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04UNITED STATES ENVIRONMENTAL PROTECTION AGENCYOFFICE OF LEGAL AND ENFORCEMENT COUNSEL

EPA-330/2-82-001

I SUMMARY OF PINE RIVER RESERVOIRSEDIMENT SAMPLING SURVEYSt. Louis, MichiganNovember 20-22, 1981

April 1982

Russell Forba

NATIONAL ENFORCEMENT INVESTIGATIONS CENTERDenver, Colorado

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CONTENTS

INTRODUCTION ............................. 1

CONCLUSIONS ............................. 1

METHODS ............................... 3

SURVEY FINDINGS ........................... 8PHYSICAL OBSERVATIONS ....................... 8ANALYTICAL RESULTS ......................... 8

Tables

1 Sediment Sampling Locations ................... 42 Sediment Core Descriptions ................... 63 Total DDT, HBB, and PBB Concentrations In Sediments By Basin . . 104 Total DDT, HBB, and PBB Concentrations In Sediments By Depths . . 15

Figures

I 1 Sediment Sampling Locations ................... 22 Total DDT Contamination ..................... 11

§ 3 HBB Contamination ........................ 124 PBB Contamination . . . . . . . . . . . . . . . . . . . . . . . . 13

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APPENDICES

A TOTAL DDT, HBB, AND PBB LOADING APPROXIMATIONSB COMPLETE ANALYTICAL DATA AND METHODS AND ASSOCIATED QUALITY

CONTROL DATA

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INTRODUCTION

In June 1980* NEIC collected water and sediment samples from the PineRiver to document the contamination contributed to the Pine River by pre-vious operations of the Velsicol Chemical Corporation (VCC) at its St. Lou-is, Michigan facility.

At the request of Region 5, Enforcement Division, additional sedimentsampling was conducted November 20 to 22, 1981 to supplement the June 1980sampling and to more adequately define the areal and vertical distributionof total DOT, HBB, and PBB in the Pine River Reservoir. This new informa-tion was needed to support settlement negotiations between the regulatoryagencies and VCC.

CONCLUSIONS

The NEIC sediment sampling data showed widespread contamination of thePine River Reservoir by DOT, hexabromobenzene (HBB), and polybrominatedbiphenyl (PBB). An estimated 56,000 Ib DOT, 10,000 Ib HBB, and 800 Ib PBBare contained in the Pine River Reservoir sediments.

The highest levels of contaminants were found in the middle basin (sam-pling Stations 04 to 18) of the reservoir located between the VCC PlantSite Jetty and the Mill Street Bridge [Figure 1]. Within this basin, thehighest concentration of contaminants was found near the VCC plant siteboundary, offshore from the former discharge points for the VCC organicsproduction area. The maximum concentrations of total DOT, HBB, and PBBfound in the segments of cores were 26,000 ug/g, 9,300 ug/g, and 330 ug/g,respectively. The lower basin (sampling Stations 19 to 23), located between

EPA-330/2-8-031 - Pine River Contamination Survey, St. Louis, Michigan -October 1980,EPA-330/2-8-030 - Investigation for Hazardous Waste Contamination, Velsi-col Chemical Corporation Plant Site, St. Louis, Michigan - October 1980.

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FIGURE 1SEDIMENT SAMPLING LOCATIONS

PINE RIVER RESERVOIRSt. Louis, Michigan

November 20-22, 1981

Sampling Location

ST. LOUISMUNICIPAL DAM

VEISICOLCHEMICALCOMPANY

PLANTSITE

tIII

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the Mill Street Bridge and the St. Louis Dam, was found to be contaminated,but to a lesser degree than the middle basin. Maximum concentrations oftotal DOT, HBB, and PBB found in this area were 560 ug/g, 180 ug/g, and5.2 ug/g, respectively. In the upper basin (sampling Stations 01, 02, and03), located upstream of the VCC plant site jetty, the contaminant levelswere lower with maximum total DOT, HBB, and PBB concentrations of 25 ug/g,3.2 ug/g, and 2.8 ug/g, respectively.

Regardless of the areal distribution of the contaminants, the highestDOT levels were found in the deeper portions of the sediment cores withlower concentrations in the top 4 inches. High levels of DOT are also foundin surface sediments (4,000 ug/g at Station 14) in areas of the reservoirwhere scouring had apparently exposed the older sediments. The highestlevels of HBB and PBB were found in the top (0 to 16 in.) of the cores.Logically, the HBB and PBB should be more prevalent in the surface sedi-ments, and DDT should be prevalent in the deeper sediments because HBB andPBB were produced until the mid-1970s, while DDT production ceased in 1959.

METHODS

Sediment cores were collected and water and sediment depths measuredat 23 sampling locations [Figure 1, Table 1]. The sediment depths weremeasured by penetrating the reservoir bottom with a % in. diameter steelrod until resistance was met. Water depth was obtained by dropping a disc(approximately 16 in. diameter) into the reservoir bottom and measuring thesubmerged portion of the attached cord.

