NOAA Technical MemorandumNMFS-SEFC- 31

NOAA/NMFS FINALREPORT TO DOE

Biological/ Chemical Survey ofTexo~a and Capline SectorSalt Dome Brine DisposalSites Off Louisiana, 1978-1979

A report to the Department of Energy on work conducted under provisionsof Interagency Agreement El- 78-1-0-7146 during 1978-1979.

Volume VII

TRACE METALS

NOVEMBER 1980

u.s. DEPARrMENT OF COMMERCENational Oceanic and Atmospheric AdministrationNational Marine Fisheries Service

Southeast Fisheries CenterGalveston LaboratoryGalveston. Texas 77550

NOAA Technical MemorandumNMFS-SEFC- 31

Biological/Chemical Survey of Texoma andCapline Sector Salt Dome Brine DisposalSites Off Louisiana, 1978-1979

VOL. VII - DETERMINE TRACE METAL COMPOSI-TION AND CONCENTRATION IN MAJORCOMPONENTS OF THE ECOSYSTEM

BYJ. B. Tillery

Southwest Research Institute6228 Culebra

San Antonio, Texas 78284

A report to the Department of Energy on work conducted under provisionsof Interagency Agreement El-78-I-O-7146 during 1978-1979.

EDITORS

William B. JacksonSenior Advisor

Contracts & Deliverablesand

Gary M. FawFishery Biologist

U. S. DEPARTM ENT 0 F COMMERCEPhilip M. Klutznick. Secretary

National Oceanic and Atmospheric AdministrationRichard A. Frank. Administrator

National Marine Fisheries ServiceTerry L. Leitzel!. Assisistant Adm in istrator fo r Fisheries

This TM series is used for documentation and timely communication ofpreliminary results. interim reports. or similar special purpose informa-tion. Although the memos are not subject to complete formal review,

editorial control. or detailed editing. they are expected to reflect

sound professional work.

DISCLAIMER

This document is a Final Report. It has been reviewed by the NationalMarine Fisheries Service and the National Oceanic and AtmosphericAdministration and approved for printing. Such approval does notsignify that the contents necessarily reflect the views and policiesof the U.S. Department of Energy, NOAA or NMFS. This Report has notbeen formally released by the DOE. Mention of trade names and com-mercial products herein does not constitute endorsement or recommen-dation for use.

ii

NOTICE

This document is a Final Report.by the U.S. Department of Energyconstrued to represent Department

It has not been formally releasedand should not at this stage bepolicy.

This Report should be cited as follows:

Tillery, J. B. 1980. Determine trace metal composition and concen-tration in major components of the marine ecosytem. Vol. VII.In: Jackson, W. B. and G. M. Faw (eds.). Biological/chemicalsurvey of Texoma and Capline sector salt dome brine disposal sitesoff Louisiana, 1978-1979. NOAA Technical Memorandum NMFS-SEFC-31,72 p. Available from: NTIS, Springfield, Virginia.

iii

Volume VII - TRACE METALS

TABLE OF CONTENTS

Page

Li sto f Volumes .•••..............•••.•......•...•...•...•

Editors1 SectionProject Administration

I.

IntroductionFig. 1.

......................... ' .Regions of Study for Brine DisposalAssessment-DOE/NOAA Interagency Agreement

viviii

x

xiii

Fig. 2.

Fig. 3.

Fig. 4.

Proposed Texoma Brine Disposal Site ••••••• xiv

Proposed Capline Brine Disposal Site •••••• xvSampling Scheme for Proposed Brine Disposalsi tes ~...•....•.......... -.- xv-i

List of Reports and Publications xviiII. Principal Investigators' Section

Work Unit 3.3 Determine Trace Metal Composition and Con-centration in Major Components of theMarine Ecosystem •••.••••••••••••••.••••••• xx

iv

I. EDITORS' SECTION

v

PROJECT ADMINISTRATION

NOAA Program Management:

Program Manager

Capt. Charles A. BurroughsNOAA/EDIS/CEAS/MEAD

NMFS Project Management:

Contracting Officer's Technical RepresentativeEd~ard F. Klima, Ph.D.DirectorGalveston LaboratoryNMFS Southeast Fisheries CenterProject ManagerCharles W. Caillouet, Ph.D.Chief, Environmental Research DivisionProject StaffWilliam B. JacksonSenior AdvisorContracts and DeliverablesGregg R. GitschlagSenior AdvisorField Operations and LogisticsGary M. FawFishery BiologistE. Peter H. WilkensFishery Biologist

