GC/MS/MS analysis.

1.12.2.3 The final extract should be 1 mL of isooctane or toluene.If this is not the case, solvent exchange to 1 niL of f-iisooctane at this time. g

o

1.12.2.4 Inject a 1 to 2 uL aliquot of the sample extract.

1.12.2.5 The presence of TCDO is qualitatively confirmed if thecriteria of Section 1.8.6, are achieved.

1.12.3 Quantitation

For quantitation, measure the area response of the m/z 257 and 259 peaksfor 2,3,7.8-TCOO; the m/z 268 peak for ^C^^^S-TCDO. Calculate theconcentration using the following equations:

Equation v: (Calculation of concentration of native TCDO in sample, C.)

, (y^s^ ^^-s "' RRF x Vn

where C * the concentration of native TCDO in ng/L

A » the sum of the area responses for the ions,m/z 257 and 259

A;^ « the area response for the ion m/z 268

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^•vision So. 0Oeewioer 1539''age 30 of i6

0..^ * quantity ( in nanograms) of ^C^-S.S./.S-TCDDadded to the sample before extraction

RRF^ « Relat ive response factor for 2,3,7,8-TCOOcalculated previously (Equat-ton I)

V * volume (in l i ters) of water sample (should beapproximately 1 liter).

1.12.4 Quant i ta t ive /Qual i ta t ive Dist inct ions

In eva lua t ing the results, a d is t inc t ion must be made between quan t i t a t ivemeasurement and qua l i t a t ive ident if icat ion of 2.3,7,S-TCDO. The fo l lowingsteps must be followed in the treatment of al l sample results:

1.12 .4 .1 Calculate the concentration of native 2,3,7,8-TCDO using EquationV.

1.12.4.2 Determine if all of the qualitative identification criteria aremet.

1.12.4.3 If al l quali tat ive identification criteria are met, report theconcentration found by Equation V, regardless of concentration.

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TABLE C-I-1-1

OPERATING CONDITIONS FOR DB-5 SAS CHROMATOGRAPHY COLUMN

Column

LengthI.D.Film Thickness

2.3,7,8-TCDD Retention Ti'me (approx.)Carrier gasrniftal TemperatureInltUI T^meSpHtIess TimePrograffl RateFfnal TemperatureSpHt F7owSeptum Purge F7owCaplHary Head PressureTransfer Lfne Temperature

OS-5

15 m0.32 inn1.0 micron5-6 m-in.

^150*C1.0 min.1.0 min.20*C/min.240 •C20 mL/mln.0.6 mL/mln.8 psi240*C

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InstrumentIon SourceCI Reagent GasReagent Gas FlowSource TemperatureDischarge CurrentQl Resolution

Q3 Resolution

Collision Energy (LAB)Collision GasCollision Gas Thickness

Ions Monttored:

TABLE C-I-1-2

MS/MS OPERATING CONDITIONS

Set ex TAGA 6000E

Townsend/gTow discharge CIZero grade air (H^ and He free)1 inL/mln.200 •C-i mA

3 amu at 50< peak height at m/z -320 (s1ng Fe"MS)"

3 amu at 50X peak height at m/z «320 (single MS)

55eV ((OR + GR)1 or 55eV (OR - R^)Ar400 x 10'2 [nolecules/on 2

01

320322332

21257 (natlve-TCDO)259 (natlve-TCOO)268 (Internal standard)

C-I-32t2-06-<9) C2-MAJO

^OOTIdn (;.|revision MO. oSceeaoer ;9j9^g* 33 o^ 4$

1.13 METHOD PERFORMANCE

For certain samples, the detection limit may be raised because of inter-ferences. These samples require cleanup as described in Sect-ion 1 . 1 1 .This method has been compared with the EPA-IFB GC/MS Method for 2 , 3 , 7 , 3 - (N

r'lTCOO and found to be applicable to analyses of waters where 2,3,7,8-TCDO is ^the only tetrachloro isomer known to be present. §

1.14 DATA REPORTING

Report all data in units of nanograms per liter. Use three significantfigures at concentrations above 1 ng/L and 2 significant figures atconcentrations below 1 ng/L. The data package must include the informationon the following:

Individual and mean response factor for the three-pointcalibration run in triplicate of unlabeled 2,3,7,8-TCOD.

• The daily or shift verification of the mean response factors.

• The result for the method blanks.

The percent recovery of native TCDO from the spiked sample.

• The result for the PE sample if submitted.

The data filename (to facilitate data retrieval).

The sample identification number (as assigned by the fieldsampling team).

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Analytical d'ate and time.

The area response for ions 257, 259, and 268.