The sediment samples were collected in 1-3/4 in; I.D. hexane-rinsedaluminum or galvanized steel core tubes. To facilitate sampling and han-dling, core tubes of 3, 4, or 6 ft in length were used. The samples werecollected by slowly pushing or driving the core tubes into the sediment un-til a sediment layer, which was compacted hard enough to plug the end of thecore tube, was reached. Care was taken to allow several inches of water to

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Table 1SEDIMENT SAMPLING LOCATIONS

PINE RIVER RESERVOIRST. LOUIS, MICHIGANNovember 20-22, 1981

CoreSampling

01

02

03

04

05

06

07

08

09

10

11

12

13

14

15

16

17

18

18-dup

19

20

21

21 dup

22

23

SamplingDate & Time

(ft)

11/20/811315 hrs

11/20/811340 hrs11/20/811420 hrs11/20/811530 hrs

11/20/811545 hrs11/20/811600 hrs11/21/81 •1125 hrs

11/21/811140 hrs11/21/811200 hrs11/21/811215 hrs11/21/811230 hrs

11/21/811245 hrs11/21/811300 hrs11/21/811335 hrs11/21/811430 hrs

11/21/811445 hrs11/21/811500 hrs11/21/811520 hrs11/21/811520 hrs11/22/810930 hrs11/22/810945 hrs11/22/811000 hrs11/22/811000 hrs11/22/811015 hrs11/22/811020 hrs

Depth ofWater(ft)

8

2

4

1

1.5

5

4 '

3

3

3

5.5

5

4

4

7

5

5

7

7

8

8

7

7

8

8

Depth ofSediment(ft)

1.5

1.5

9

8

9

9

6

3

4.5

7

4

8

8

2

7

8

8

3

3

2

2

4

4

6

3

Core TubeLength

3

3

. 4

4

6

6

4

3

4

6

4

6

6

4

6

6

6

4

4

3

3

3

3

3

3

Station Description

SO feet from the shoreline adjacent to theVelslcol Chemical Corporation (VCC) plantsite, 2100 feet upstream of the VCC Jetty.Same as above (01) except 900 feet upstreamof the VCC jetty.Same as above (01) except 300 feet upstreamof the VCC jetty.50 feet from the shoreline adjacent to theVCC plant site on the north-south transectlocated 1200 feet west of the Mill StreetBridge.Same as above (04) except 150 feet from theVCC shoreline.Same as above (04) except 300 feet from theVCC shoreline.50 feet from the shoreline adjacent to theVCC plant site on the north- south transectlocated 900 feet west of the Mill StreetBridge.Same as above (07) except 150 feet from theVCC shoreline.Same as above (07) except 300 feet from theVCC shoreline.Same as above (07) except 500 feet from theVCC shoreline50 feet from the shoreline adjacent to theVCC plant site on the north-south transectlocated 600 feet west of the Mill StreetBridge.Same as above (11) except 150 feet from theVCC shoreline.Same as above (11) except 300 feet from theVCC shoreline.Same as above (11) except 500 feet from theVCC shoreline.50 feet from the shoreline adjacent to theVCC plant site on the north-south transectlocated 300 feet west of the Mill StreetBridge.Same as above (15) except 150 feet from theVCC shoreline.Same as above (15) except 300 feet from theVCC shoreline.Same as above (15) except 500 feet from theVCC shoreline.Same as above (18)

150 feet east of the midpoint of the MillStreet Bridge.300 feet east of the midpoint of the MillStreet Bridge.450 feet east of the midpoint of the MillStreet Bridge.Same as above (21)

150 feet north of Station 20.

150 feet north of the midpoint of the Cityof St. Louis municipal dam.

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remain in the top of the core tubes to ensure that there was minimal dis-turbance of the surface sediment. The filled tubes were extracted from thebottom, the ends were sealed with aluminum foil, and then they were cappedand frozen in an upright position.

After freezing, the 4 and 6 ft core tubes were cut in half, the openends covered with aluminum foil, and stored in dry ice. At the NEIC labor-atory, the frozen samples were extruded from the core tubes by warming the

* outside of the tubes with water and pushing the frozen cores from the tubes.After extrusion, each frozen core was observed and the physical characteris-tics recorded [Table 2]. The top 4 inches of each sediment sample was sep-arated from the core and the remainder divided, from top to bottom, in 1 ftintervals or fractions of a foot, as applicable. All segments of each sedi-ment core were wrapped in aluminum foil. These segments were subsequentlythawed, thoroughly mixed, and analyzed for PBB, total DOT, and HBB. Com-plete analytical methodology is shown in Attachment A. NEIC chain-of-custodyand document control procedures were followed throughout the survey.

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Table 2SEDIMENT CORE DESCRIPTIONS

PINE RIVER RESERVOIRSt. Louis, MichiganNovember 20-22. 1981

StationNumber

01

02

03

04

05

06

07

08

09

10

11

12

13

14

15

ExtrusionDate and TiMe

12/1/811200 hrs

11/30/811400 hrs

12/1/810955 hrs

11/30/811425 hrs

11/30/811335 hrs

11/30/811440 hrs

11/30/811450 hrs

11/30/811325 hrs

11/30/811315 hrs

11/30/811500 hrs

11/30/811310 hrs

11/30/811520 hrs

11/30/811300 hrs

12/1/810830 hrs

12/1/810915 hrs

TotalLength(In.)