Robert M. Avent, Ph.D.Oceanographer

Maurice L. Renaud, Ph.D.Oceanographer

vi

Petronila C. PradoClerk Stenographer

Dennis B. RoiComputer Programme~

Beatrice RichardsonClerk Typi.st

Susan E. GrayClerk Typist

Julie MellenStudent AideHoward S. HadaFishery Biologist

vii

LIST OF VOLUMES

This Final Report is printed in nine separate volumes:

Volume I - BENTHOSWork Unit 2.1 Describe Living and Dead Benthic (Macro-

and Meio-) Communities

Coastal Ecosystems Management, Inc.

R. H. Parker, Ph.D.A. L. CroweL. S. Bohme

Volume II - ZOOPLANKTONWork Unit 2.2 Determine Seasonal Abundance, Distribution

and Community Composition of ZooplanktonLGL Ecological Research Associates, Inc.

L. A. Reitsema, Ph.D.

Volume III - BACTERIA

Work Unit 2.3 Describe Bacterial Communities

Texas A & M University

J. R. Schwarz, Ph.D.S. K. Alexander, Ph.D.S. J. SchroppV. 1. Carpenter

Volume IV - DEMERSAL FISHES AND MACRO-CRUSTACEANS

Work Unit 2.4 Determine Seasonal Abundance, Distributionand Community Composition of DemersalFinfishes and Macro-crustaceansTexas A & M University

A. M. Landry, Ph.D.H. W. Armstrong, Ph.D.

viii

\

Volume V - SEDIMENTSWork Unit 3.1 Describe Surficial Sediments and Suspended

Particulate MatterEnergy Resources Company, Inc.K. A. Hausknecht

Volume VI - HYDROCARBONSWork Unit 3.2 Determine Hydrocarbon Composition and

Concentration in Major Components of theMarine Ecosystem

Energy Resources Company, Inc.

P. D. Boehm, Ph.D.D. L. Fiest

Volume VII- TRACE METALS

Work Unit 3.3 Determine Trace Metal Composition andConcentration in Major Components of theMarine EcosystemSouthwest Research Institute

J. B. Tillery

Volume VIII - INORGANIC NUTRIENTS

Work Unit 3.4 Determine Seasonal Variations in InorganicNutrients Composition and Concentrations inthe Water Column

Texas A & M UniversityJ. M. Brooks, Ph.D.

Volume IX - SHRIMP DATA ANALYSISWork Unit 5.1 Analysis of Variance of Gulf Coast Shrimp Data

LGL Ecological Research Associates, Inc.F. J. Margraf, Ph.D.

ix

INTRODUCTION

In compliance with the Energy Policy and Conservation Act of 1975,Title 1, Part B (Public Law 94-163), the Department of Energy (DOE)implemented the Strategic Petroleum Reserve (SPR). The SPR prDgramwas implemented in August Df 1977 with the gDal Df stDring a minimumDf Dne billiDn barrels Df crude Dil by December 22, 1982. After eva-luating several physical stDrage pDssibilities, DOE determined thatstDrage in cDmmercially develDped salt dDme cavities thrDugh solutiDn-mining prDcesses was the mDst econDmically and envirDnmentally advan-tageDus aptian.Six areas alDng the nDrthwestern Gulf af Mexico.were to. be investi-gated as pDtential starage cavern sites. These areas are shawn inF'igure 1. This praject, "Bialogical/Chemical Survey af TeXDma andCapline Sectar Salt Dome Brine DispDsal Sites Off Louisiana", dealswith prapDsed dispDsal sites assDciated with two. of the cavern sites,West Hackberry and Weeks Island. The BiDIDgical/ Chemical Survey wasinitiated in April 1978 and was cDmpleted in December 1979. Its majDrproducts are Final RepDrts available thrDugh the NatiDnal TechnicalInfDrmatiDn Service (NTIS), Springfield, Virginia; data files avail-able thrDugh the EnvirDnmental Data and InfDrmatiDn Service (EDIS),WashingtDn, D.C., and any research papers that may be.written by par-ticipating principal investigatDrs and published in scientific Drtechnical journals. preliminary results were also.made availablethrDugh DOE/NOAA/NMFS prDject reviews and wDrkshDps attended by prD-ject participants and variDus gDvernmental, private and public usergrDups.The Dbjectives Df the BiDlDgical/Chemical Survey were: (1) to.describe the bialDgical, physical and chemical cDmpDnents af themarine eCDsystem fDr each dispDsal site; and (2) to. assess, by analy-sis Df Gulf CDast shrimp data, the impDrtance Df the LDuisianashrimping grDunds in the vicinity Df the prDpDsed salt dDme brinedispDsal sites. These Dbjectives were achieved using histDrical andnew data to.describe and quantify the biDlagical, chemical, and physi-cal characteristics and the tempDral variations Df these characteris-tics in the envirDnments Df each prDpDsed dispDsal site.