The observed response ratio of ions 257/259 for the sample.enmThe calculated value for native 2.3,7,8-TCDO. (Values are to be . §- - -— . - - - - - - - - — ' ' ' ^reported only If qualitative Identification criteria are m e t . )

If no 2,3,7,8-TCDO was detected, report "not detected" or N . O .and perform the LOO calculation (Figure C-I-1-1) and report it.

The mass chromatograms for all samples and standards. Includeboth the real-time display data and reduced data showing lim'itsof integration. Include any computer response tables.

The volume of the water sample.

Documentation on the source and history of the native and labeled2,3,7,8-TCOO standards used.

A chronological list of all sample analyses.

Any other supporting documentation.

C-I-342233^£-220a9 (2233<r2Cl \2-Q6-99) CZ-MAX)

•^•-•-•••:'4'^7—-• --.;7.-t--.'y'»pe.-i-^-s---":'-'

1'- • . •*l

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k'•f.

^^W^^'-- '. "''*•?k^^>••^

.. ..•A'--S,1

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••ooenaix C-frevision No. 0OeceaoT 1989Page 35 of <6

2.0DATA VALIDATION PROCEDURE

2.1 OELIVERA8LES

An dellverables must be clearly labeled with the case number and theassociated sample/traffic number. Review the data package to assure thata11 items listed below are provided. Missing, Illegible or incorrectlylabeled items must be checked off. The contractor should immediately becontacted and requested to submit the missing or incorrect items.

2 . 1 . 1 Forms

Are the following present? Yes No

a. TCOD Data Report Formb. Initial Calibration Summaryc. Continuing Calibration Summaryd. A Chronological List of All Sample Analyses

2.1.2 GH/HS Displays

a. Significant Ion Current Profiles (SICPs) forthe Triplicate Analysis of the ThreeConcentration Calibration Solution

b. SICP for Each Shift Standardc. Plotted Concentration Calibration Curved. SICPs for Each Sample Run

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2.2 CALIBRATION

2.2.1 Initial Calibration

Initially the standard solutions containing 5, 25. and 125 ng/L ofunlabeled 2,3.7.8-TCDO and 25 ng/L of the internal standard '3 C^-2, 3, 7, 28-TCOD win be injected in triplicate. These solutions may also contain °1.5, 3, and 5 ng/L. respectively of the surrogate standard 37 C'1,-2, 3, 7,8-TCOO. The concentration of these solutions may only vary slightly fromtime to time. The calibration standards must be analyzed using the same GCconditions that are used for sample analysis.

Yes No

Scanning time must be such that there are atleast 5 scans per chromatographic peak. ____ _____

The retention time must be within 3 secondsof the retention time for the internalstandard.

The signal to noise ratio for peaks m/z257 and 259 must be 2.5.

The signal to noise ratio for peak. m/z *268 must be > 10.0.

For each concentration Tevel, calculate the relative response factors forunlabeled 2. 3, 7. 8-TCOO vs. the internal standard '3 C^-2, 3, 7, 8-TCOO.

^ x ^sRRF. « x , lss ^s x °x

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where:

A - the sum of the area for the Ions, m/z 257 and 259, correspondingto the unlabeled standard

A . « the area response of the ion m/z 26S, corresponding to theinternal standard

Q " quantity of unlabeled standard

Q. • quantity of internal standard.Yes No

The variation of the RRF at each concentrationlevel for the triplicate analysis must notexceed 10% relative standard deviations (RSD)

The variation of the three mean RRF values mustnot exceed IDS RSO.

The mean of the 3-mean RRF- (RRF } for the internalstandard established in the initialcalibration must be used for concentrationcalculations.

Action: 1) If the required initial calibrationdata were not supplied, notify thelaboratory. If they are un-available, red-line (reject) alldata; 2) If any of the calibrationcurve standards fail to meet the

C-T-3712-06-M) C2-MAX)

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above acceptance criteria, red-lineaH data associated with the calibrationcurve.

2.2.2 Isotopic Ratio Calibrations oo-——————————————————— m

Owing to the Tow resolution of the quadrapoles used in this type ofanalysis, the ratio of area response for m/z 257 to 259 ions for theunlabeled 2, 3, 7, 8-TCOO must initially be determined empirically.

A"7Ratio « —

A

where:

A257 « Area response for m/z « 257

A259 - Area response for m/z » 259

Calculate the mean of these ratios for the nine analyses (triplicateanalyses on three standard solutions).

Yes NoIs the range of the values for the ratiosless than ±10% of the mean value? __

2.2.3 Calibration Checi; Standard

A 1-point calibration check using the 5 ng/L equivalent native TCOD and25 ng/L equivalent internal standard must be run once every 8 hours or onevery shift, whichever is more frequent.