13

17

24

13

40

32

36

28

34

24

16

30

46

28

46

CoreSegment

0-3

3-1010-13

0-48-1414-17

0-66-1010-24

0-99-13

0-4

4-1313-1515-40

0-4

4-1313-32

0-66-2020-36

0-4

4-28

0-34

0-8

8-1414-24

0-4

4-16

0-3

3-30

0-6

6-46

0-4

4-88-28

0-22-46

Visual Description*

gray-brown flock grading Intogray-brown silt

gray-brown siltgray-black sludge

brown sandy siltwhite silt (MgOx)black sludge

black sludgegray-white silt (MgO,)white silt (Mg02)

dark gray-brown sandy siltblack silt

brown-gray floe grading Intogray-brown silt

gray-black sludgewhite silt (Mg02)gray-black sludge

gray-brown floe grading intogray-brown sandy silt

gray sandy siltgray-white silt

brown floeblack silty sandgray-black sandy silt

brown-gray floe grading Intobrown-gray silt

gray-black silt

gray-black silt

gray sand with streaks ofwhite silt (MgO)

gray sandblack sandy silt

gray-brown floe grading Intogray-black silt

gray-black silt

gray-brown floe grading Intogray-black silt

gray-black silt

gray-brown floe grading Intosilty gray-black

gray-black silt

gray-brown floe grading intogray-black silty sand

b^ack silty sandgray-brown coarse sand

black floedark black sludge

II1 Station|_ Number

I "17I

18

K*" 18-dup

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I .•. 20

I -

I21 dup

. s

1 ^ 22

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Table 2 (Cont.)SEDIMENT CORE DESCRIPTIONS

PINE RIVER RESERVOIRSt. Louis. MichiganNovember 20-22. 1981

ExtrusionDate and TIM

11/30/811250 nrs

12/1/810935 hrs

11/30/811220 hrs

11/30/811240 hrs

12/1/811015 hrs

11/30/811345 hrs

12/1/811035 hrs

12/1/811135 hrs

12/1/811145 hrs

12/1/811200 hrs

TotalLength

42

45

35

34

22

27

21

14

23

34

CoreSegment(in.)

0-1212-42

0-44-99-4040-45

0-11

11-35

0-11

11-34

0-3

3-1818-22

0-55-1919-27

0-5

5-1313-21

0-4

4-14

0-6

6-1818-23

0-33-2828-34

Visual Description*

gray-brown siltblack sludge

brown floeblack and gray-white silt layersblack siltbrown-gray clay

gray-brown floe gradingfine gray-brown silt

black silt

gray-brown floe gradingfine gray brown silt

black silt

brown-gray floe gradingblack silt

black sludgefine gray-brown silt

gray-black tiltblack sludgelight brown clay

brown-gray floe gradingblack silt

black siltgray-black silt

brown- gray floe gradingInto black silt

black silt

brown-gray floe gradinginto black silt

black siltgray-black silt

gray-brown floeblack siltgray- brown silty sand

into

into

into

into

* Descriptions are from visualcore tubes.

observations of the outside of the frozen cores after extrusion from the

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SURVEY FINDINGS

PHYSICAL OBSERVATIONS

Total sediment depth at the sampling Stations varied between 1.5 and9 ft [Table 1]. The deepest sediments (8 to 9 ft) were found in the ex-treme upper end (Stations 04, 05, and 06) and lower end (Stations 12, 13,16, and 17) of the middle basin.

After extrusion of the sediment cores, the physical characteristics ofthe sediment cores were observed and recorded [Table 2]. Many of the cores(78%) contained a surface layer (1 to 6 inches) of gray-brown floe (lightsilty filamentous material). Nearly all the cores contained layers of vary-ing thickness of black or gray-black sludge. A sulfurous odor was noticedin the cores which contained this black sludge. The strongest odors werefrom samples collected at Stations 07, 08, 15, 19, 20, and 23. Many ofthe cores contained layers of white sludge which, according to Company of-ficials, is probably magnesium oxide (MgO). Both the black and white lay-ers had a very small grain size, usually indiscernible to the naked eye.

The black and white layers of materials seen in the cores varied inthickness and depth; hence, no visual correlation of the layers betweensampling stations could be made. These varying depths and thicknesses ofsediment layers and the differences in total sediment depths at the sam-pling stations showed the expected variability in deposition rates withinthe reservoir.

ANALYTICAL RESULTS

Approximately 56,000 Ibs DOT, 10,000 Ibs HBB, and 800 Ibs PBB are con-tained in the Pine River sediments. Less than 5% of the DOT is found inthe top 4 in. of sediment, but over 13% of the HBB and 57% of the PBB wasfound in the top 4 in. of the cores. These loadings were calculated by

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Integrating sediment density, contaminant concentration by depth, and theareas assigned to each of the sampling Stations [Appendix A].

The highest concentrations of total DOT, HBB, and PBB [Table 3] werefound in the middle basin of the Pine River Reservoir (Stations 04-18) whichextends from the VCC plant site jetty to the Mill Street Bridge [Figure 1].Average maximum total DOT, HBB, and PBB concentrations* In the samples col-lected in this basin were 3,500 ug/g, 1,000 ug/g, and 42 ug/g, respective-ly. Wastewater from the former VCC organics production area was dischargedto this portion of the basin. Within this basin, the highest total DOT

I (_ concentrations were found at Stations 07 (26,000 ug/g) and 08 (8,800 ug/g).The highest concentrations of HBB were also found at Station 07 (9,300 ug/g)

f and 08 (2,600 ug/g). Highest PBB concentrations were found at Station 04L (330 ug/g), 10 (66 ug/g), 07 (64 ug/g), and 08 (58 ug/g). Stations 07 and

1 08 are the Stations nearest to the former organics wastewater discharges,and they are close to the location where the highest total DOT concentra-tion (44,000 ug/g) was found during the June 1980 NEIC survey.** Contami-

I nant concentrations within the middle basin generally decreased [Figures 2,3, and 4] toward the northern shore. The old river channel is located along

I this shoreline.