The two.prDpDsed dispDsalsites have been extensively examined, usingavailable meteDrDIDgical, DceanDgraphic, bathymetric and eCDIDgicaldata, in the follDwing two.repDrts:

x

Env~ronmental Data Service, DOC/NOAA. 1977.Analysis of Brine Disposal in the Gulf of Mexico, #2 WestHackberry. Report to Federal Energy AdministrationStrategic Petroleum Reserve Program Salt Dome Storage.Center for Experiment Design and Data Analysis, NOAA, EDS,Marine Assessment Division, Washington, D.C.

Environmental Data Service, DOC/NOAA. 1977.

Analysis of Brine Disposal in the Gulf of Mexico, #3Capline Sector. Report to Federal Energy AdministrationStrategic Petroleum Reserve Program Salt Dome Storage.Center for Experiment Design and Data Analysis, NOAA, EDS,Marine Assessment Division, Washington, D.C.

The above reports and other pertinent documents are available from theDepartment of Commerce, National Technical Information Service, 5285Port Royal Road, Springfield, Virginia, 22151.Proposed locations of the West Hackberry (Texoma Sector) and WeeksIsland (Capline Sector) brine disposal sites are shown in Figures 2and 3, respectively. These sites are subject to change within thesame geographic area pending results of baseline surveys presentlyunderway.The proposed West Hackberry disposal site is located approximately 9.7km (6 miles) south off the coast from Mud Lake at Latitude 29°40' Nand Longitude 93 "28' W at a bottom depth of about 9 m (30 feet).Operational requirements and engineering limitations of the proposedbrine diffuser at this site are as follows: length ....933.3 m (3070feet); orientation -normal to coast; number of ports - 52; length be-tween ports"" 18 In (59 feet); port diameter - 7.6 cm (3 inches);orientation of port riser - 90° to bottom; and port exit velocity ....7.6 m/sec (25 ft/sec).The proposed Weeks Island (Capline Sector) disposal site is locatedapproximately 41.8 km (26 miles) off Marsh Island at Latitude 29004'Nand Longitude 91°45' W at a bottom depth of about 9 m (30 feet).Operational requirements and engineering limitations of the proposedbrine diffuser at this site are as follows: length - 608 m (2000feet); orientation -normal to coast; number of ports - 34; orientationto port riser"" 90° to bottom, and port exit velocity - 7.6 m/sec (25ft/sec) •The Biological/Chemical Surveys in the proposed salt dome brine dispo-sal sites described seasonal abundance, distribution and community

xi

composition of major benthic, planktonic, bacterial and demersal fin-fish and macro-crustacean ecosystem components; the sediments; thehydrocarbons and trace metals composition and concentration in themarine ecosystem; and the seasonal variations in inorganic nutrientscomposition and concentration of the water column. The samplingscheme used for sample collections around the two sites is shown inFigure 4. A separate data analysis assessed the importance of shrimp-ing grounds in the vicinity of the proposed brine disposal sites interms of historical data on species composition, marketing size cate-gories and location of commercial shrimp catches within statisticalreporting zones off the Louisiana coast.

Information concerning data from this project is available through theProgram Data Manager: Mr. Jack Foreman, Environmental Data andInformation Service, Page Building No.2, 3300 Whitehaven Street,N.W., Washington, D.C.

xii

TEXAS

96°W

I

( LOUISIANAWUT HACKBERRY

alii HIll •

GULf Of MEXICO

Figure 1. Regions of Study for Brine Disposal Assessment-DOE/NOAA Interagenc1'Agreement (adapted from EnvironMental Data Service, DOC/NOAA. Analysis ofBrine Disposal in the Gulf of Mexico, #2 West Hackberry. 1977.).