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^soendi'x c-i^•vision No. 03ecwioer ;989^age 39 of 46

Yes ^o

The scanning time must be such that thereare at least five scans per chromato-graphic peak. ____ __

The retention time for 2,3,7,8-TCDO must bewithin three seconds of the retention timefor the Internal standard. ____ ____

The signal to noise ratio for peaks m/z 257and 259 must be ^ 2.5. ____ ____

The signal to noise ratio for peak m/2 268must be ^ 10.0.

Check the calculation for the response factor for 2,3,7.8-TCDO vs. thelnterna-1 standard '^-Z.aJ.S-TCDO.

Are there any errors? ____ ____

The response factor of 2,3,7,8-TCOO relativeto '^-Z^J.S-TCDO must be within tl0< ofthe mean value for the initial 3-po1ntcalibration curve.

Action: 1) If the required number of analysesof calibration check solutions werenot submitted notify the laboratory.If they are unavailable, reject all

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A o o e n f l i x C-iSevision NO. 0Oecfnaep 1939Psgt 40 of 46

data without an associated calibrationcheck standard; and 2) if the calibra-tion check standard fails to meet theacceptance en ten a, reject all of thedata associated with this standard.

2.3 SAMPLE DATA

2.3.1 Qualitative RequirementsYes

The Retention Time (R T ) of 2,3,7,8-TCDO mustbe within three seconds of the RT of the^C^-2,3,7,8-TCDQ.

The signal to noise ratio for peaks m/z 257and 259 must be 2.5.

The signal to noise ratio for peak m/z 268must be 10.0.

Action: 1) If the 2,3,7.8-TCOO qualitativecriteria were not met, 2,3,7,8-TCOOwas not qualitatively identified,red-line positive value; 2) if thesignal to noise criteria for ionsm/z 257, 259, 268 were not met, red-linepositive or NO dioxin values

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2 . 2 . 2 Quantitative Requirements

Recalculate the concentration of 2,3,7,8-TCDO which was found in the sampleusing the equation:, (VA^) x ((^)"S s RRF x V———n

where:

C^ « the concentration of native TCDO In ng/L, ng/kg or ng/cro2 insample

A^ - the sum of the area responses for the ions, m/z 257 and 259

A ; ^ « the area response for m/z 268

Q;^ " quantity (In nanograms) of "C^-^^/.S-TCuO added to thesample before extraction

RRF^ « Overall mean relative response factor for 2,3,7,8-TCDDcalculated previously

V • volume of the sample ( i n liters) for liquids, weight in kg forsolids, or area in on2 for wipes

Calculate the EMPC - when no unTabeled dioxin is detected.calculate the EMPC which is the concentration required toproduce a signal with an area 2.5 times the background signalarea. The EMPC is calculated using the following formula:

EMPC «2.5 x A^ x Q^

^52 x ^n v

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••ooenaix c-(^evi'si'on n<s, QOceereser '989Page 43 of AS

where:

EPMC = estimated maximum concentration in ug/L.

A^ a the sura of the area or height responses for the ions, m/z 257and 259 ^

rr—<sA;^ « the area or height response for ion m/z 268 °

Q. « quantity of internal standard ( in ng) added to the samplebefore extraction

RRF " Overall mean re la t ive response factor for 2,3,7,8-TCDOcalculated previously

V * volume ( in liters) of water sample, weight in Kg or area in era2

Action: If the calculated amount ofunlabeled dioxin is outsidethe linear range determined on theinitial calibration, red-line the data.

C-I-42223W-22Q89 <2233*'-2C1 12-06-89) C2-MAX)

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2.4 QUALITY CONTROL

2.4.1 Method Blanks

Was a laboratory "method blank'1 run onpure water with each batch of 20 or fewersamples or each sample extraction group?

Was a method blank on the Background.Matrixrun for each sample analyzed?

Action: If the proper number of method blankswas not run, contact the laboratoryfor corrective action.

Check the calculation of the equivalentconcentration of native TCDO in themethod blanks.

Is this concentration greater than 1.0 ng/Lfor pure water?

If so, was a second method blankanalyzed?

Is the equivalent concentration of nativeTDCC in this method blank greater than1.0 ng/L for water?

Action; If the equivalent concentration ofnative TCOO in the first method blank

C-I-4322334E-220M (2233<r2Cl 12-06-W C2-MAX)

Yes No

lBB«"a'x C-l

revision NO. 0OecMieer '•9S9P»ge A4 ot 46

is greater than 1.0 ng/L and a secondmethod blank w&s not analyzed, red-line(reject) all positive resuKs associatedwith this blank. 2) If the equivalentconcentration of native-TCDO in both method

^fblanks is greater than 1.0 ng/L, red-line all ^positive associated results. S

c?