Compared to the middle basin, the average concentrations of contami-nants in the upper basin are low. Average maximum core concentrations oftotal DOT, HBB, and PBB of 11 ug/g, 1.8 M9/9, and 1.5 ug/g, respectively,were found in this portion of the reservoir which extends from the Washing-ton Street Bridge to the VCC plant site jetty (Stations 01, 02, and 03).

The lower basin (Stations 19 to 23) of the reservoir between the MillStreet Bridge and the St. Louis Municipal Dam was found to be contaminated;however, contaminant concentrations were lower than the levels found in themiddle basin. Average maximum core concentrations of total ODT, HBB, andPBB found in this area were 310 ug/g, 81 ug/g, and 4.2 ug/g, respectively.

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* The average maximum concentrations were calculated by averaging the con-centrations of the most contaminated segment of each core.

** EPA-330/2-80-031 - Pine River Contamination Survey, St. Louis, Michigan- October 198O.

Table 3TOTAL DOT, HBB, AND PBB CONCENTRATIONS

IN SEDIMENTS BY BASINPINE RIVER RESERVOIRSt. Louis, MichiganNovember 20-22, 1981

SampleBasin Size

Stations

UPPER 3Stations01-03

MIDDLE 15Stations04-18

LOWER 5Stations19-23

Total DDTAvg.- Maximum MaximumConcentration Concentration

Mg/g Mg/g11 25

3500 26,000

300 560

HBBAvg.- Maximum MaximumConcentration Concentration

Mg/g Mg/g1.8 3.2

1000 9300

81 180

Avg.- MaximumConcentration

pg/g1.5

42

4.2

PBBMaximum

ConcentrationMg/g2.8

330

5.2

This average maximum concentration was calculated by averaging the concentrationsof the most contaminated segment of each core.

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FIGURE 2TOTAL DOT CONTAMINATIONPINE RIVER RESERVOIRSt. Louis, Michigan

November 20-22, 1981

Total DOT Concentration*

> 600 pg/g

60-600 yg/g •

_J < 60 yg/g

ST. LOUISMUNICIPAL DAM

VELSICOLCHEMICALCOMPANY --

PLANT iSITE

Based on maximum concentrations found in individual sediment cores

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FIGURE 3HBB CONTAMINATION

PINE RIVER RESERVOIRSt. Louis, Michigan

November 20-22, 1981

Sampling Location

S^Jl £!/)

<

Of

OD

HBB Concentration*_^_««i

f j

\SN

rSf.

> 100 yg/g10-100 yg/g

< 10 yg/g

PROSPECT AVENUE

¥ . LOUISMUNICIPAL DAM

VELSICOLCHEMICALCOMPANY

PLANTSITE

ro* Based on maximum concentrations found in individual sefH«"ent cores

4 -••".,.-•«». -

•tatfl •*

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FIGURE 4PBB CONTAMINATION

PINE RIVER RESERVOIRSt. Louis, MichiganNovember 20-22, 1981

PBB Concentration*

> 15 pg/g

3-15 yg/g

< 3 yg/g

. LOUISMUNICIPAL DAM

VELSICOLCHEMICALCOMPANY -•

PLANT ISITE

CA>

* Based on maximum concentrations found in individual sediment cores

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14

A concentration profile by depth [Table 4] was developed by summarizingthe data from each of 5 specified depths (0 to 4 in., 4 to 16 in., 16 to28 in., 28 to 40 in., and 40 in. and below) from the 20 sampling Stationsin the middle and lower basins (Stations 04 to 23)." This profile showedthe highest average total ODT concentrations were found to be in the deepersediment layers (16 to 28 in. and 28 to 40 in. layers). An average totalDOT concentration of 960 ug/g was found in the 16 to 28 in. segments of thesediment cores, and 1,000 ug/g was found in the 18 to 40 in. segments.

Conversely, lower concentrations of total DOT were generally found inthe surface portion (0 to 4 in.) of the sediment cores. One station (14),however, had a surface sediment total DOT concentration of 4,000 ug/g.This high concentration Is probably due to the deposition and erosion pat-terns in the reservoir. Station 14 is located at the edge of the main riverchannel which runs along the north side of the reservoir. The velocity ofthe currents would be expected to be higher in this area of the reservoirduring high flow periods, increasing scouring and exposing the older anddeeper layers of sediment which contain higher total DOT levels. The ana-lyses of the three cores which were greater than 40 in. in length showedvery low concentrations of contaminants below the 40 in. level.

Maximum HBB and PBB concentrations were generally found to be in theupper sediments (0 to 16 in.). A maximum HBB concentration of 9,300 ug/gwas found in the 4 to 16 in. layer at Station 07, and a maximum PBB concen-tration of 330 ug/g was found in the 0 to 4 in. layer at Station 04.

Complete analytical data for all the sediment samples, as well as theanalytical methods and associated quality control data, can be seen inAppendix B.

Sediment cores were divided into two to five segments depending on eachcore's length.