1 Texas Coastal Ocean, Colorado River to San Luis Pass (Bryan Mound)

2 Louisiana Coastal Ocean, Sabine Lake to S.vi. Pass of Vermilion Bay(West Hackberry)

3 Louisiana Coastal Ocean, S.W. Pass, Vermilion Bay to Timbalier Island(Capline Sector)

4 Texas Coastal Ocean, Port Bolivar to Sabine Pass

5 Texas Coastal Ocean, Freeport Harbor to Galveston South Jetty

6 Louisiana Coastal Ocean, Offshore from Vermilion Bay to Terrebone Bay

xiii

30 -FT .••••••• .,..---- •.•. -.

HOLLY BEACH

CAlCASJEU PASS., PIPELINE 0.1PLAtfORM• I

0.1

MUD LAKE

BEACH

•• PLATFORMS- "...,-...~ ..". -.-

Figure 2. Proposed Texoma brine disposal site.

PRQPOSEDPIPELINE

GRAPHIC SCALEI I Io , 10n.m.

.,'"- .-. - -.- ••••••• 'FATHOMS _ ." /' ~,., "......... - --- "it~

3 FATHOMS••• "I .•~•••••••"'''••••I'' •••••

_ ••",•••••• ; . "J'" ••••"'\ •••••••

.l <..' ·,· .••• 1 .,....,.,....,...

t;;..\:.IIj

TRINITYjSHOAL,:

J .-,'I ~-",. ,

,,' "'~.•..;,--

Figure 3. Proposed Capline brine disposal site.

Transect perpendicularto coast

2

Proposed locationof diftuser

Scale:Nautical

I1.0

Miles

14

Figure 4. Sampling scheme for proposed salt dome brine disposal sites.

REPORTS AND PUBLICATIONS

Boehm, P. D. and D. L. Fiest. 1980. Determine hydrocarbons com-position and concentration in major components of the marine eco-system. Vol. VI. In: Jackson, W. B. and G. M. Faw (eds.).Biological/chemical-Survey of Texoma and Capline sector salt domebrine disposal sites off Louisiana, 1978-1979. NOAA TechnicalMemorandum NMFS-SEFC-30, 136 p. Available from: NTIS,Springfield, Virginia.

Brooks, J. M. 1980. Determine seasonal variations in inorganicnutrient composition and concentration of the water column. Vol.VIII. In: Jackson, W. B. and G. M. Faw (eds.). Biological/chemicarsurvey of Texoma and Capline sector salt dome brinedisposal sites off Louisiana, 1978-1979. NOAA Technical Memo-randU1l1NMFS-SEFC-32, 31 p. Available from: NTIS, Springfield,Virginia.

Caillouet, C._W., F. J. Patella and W. B. Jackson. 1979. Relation-ship between marketing category (count) composition and ex-vesselvalue of reported annual catcbes of shrimp in the eastern Gulf ofMexico. Marine Fisheries Review 41(5-6):1-7.

Caillouet, C. W'.,F. J. Patella and W. B. Jackson. 1980. Trendstoward decreasing size of brown shrimp, Penaeus aztecus~ and whiteshrimp, Penaeus setiferus, in reported annual catches from Texasand Louisiana. NOAA/NMFS Fishery Bulletin 77(4):985-989.

Caillouet, C. W., D. B. Koi and W. B. Jackson. In press. Relation-ship between ex-vessel value and size composition of annual lan-dings of shrimp from the Gulf and South Atlantic Coasts. MarineFisheries Review.

_Caillouet, c. W. and D. B. Koi. In press.and size composition of annual landingsshrimp from the Gulf and South AtlanticStates. Marine Fisheries Review.