2.4.2 Performance Evaluation SamoleYes No

Was a performance evaluation sample analyzed?

If "yes 1*, do the analytical results fallwithin the 99X EMS-LV confidence limitacceptance criteria?

Action: 1) The PE raw data must be reviewed asif it were an environmental sample;2) If 2,3,7,8-TCOO was not qualita-tively identified, reject all associateddata; 3) If the reported value for thePE sample exceeds the upper acceptanceMalts, reject all positive values inthe entire associated batch of samples,but not the NO values; and 4) If thereported value exceeds the Toweracceptance limits, an positive and notdetected values are rejected.

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2.5 HOLDING TIMES

*OBengi» C-l

revision No. 0O^Cfnoer 1989''sg* <5 of 45

Yes NO

Have Any holding times been exceeded for aqueous samples?

a) Ten days to extraction from verified time ofspiking for the PQL study. ____ _

b) 40 days after extraction for analysis.

Action: If these holding times are exceeded,red-line the value on the datasheet (including detection limits)indicating rejection.

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Aoo»ndix C-l

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2.6 CONCLUSIONS

(Hots: Reviewers must red-Una unacceptable data on sample data sheets;red-line data do not fmply the compound is not present).

'so•

Casef__________ Lab___________ S i t e _ _ _ _ _ _ _ _ §

Data AssessmentNarrative ___.______________________________

ContractProbTeni/Nonconipl fance_

Rev-fewer's Signature;

Verified By:_____

Date,

Date

C-I-462233<E-220M (2223<r2Cl 12-06-C9) C2-MAX)

APPENDIX II

Data Sheets

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APPENDIX III

Sample Locations by Compass Direction

Location

Sample ^

JK-LC1-01JK-LC1-02JK-LC1-03JK-LC1-04JK-LC1-05JK-LC1-06JK-LC1-07JK-LC1-08JK-LC1-09JK-LC1-10JK-LC1-11JK-LC1-12JK-LC1-13JK-LC1-14JK-LC1-15JK-LC1-16JK-LC1-17JK-LC:1-18JK-LC1-19JK-LC1-20

JK-LC1-SB-01JK-LC1-SB-02JK-LC1-SB-03JK-LC1-SB-04JK-LC1-SB-05

JK-LC2-01JK-LC2-02JK-LC2-03JK-LC2-04JK-LC2-05

JK-LC2-SB-01JK-LC2-SB-02

JK-LC3-01JK-LC3-02JK-LC3-03JK-LC3-04JK-LC3-05JK-LC3-06JK-LC3-07JK-LC3-08

Az imuth(degrees)

2700

90ISO270

090

18090

180270

90180315

45225

67135255281

070

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0

148326

084

271

32684

090

180270

090

180270

Distance(feet)

5555555545454545403540352530353040204340

15251633

0

3.53.58.5

1010

3.510

5020505040154040

Depth(inches)

55555555555555555555

1818181818

55555

1818

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III-1

Location

Sample ^

JK-LC3-09JK-LC3-10JK-LC3-11JK-LC3-12JK-LC3-13JK-LC3-14JK-LC3-15JK-LC3-16JK-LC3-17JK-LC3-18JK-LC3-19JK-LC3-21JK-LC3-22JK-LC3-23JK-LC3-24JK-LC3-25

JK-LC3-SB-01JK-LC3-SB-0 2JK-LC3-SB-0 3JK-LC3-SB-04JK-LC3-SB-0 5

JK-LC4-01JK-LC4-02JK-LC4-03JK-LC4-05JK-LC4-06JK-LC4-07JK-LC4-08JK-LC4-09JK-LC4-10JK-LC4-11JK-LC4-12JK-LC4-13JK-LC4-14JK-LC4-15JK-LC4-16JK-LC4-17JK-LC4-18JK-LC4-19JK-LC4-20

Azimuth(degrees)

27045

135225315332

22165204165157

2245

135123

35

90180270

00

090

1800

90180270

090

18013

0315

45225248278251

45

Distance(feet)

20204025304040414058505034182745

7223015

0

75100

6355805065355041502540427041466547

Depth(inches)

5555555555555555

1818181818

5555555555555555555

M00

(N00

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III-2

AzimuthSample ^ (degrees)

LocationDistance(feet)

Depth(inches)

JK-LC4-SB-01 90JK-LC4-SB-02 180JK-LC4-SB-03 270JK-LC4-SB-04 0JK-LC4-SB-05 0

20223015

0

1818181818

III-3