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Table 4TOTAL DOT, HBB, AND PBB CONCENTRATIONS1

IN SEDIMENTS BY BASINPINE RIVER RESERVOIRSt. Louis, MichiganNovember 20-22, 1981

Total DOT HBB PBBCore Seg. Sample Avg. 2-MaximumMaximum Avg. 2-MaximumMaximum Avg. 2-MaximumMaximumDepth Size Concentration Concentration Concentration Concentration Concentration Concentration(in.) Stations ug/g ug/g ug/g ug/g ug/g ug/g

0-4 194-16 1916-28 1728-40 93

40-46 3

3415995710143.3

4,0002,90026,0004,8009.5

612555.80.130

2,6009,300100440

8.67.4000

33066100

1 Dry weight concentrations2 This average was derived by ccimparing the mean concentration of the entire set (Stations 04-23) at the

various depths with individual values, dismissing values which were more than 2 standard deviations fromthe mean, and calculating a new average with the remaining values. This average 1s not the true averagebut an expected average with depth. The high values dismissed are valid concentrations although not typ-ical for the majority of the cores.A sample size of 8 was used to derive the average concentrations for HBB.

PrLfe-...u

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APPENDIX A

TOTAL DOT, HBB, AND PBB LOADING APPROXIMATIONS

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TOTAL DOT, HBB, AND PBB LOADING APPROXIMATIONS*PINE RIVER RESERVOIRSt. Louis, Michigan

A-l

SampleNumber*

01-101-202-102-203-103-203-304-104-205-105-205-305-406-106-206-306-407-107-207-307-408-108-208-309-109-209-309-410-110-210-311-111-212-112-212-313-113-213-313-413-514-114-214-315-115-215-315-4

% H20

54.363.955.448.264.964.151.834.845.263.265.368.161.657.143.760.551.972.071.561.363.470.370.863.265.668.359.662.468.064.156.368.565.668.763.555.967.167.767.462.255.266.513.515.171.968.967.158.8

SedimentDensitylbs/ft3

80.681.087.393.680.182.990.2107.296.581.379.978.182.485.898.883.390.275.876.082.781.276.776.581.379.878.084.081.878.280.786.677.979.877.881.286.978.778.378.582.087.479.1140.0137.075.877.778.784.5

Areaft3

„-

185,760n216,000n

n54,000ii36,000n

iiii

54,000nnn

18,000nnn

50,400nn

54,000nnn

57,600nn

25,200ii32,400n

n61,200n

nnii

64,000nn

12,960niiii

Total DOTLoadingIbs

—-

12.163.03.441252353403435.0324.0888-1.7110.513.9-12.7148

149802.5113.832651494016.38011439.132.7975117.03.522.83.9415.4-7.9224.8345910518

2289243-1.936.5818041940

HBBLoadingIbs

m _

-2.419.911.94--18.925733.06.19--7.9584.11.63--362657.60.539942027-69.232--26.473430.520.042223.7163-23.277443.9--3.26--7.3620718

19.9

PBBLoadingIbs

^

-2.416.841.70--41565.70.34---1.461.68--1.7825.0--22.2--8.9024--6.73110-1.014.51.317.68-2.2238.71.57--1.55--0.375.01--

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A-2

TOTAL DOT, HBB, AND PBB LOADING APPROXIMATIONS* (Cont)PINE RIVER RESERVOIRSt. Louis, Michigan

SampleNumber*

15-516-116-216-316-417-117-217-317-417-518-118-218-318-4 dup.18-2 dup.18-3 dup.19-119-219-320-120-220-321-121-221-321-1 dup.21-2 dup.22-122-222-323-123-223-323-4

Total0 to 4 in.4 to 16 in.16 to 18 in28 to 40 in40 in. and

* Based on** Tho fi»*c

% H20

56.364.164.567.155.064.268.063.757.336.864.031.361.666.330.256.956.570.534.861.868.618.466.669.451.967.970.070.372.364.966.667.667.146.6

.

.

over

NEIC data•f tun rli n-i H

SedimentDensitylbs/ft3

86.580.780.578.787.580.678.281.185.710580.7111.782.479.211386.086.476.6107.282.377.8131.079.177.490.178.276.976.775.780.179.178.478.795.1

from samplestc r>ofaY* tn tf

Total DOT HBBAreaft3

„58,464n

nn

64,800"nnn

102,600nn

102,000iiii

43,200"n

37,440nn

48,960n"

48,960n90,514"n

50,914"nn

LoadingIbs

.1221.550.181.725.314.39.24496.78-20.92.8339012.831.65325.9585.9-0.515124.44.05232-3.691815.9170240.7345113409—

56,2862,7877,94034,85911, 083

18

collected November 20 toto camnlinn ctatinn niimhoi

LoadingIbs

—

48.6368--321953.62

.-4.274.57-4.566.55-18.441

-32.225.6-23.237.1-21.344.124.191.1-80.728.5-—

10,8081,4949,138155200

22, 1981.Tho

PBBLoading

Ibs

fm

6.7810.9--3.32.59---1.19--1.1955-1.624.69-1.33--1.47--1.35-1.449.87-1.97--—

843486355200

last digit refers to the depth of each sediment core portion asfollows: 1 = 0 to 4 in., 2 = 4 to 16 in., 3 = 16 to 28 in.,4 = 28 to 40 in., 5 = 40 in. and over.