Trends in ex-vessel valueof brown, pink and whitecoasts of the United

Hausknecht, K. A. 1980. Describe surficial sediments and suspendedparticulate matter. Vol. V. In: Jackson, W. B. and G. M. Faw(eds.). Biological/chemical sm;vey of Texoma and Capline se¢.torsalt dome brine disposal sites off Louisiana, 1978-1979. NOAATechnical Memorandum NMFS-SEFC-29, 56 p. Available from: NTIS,Springfield, Virginia.

xvii

Landry, A. M. and H. W. Armstrong. 1980. Determine seasonal abun-dance, distribution and community composition of demersal fin-fishes and macro-crustaceans. Vol. IV. In: Jackson, W. B. andG. M. Faw (eds.). Biological/chemical survey of Texoma andCapline sector salt dome brine disposal sites off Louisiana,1978-1979. NOAA Technical Memorandum NMFS-SEFC-28, 180 p.Available from: NTIS, Springfield, Virginia.

Margraf, F. J. 1980.-Analysis of Variance of Gulf Coast shrimp data.Vol. IX. In: Jackson, W. B. and G. M. Faw (eds.). Biological/chemical survey of Texoma and Capline sector salt dome brine dis-posal sites off Louisiana, 1978-1979. NOAA Technical MemorandumNMFS-SEFC-33, 293 p. Available from: NTIS, Springfield,Virginia.

Parker, R. H. and A. L. Crowe. 1980. Describe living and deadbenthic (macro- and meio-) communities. Vol. I. In: Jackson, W.B. and G. M. Faw (eds.). Biological/chemical survey of Texoma andCapline sector salt dome brine disposal sites off Louisiana,1978-1979. NOAA Technical Memorandum NMFS-SEFC-25, 103 p.Available from: NTIS, Springfield, Virginia.

Reitsema, L. A. 1980. Determine seasonal abundance, distribution andcommunity composition of zooplankton. Vol. II. In: Jackson, W.B. and G. M. Faw (eds.). Biological/chemical survey of Texoma andCapline sector salt dome brine disposal sites off Louisiana,1978-1979. NOAA Technical Memorandum NMFS-SEFC-26, 133 p.Available from: NTIS, Springfield, Virginia.

Schwarz, J. R., S. K. Alexander, A. J. Schropp and V. 1. Carpenter.1980. Describe bacterial communities. Vol. III. In: Jackson,W. B. and G. M. Faw (eds.). Biological/chemical survey of Texomaand Capline sector salt dome brine disposal sites off Louisiana,1978-1979. NOAA Technical Memorandum NMFS-SEFC-27, 48 p.Available from: NTIS, Springfield, Virginia.

Tillery, J. B. 1980. Determine trace metal composition and con-centration in major components of the marine ecosystem. Vol. VII.In: Jackson, W. B. and G. M. Faw (eds.). Biological/chemicalsurvey of Texoma and Capline sector salt dome brine disposal sitesoff Louisiana, 1978-1979. NOAA Technical Memorandum NMFS-SEFC-31,72 p. Available from: NTIS, Springfield, Virginia.

xviii

II. PRINCIPAL INVESTIGATORS' SECTION

xix

WORK UNIT 3.2 - DETERMINE TRACE METAL COMPOSITION ANDCONCENTRATION IN MAJOR COMPONENTS OF THEMARINE ECOSYSTEM

J. B. Tillery

Southwest Research Institute

xx

ABSTRACT

This report is the result of the trace (or heavy) metalinvestigations at the West Hackberry (Texoma) and Weeks Island(Capline) proposed brine diffuser sites during four consecutiveseasons (1978.79). Samples of suspended particulate matter,epibenthic organisms and macrocrustaceans were collected duringall four seasons. Surficial sediments were collected duringtwo seasons (summer and wi nter). The spaci al and temporal distributionsof 13 trace metals (Al, Ba, Cd, Cr, Cu, Co, Fe, Hg, Mn, Ni, Pb,Sr, and Zn) were determined in eaCh sample matrix.

Higher metal concentrations in sediments from the West Hackberrysite are in agreement with the higher amounts of silt, clay andorganic carbon reported in these sediments. Lower metal con<:entrationsin Weeks Island sediments are due to the higher amounts of siltysand and low organic carbon content.

There are seasonal vari ations in sediment Ba, Cd and Hgconcentrations at the West Hackberry site. However, Ba, Sr andCd concentrations in the summer (West Hackberry) did not correlatewith other geOChemical parameters and are suspected of comingfrom terrigenous sources and offshore oilfields. Sediment concentrationsof Ni and Zn from the Weeks Island site did not correlate withother geochemical parameters (e.g., hydrous Fe fraction, % CaC03)and are thought to originate from the offshore oilfield to thesoutheast.