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t T 0 APPENDIX B

L COMPLETE ANALYTICAL DATA AND METHODSAND ASSOCIATED QUALITY CONTROL DATA

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SUBJECT:

ENVIRONMENTAL PROTECTION AGENCYOFFICE OF ENFORCEMENT

NATIONAL ENFORCEMENT INVESTIGATIONS CENTERBUILDING 53, BOX 25227. DENVER FEDERAL CENTER

DENVER, COLORADO 80225

D

Russell Forba, Project Coordinator D;TE; January 14, 1982

emis/J/fWf7'

Charles P. Rzeszutko ̂ Chemi,s.1Dean F. Hill, Chief £,Pesticide and Toxic Substances BranchProject #624, Pine River, St. Louis, MI

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Attached you will find the results of analysis for all core samplesreceived for Project #624. All cores were analyzed for DOT and relatedcompounds, hexabromobenzene (HBB), and polybrominated biphenyls (PBB).Methodology and quality control data are provided. Results previouslyreported on December 16, 1981, are included in this report.

If you have any questions, please contact me at your convenience.

cc: R. LaidlawT. MeiggsAttachments

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B-2

BACKGROUND

On November 30, 1981, 23 core samples were received for analysis bythe Pesticide and Toxic Substances Branch as part of the Pine River Reser-voir survey (Project 624). The core samples had been collected, extruded,and sectioned into various lengths by NEIC field personnel. Each sectionwas wrapped in aluminum foil, labeled, and stored in a locked freezer untilextracted for analysis. A total of 83 separated core fractions were thenanalyzed for total DOT compounds, polybrominated biphenyls, and hexabromo-benzene. Empty aluminum and galvanized steel core sampling tubes were alsoreceived with the samples to be analyzed as field blanks.

METHODOLOGY

The core samples were placed in a fumehood in aluminum foil dishes tothaw overnight. Any excess water in the sample dish was discarded and thesample mixed with a clean spatula. Approximately 10 grams of each samplewere weighed into a pre-weighed dish and placed in a fumehood to air-dry.After several days, the sample and dish were re-weighed to determine the %of moisture in each sample.

Except as noted below, approximately 2 grams of each sample (non-dried) were weighed into clean glass vials (VOA bottles) fitted with screwcaps and Teflon-liners. Two grams of anhydrous Na2S04 were also added toeach vial and the samples were extracted by sonification with 10 m£s of a50% acetone/hexane solvent mixture. The solvent was decanted off and theextraction repeated with a fresh 10 m£ portion of solvent. The sonifica-tion was carried out for 2 minutes using an intermediate-size probe with apower level setting of 100 watts. The solvent extracts from each samplewere combined and passed thru a funnel containing anhydrous Na2S04 whichhad been pre-washed with hexane. The extracts were concentrated to 10 m£using a nitrogen blowdown apparatus.

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B-3

All samples were screened for compounds of interest by packed columnelectron-capture gas chromatography. Based on the screening results, high-level samples were simply diluted, whereas low-level samples were cleanedup by column chromatography. All samples requiring dilutions were dilutedto the appropriate levels with hexane. All samples that did not require adilution were cleaned up using Florisil column chromatography. The sampleextract was placed on the head of a glass column packed with 20 grams ofactivated Florisil and eluted with 200 m£s of 6% ethyl ether in hexane.The fraction was concentrated to less than 25 m£s using a Kuderna-Danishevaporation apparatus and further concentrated to an appropriate volumeusing a nitrogen blowdown apparatus.

All sample extracts were analyzed by fused silica capillary columnelectron-capture gas chromatography using a 15 meter DB-5 column and a 25meter OV-101 column. All extracts were analyzed for (1) Total DDT's, whichincluded o.p'-DDE, p.p'-DDE, o.p'-DDD, p,p'-DDD, o.p'-DDT, p.p'-DDT; (2)hexabromobenzene (HBB); and (3) polybrominated biphenyls (PBB).

Several of the sample extracts were also analyzed for these compoundsf by gas chromatography/mass-spectroscopy (GC/MS).

NOTE: The following samples were extracted in the same manner as des-cribed above with the exception that a lOg sample size was weighed-out with5 g of anhydrous Na2S04 and extracted with 20 m£s of 50% acetone in hexanefor,the first extraction: 09-1, 09-2, 09-3, 11-1, 11-2, 13-1, 13-2, 13-3,16-1, 16-2, 16-3, 18-1, 18-2, 18-3, 18-1 Dup., 18-2 Dup., and 18-3 Dup.

RESULTS

The results of analysis by fused silica capillary column electron cap-ture gas chromatography are given in Table 1. All results were calculatedon a dry weight basis. Also listed in this table are the results for thepercent moisture determinations for each core section. The results of analy-sis by GC/MS for several selective samples are listed in Table 2. A listof the gas chromatographic conditions are provided in Table 3.

B-4

QUALITY CONTROL

Four core samples were analyzed in duplicate and are designated aslaboratory duplicates to differentiate them from the field duplicates col-lected by the field personnel. The results of these duplicate analyses aregiven in Table 4. The large, i.e., >40% relative percent difference (RPD)observed for several parameters in several samples is not unexpected fornon-uniform samples of this sort.

Five solvent blanks were also analyzed along with the samples. Theseserved as laboratory blanks and exhibited no significant interferences.Two field blanks were submitted for analysis consisting of one 3-foot unusedgalvanized steel core tube and one 3-foot unused aluminum core tube. Theinside of the tubes were rinsed with 100 m£s of 50% acetone in hexane andconcentrated to a final volume of 10 m£s. The aluminum tube blank exhibi-ted no significant interferences while the galvanized steel tube blankshowed trace levels of several of the DOT analogs along with a multitude ofother unidentified electron capturing compounds. These trace level inter-ferences did not affect results, however. The results of the blank analysesare also listed in Table 4.