Seasonal concentrations of trace metals in suspended particulatematter were similar for both West Hackberry and Weeks Island.Concentrations of Al and Fe were high in the winter (season ofhighest loading) which suggest a significant amount of resuspension'of bottom sediments.

The lack of adequate quantities of a single species of epibenthicorganism through all seasons limited the use of these animal s

3.3-ii

as trace metal pollution indicators. Only Portunus gibbesiiwere available in sufficient numbers to detennine seasonal andintraspecies variations. No seasonal variations were observed,but the intraspecies variation of Al, Cu, Fe, Hg, Mn, Sr,andZn concentrations were high.

There are indications of seasonal variations of Ba, Cd andHg in Penaeus setiferus (white shrimp) muscle tissues. No significantsite differences in metal concentrations were observed in P.setiferus. Comparison of Trachypenaeus contrictus andTrachypenaeussimilis trace metal burdens with other Gulf of Mexico studiesindicates our concentrations of Cd, Pb and Sr are higher.

3.3-iii

TABLE OF CONTENTS

AbstractList of TablesList of Figures

I. INTRODUCTIONII. METHOD AND MATERIALS

A. InstrumentationB. Sample CollectionC. Methodologies

1. Surficial Sedimentsa. Partial Digestionb. Total Digestion

2. Suspended Particulate Matter

Pageiivivi i

1

6

666

6

67

8

a. Leach Procedure for Adsorbed Elements 8b. Rigorous Digestion for Total Metals 9

3. Epibenthi ca. Microdigestionb. Macrodigestionc. Mercury in Epibenthic Tissue

4. MacrocrustaceaD. Analytical Parameters and Quality Assurance

1. Sed;ments2. Suspended Particulate Matter (SPM)3. Biota

II1. RESULTS AND DISCUSSIONA. Surficial SedimentsB. Suspended Particulate Matter (SPM)C. Biota

1. Macrocrustaceans2. Epibenthic

3.3-iv

10

10111213

13

13131417

1723232330

IV. CONCLUSIONSA. West Hackberry Disposal SiteB. Weeks Island Disposal Site

ReferencesAppendix A ••FiguresAppendix B ..Sample and Data Inventories

3.3-v

Page36

3637404271

Number

LIST OF TABLES

Page1. Trace Metal Concentrati ons and Percent Recovery in NBS 14

SRM 1645 River Sediment2. Trace Metal Concentrations and Percent Recovery in NBS 16

SRM 1577 Bovine Liver3. Seasonal Comparison of Average Trace Metal Concen- 18

trations in Surficial Sediments from West Hackberry(A) and Weeks Island (B) Disposal Sites

4. Mean Trace Metal Concentrations (~g/L) and Mean 24Particulate (mg/L HOH) by Site in SuspendedParticulate Matter

5. Seasonal Trace Metal Concentrations (~g/g dry weight) 25in Macrocrustacean from West Hackberry (A) ProposedDisposal Sites

6. Seasonal Trace Metal concentrations (j.Ig/gdry weight) 26in Macrocrustacean from Weeks Island (B) ProposedDisposal Sites

7. Comparison of Seasonal Variations in Average Trace Metal 29Concentrations in Trachypenaeus simi1is (Sugar Shrimp)and T. constri ctus( Broken Neck Shrimp) Muscle Tissues(1-1 g/9 dry wei ght) with Other Gulf Studi es

8. Species of Epibenthic Organisms Collected by Season at 31West Hackberry and Weeks Island Proposed Disposal Sites

9. Trace Metal Concentrations (~g/g wet weight) in Epi- 32benthic Organisms by Season at the West Hackberry ProposedDisposal Site

10. Trace Metal Concentrations (~g/g wet weight) in Epi- 34benthic Organisms by Season at Weeks Island ProposedDisposal Site