Several core samples were spiked with the various compounds of interestand analyzed in the same manner as the samples. These results are listedin Table 5. The recoveries are considered very good considering the poten-tial non-homogeniety of sediment samples.

Table 1RESULTS

Sample #

01-101-2

02-102-2

03-103-203-3

04-104-2

05-105-205-305-4

06-106-206-306-4

07-107-207-307-4

08-108-208-3

09-109-209-309-4

% Moisture

64.363.9

55.448.2

64.961.151.8

34.845.2

63.265.368.161.6

57.143.760.551.9

72.071.561.363.4

70.370.863.2

65.668.359.662.4

DDEo.P1

ND2'6ND6

ND30.06

ND3NO40.12

0.27ND4

0.061.22.2ND6

ND30.080.24ND3

0.313.81300.06

ND3ND321

0.12ND3ND3ND3

P.P1

0.070.10

0.310.48

0.321.11.0

2.27.2

0.482.85.3ND6

0.180.340.68ND3

1.89.71600.05

2.12247

0.644.5ND3ND3

Concentrations (pg/g)1ODD DOT

o.p1

0.080.12

0.220.22

0.224.24.8

1232

0.644.222ND3

0.320.622.1ND4

9.77.034000.68

6.07002000

2.3180272.5

PiP1

0.100.13

0.580.58

0.571212

2032

1.58.858ND3

1.10.662.6ND4

2422037000.85

1711002200

6.5260261.6

o,p'

ND3ND3

0.100.36

ND3ND50.49

324.8

0.110.22110ND3

0.190.21ND4ND4

4.6ND873001.1

ND101401400

1.6326.50.39

Total HBB PBBp,p* DOT and Analogues

0.18ND

3.85.3

0.611.26.4

20047

117.2790ND3

0.841.62.2ND4

6474110002.0

118903200

22130181.0

0.430.35

5.07.0

1.71825

270120

1424990-

2.63.57.8-

100380260004.7

3629008800

33600785.5

3.20.42

1.01.1

0.96NO7ND4

1590

926.2ND5NDS

12280.92ND5

NO593001001.0

26001800NDS

14024NO5ND5

2.80.46

1.00.76

0.84ND7ND4

33023

0.94NO5ND5NDS

2.20.56ND5NO5

1464ND9NO5

58ND5ND5

1818ND5ND5

00

01

Table 1 (Cont'd)CD

cn

Sample # % Moisture DDEConcentrations (ng/g)1ODD DOT Total HBB PBB

10-110-210-3

11-111-2

12-1 _12-212-3

13-113-213-313-413-5

14-114-214-3

15-115-215-3-15-415-5

16-116-216-316-4

17-117-217-317-417-5

0.964.156.3

68.565.6

68.763.555.9

67.167.767.462.255.2

66.513.515.1

71.968.967.158.856.3

64.164.567.155.0

64.268.063.757.336.8

o,p'

ND3ND10ND10

0.130.28

0.100.19ND6

0.070.15ND3400.12

9.30.12ND6

0.120.329035ND3

ND30.140.660.18

0.060.223.4ND6ND6

P,P'

0.17ND10NO10

0.610.74

0.390.25ND6

0.310.74ND3320.06

230.28ND6

0.441.06637ND3

0.410.550.800.16

0.270.824.6ND6ND8

o,p'

0.602754.0

4.08.0

2.94.8ND3

2.03.84615003.4

7407.0ND3

4.15.7150012000.20

2.51.4184.8

2.01.1900.12MJ)3

P.P1

1.51753.8

7.012

6.46.2ND3

4.79.26214004.4

130013ND3

7.812140015000.29

123.4205.0

5.21.81200.21ND3

o,p'

0.48ND8ND8

0.473.6

1.12.0ND3

2.8ND5307000.40

1400.80ND3

0.74ND41100530ND4

3.0132.4ND4

1.2ND410NO3ND3

p,p' DOT

3.0ND8ND8

4.98.3

3.93.0ND3

5.02.08611001.1

180010ND3

7.61.612001000ND4

2012120.48

141.830ND3ND3

and Analogues

5.84507.8

1733

1516

.

151622048009.5

400031-

2121540043000.49

38305411

235.72600.33 .-

5544014

97610

90170NDS

4450028ND8ND5

5.7ND5ND4

806605444ND5

86220ND5ND5

521201.9ND4ND4

1466ND8

4.821

5.08.0ND5

4.2251.0ND8ND5

2.7ND5ND4

4.016ND10ND9ND5

126.5ND5ND5

5.31.6ND5

- ND4ND3

Table 1 (Cont'd)

Sample # % Moisture DDEConcentrations (ug/g)1DDD DPT Total HBB PBB

18-118-218-3

18-1 Dup.>;} 18-2 Dup.'""' 18-3 Dup.

19-119-219-3

20-120-220-3

21-121-221-3

21-1 Dup.21-2 Dup.

22-122-222-3

23-123-223-323-4

64.031.361.6

66.330.256.9

56.570.534.8

61.868.618.4

66.669.451.9

67.970.0

70.372.364.9

66.667.667.146.6

o.p1

0.10ND31.0

0.10ND30.56

0.081.0ND6

0.114.0ND3

0.062.6ND6

0.062.2

0.064.50.19

0.080.703.8ND6

P,P'

0.29ND31.4

0.27ND31.1

0.281.6ND6

0.386.0ND3

0.263.0ND6

0.262.6

0.325.20.30

0.361.84.0ND6

o.p1

4.50.1248

3.40.1628

2.340ND3

1.71700.50

2.088ND3

2.078

2.31805.1

1.613150ND3

P.P1

6.20.2450

5.60.5134

5.035ND3

3.916004.6

4.284ND3

4.270

4.81709.6

3.432140ND3

o,p'

1.8ND41.2

0.81ND414

0.21ND10ND3

0.1812ND4

0.163.1ND3

0.20ND7

ND4ND7NO4

0.221.0NO5ND3

p,p' DDT and Analogues

7.8ND419

4.03.264

3.410ND3

6.72100.10

2.718ND3

2.32.3

1.17.00.74

2.0389.7ND3

210.36120

143.9140

1188-

1.35601.1

9.4200-

9.0160

8.637016

7.787310-

4.30.58ND5

5.00.81ND5

3442ND4

8228ND5

5432NO4

5239

3548ND5

18022ND7ND4

1.2ND5ND5

1.36.8ND5

3.04.8ND4

3.4ND5ND5

3.4ND7ND4

3.3ND7

2.15.2ND5

4.4ND5ND7ND4

09I•-J

(1)(2)(3)(4)(5)(6)(7)(8)(9)(10)

Concentration calculated on a dry weight basisNO = none detectedLimit of detection = 0.05 ng/gLimit of detection = 0.10 pg/g

0.50 |jg/g0.021.05.0252.0 pg/g

CO00

Limit of detectionLimit of detectionLimit of detectionLimit of detectionLimit of detectionLimit of detection

B-10

Table 3GAS CHROMATOGRAPHIC CONDITIONS

LengthCoating Thickness

Initial Temp. , °CInitial Time, min.Program Rate, °C/min.Final Temp. 1, °CFinal Temp. 1 Time, min.Program Rate, °C/min.Final Temp. 2, °C .Final Temp. 2 Time, min.

Injection Temp. , °CDetector Temp. , °C

Septum Sweep, m£/min.Carrier/Make-up Flow, HeInlet Purge, nuK/min.Linear Velocity, u

Injection Volume, ulDetector, EC

Column,DB-5

15 Meters1.0 urn

600.5010215251027030

230280

2304024

1.0D

Fused SilicaOV-101

25 Meters0.25 pm

600.5010190251027030

230280

2304026

1.0C

1

1

1

I. I

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11

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B-9

Table 2GC/MS CONFIRMATION RESULTS

Compound

o.p'-DDEp,p'-DDE

o,p'-DDDp.p'-DDD

o.p'-DDTp.p'-DDT

Hexabromobenzene

Polybrominated Biphenyl

DetectionLimit

1020

5050

5050

100

600

Concentration (M9/9)1#05-3

ND2NO

NDND

93720

ND

ND

#08-1

NDND

NDND

NDND

2500

ND

#08-2

NDND

6801100

170780

1800

ND

#08-3

2238

19002200

13003600

ND

ND

#15-4

1925

820970

210480

ND

ND

(1) dry weight basis(2) NO = none detected

Table 4QUALITY CONTROL SUMMARY

•^,-\

o.p'-DDEp.p'-DDEo.p'-DDDp,p'-DDDo,p'-DDTp.p'-DDT

HBBPBB

(1) RPD =(2) ND =

#07-31 . 2

130 120160 1603400 37003700 50007300 860011000 12000

100 100ND2 ND

Relative Percentnone detected

RPD1

80830169

0•"

Difference

1

21472000220014003200

NDND

#08-32

Dupl

25592400260022004600

NDND

RPD1 1#12-12 RPD1 1

#16-32 RPD1

icate Analyses

92318174436

_••

0.100.392.96.41.13.9

905.0

0.080.483.07.20.706.4

784.0

22213124448

1422

0.660.8018202.412

NDND

0.740.8422242.614

NOND

1151018815

-

•*

B-12

Table 4 (Cont'd)QUALITY CONTROL SUMMARY

Concentration (ug/g)DDE

Sample

Blank 1Blank 2Blank 3Blank 4Blank 5

AluminumPipe Blank

GalvanizedSteel Blank

Limit ofDetection

o.p1

NONONDNDND

ND

ND

0.10

P.P1

NDNDNDNDND

ND

ND

0.10

DODo.p1

Blank

NDNDNDNDND

ND

<0.20

0.10

P,P'

Analyses

NDNDNDNDND

ND

<0.20

0.10

DOTo,p'

NDNDNDNDND

ND

<0.20

0.10

P,P'

NDNONDNDND

ND

<0.20

0.10

HBB

NDNDNDNDND

ND

ND

0.20

PBB

NDNDNDNDND }

ND

ND

0.20

(1) Assumed a 2 g sample size for calculation purposes

.1

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8-13

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Table 5SPIKE RECOVERIES

Compound

o.p'-DDEp.p'-DDEo.p'-DDDp.p'-DDDo.p'-DDTp.p'-DDTHBBPBB

AmountAdded (MO)

2.52.52.52.52.52.52.52.5

% Recovery#10-1

8496766080NA1

NANA

#17-2

104108108100104108160180

#18-2

9597991009294118104

#20-3

8484848775718790

(1) NA = not applicable

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