3.3-vi

Number

LIST OF FIGURES

Page

1. Proposed Disposal Si te at West Hackberry 43

2. Proposed Disposal Site at Weeks Island 44

3. Sampling Grid Used at West Hackberry and Weeks Island 45Proposed Disposal Sites

4. Al versus Fe in Surficial Sediments from West Hackberry; 46Summer (I) and Winter (III) Cruises

5. Sa versus Fe in Surficial Sediments from West Hackberry; 47Summer (1) and Winter (II 1) Crui ses

6. Cd versus Fe in Surficial Sediments from West Hackberry;' 48Sumer (I) and Winter (III) Cruises

7. Co versus Fe in Surficial Sediments from West Hackberry; 49Summer (I) and Winter (III) Cruises

8. Cr versus Fe in Surficial Sediments from West Hackberry; 50Summer (I) and Winter (III) Cruises

9. Cu versus Fe in Surficial Sediments from West Hackberry; 51Summer (I) and Winter (III) Cruises

10. Hg versus Fe in Surfici al Sediments from West Hackberry; 52Summer (I) and Winter (I II) Crui ses

n. Mn versus Fe in Surficial Sediments from West Hackberry; 53Summer (I) and Winter (II 1) Crui ses

12. Ni versus Fe in Surfici al Sediments from West Hackberry; 54Summer (I) and Winter (III) Cruises

13. Pb versus Fe in Surficial Sediments from West Hackberry; 55Summer (I) and Winter (III) Cruises

14. Sr versus Fe in Surficial Sediments from West H.ackberry; 56Summer (I) and Winter (III) Cruises

15. Zn versus Fe in Surficial Sediments from West.Hackberry; 57Summer (I) and Winter (III) Cruises

16. Al versus Fe in Surficial Sediments from Weeks Island; 58Summer (I) and Winter (III) Cruises

3.3-vii

Number Page17. Ba versus Fe in Surfici al Sediments from Weeks Island; 59

Summer (I) and Winter (III) Cruises

18. Cd versus Fe in Su·rfici al Sediments from Weeks I sl and; 60Sumner (I) and Winter (III) Crui ses

19. Co versus Fe in Surficial Sediments from Weeks Island; 61Sumner (I) and Winter (III) Cruises

20. Cr versus Fe in Surficial Sediments from Weeks Island; 62Summer (I) and Winter (III) Cruises

21. Cu versus Fe in Surfici al Sediments from Weeks I sl and; 63Summer (1) and Winter (III) Crui ses

22. Hg versus Fe in Surficial Sediments from Weeks I sl and; 64Summer (I) and Winter ( III) Crui ses

23. Mn versus Fe in Surficial Sediments from Weeks Island; 65Sumner (I) and Winter (III) Crui ses

24. Ni versus Fe in Surfici al Sediments from Weeks I sl and; 66Sumner (I) and Winter (III) Crui ses

25. Pb versus Fe in Surfici.al Sediments from Weeks Island; 67Summer (I) and Winter (III) Cruises

26. Sr versus Fe in Surficial Sediments from Weeks I sl and; 68Summer (I) and Winter (III) Cruises

27. Zn versus Fe in Surfi ci al Sediments from Weeks Isl and; 69Summer (1) and Winter (III) Cruises

28. Fe versus $ Clay in Surficial Sediments from West 70Hackberry (A) and Weeks Island (B) Sites for Summer (1)Crui se

3.3-viii

I. INTRODUCTION

The Energy Policy and Conservation Act of 1975, Title I,Part B (P.L. 94••163) mandated the Department of Energy (DOE)to estabH sh a Strategic Petroleum Reserve (SPR). In responseto this mandate the DOE embarked upon a program to develop severalnatural salt dome formations along the Texas-Louisiana coastinto underground storage cavities.

It was determined that existing salt dome cavities wouldnot have sufficient volume to meet the goals of the SPR programand virgin salt domes would have to be leached to form new storagecavities. The estimated total volume of saturated brine solution(l.4••billion barrels per site) that will result from this programcannot be handled by current disposal methods (deep well injectionsand chemical feedstocks) (Bender 1978). The alternative is disposaloffshore in the Gulf of Mexico. This requires a considerationof the effect this saturated brine solution will have on themarine environment and ecosystems at the disposal (diffuser)sites.

In the last decade, a number of multidisciplinary marineenvironmental studies have been conducted on the Outer ContinentalShelf (OCS) of the Gulf of Mexico. Many of the larger studieshave been sponsored by federal and state agencies, while a significantnumber of smaller studies have been conducted by universities,nonprofit organizations, and other research groups.

One objective of these studi es has been to develop a betterunderstanding of the trace metal chemistry involved in the marineenvironment and to delineate the natural fluxes and mechanismsthat ex; st. Th;s understandi ng is becom;ngmore imperative asmanl s activities encroach further upon our coastal regions andOCS areas.

3.3••1

Information developed from these programs can be used tobetter understand the heavy metal data from the SPR program byproviding a frame of reference from which evaluations and comparisons

can be made.Two of the larger studies were the environmental baseline

studies on the Mississippi, Alabama and Florida (MAFLA)OuterContinental .Shelf (Dames and Moore 1979) and the South Texas

Outer Continental Shelf (STOCS) {Presley and Boothe 1979; Berryhillet al. 1979). These studies provided trace metal data ongeochemical, water column, and biota samples from areas of the oesnot significantly impacted by man's activities (i.e., pollution).

The objectives of the trace metal investigations were to

delineate the ambient trace metal burdens and explain their

seasonal and spacial variations and distributions in a selected

population of marine samples.This information would allow a background {baseline} from

which future comparisons could be made if extensive utilizationand development occurs in these areas. This infonnation is also

useful as a benchmark to' which other trace metal envi ronmentalstudies may be compared.

Perhaps the most significant study related to our investigation

would be the earli er basel inesurvey at the West Hackberry proposed

diffuser site (Shokes 1978). In the Shokes' study, samples fortrace metal analyses were collected in the fall 1977 and Jhewinter 1978. These included surficial sediments, selected macrobiota,suspended particulates, interstitial water, and filtered sea

water. These samples were analyzed for ten trace metals (Fe,Al, Cu, Cr, Pb,Mn, Ni, Zn, Cd, Hg).

The objective of Shokes I (1978) survey was to describe thespacial and temporal variations of the ten trace metals in each

sample type. The intraspecies 'variation in the biota samples

3.3-2

were also determined to allow estimations af sampling populationsnecessary to observe a percent change for a particular metalin a given species.

The trace metal burdens in the surficial sediments werestrongly correlated wi th the sediment mineralogy and texturewhich were controled by two factors: (1) current flows and stonnfronts that dominated this relatively shallow offshore area and(2) the terrigenous inputs from the Calcasieupass (Shokes 1978).

Concentrations of Fe and Mn in Penaeus setiferus appearedto have a seasonal variation (Shokes 1978). Other metal concentrationsin P. setiferus were similar to values obtained in other studies.

Data from Shakes' study will be used later in this report.A recently completed study which coul d impact the SPR program

is the Bureau of Land Management's (BlM) fate and effects studyof petroleum production platfonns off the louisiana coast (Ti1lery,lin preparation). Although the study area is to the southeastof the Weeks Island proposed diffuser site, there are longshorecurrents near the loui si ana-Texas coast that transport sedimentsand· suspended particulate matter from this area into both the

Weeks Island and West Hackberry sites.Ti1lery'sstudy (in preparation) has found sediment concentration

gradients of Ba, Cd, CU,Cr, Pb, Ni and Zn from the areas ofseveral petroleum production platform structures that are notcorrel ated to any geochemical parameters. These metal s are suspectedof being contaminants from the platform structures or petroleumproduction activities (past or present). The number of tracemetals in surficial sediments that could be associated with platformstructures increased with distance from the Mississippi River.This suggests that the sediment load of trace metals from theMississippi River "masks" the effect of the platfonn structures.No evidence of bioaccumulation·of trace metals in a number ofdifferent epibenthic, macrocrustacean, demersal and pelagic fish

could be detected.

3.3-3

The findings from this BLMstudy (TillerYt1 in preparation)appear to be su.ppol"tive of three other studi es conducted in theGulf of Mexico. From 1972 to 1974 an Offshore Ecological Investigation(DEI) was conducted in Timbalier BaYt Louisianat and the immediateoffshore waters (Willi ams and Jones 1974; Montal vo and Brady1974). These investigators concluded that Timbalier Bay sedimentswere contarni nated with Sa fl"om drill i ng fl ui ds (ba ri te) usedin dri 1li ng operati ons t and there were higher concentl"ati onsof Hgt Pbt Cdt Zn and As in Timbalier Bay waters than in offshore

waters. Alsot the offshore water concentrations of Znt Cd andPb decreased with di stance from production p1atfonn structures.

The second study is a four-year environmental eval uationof the Buccaneer gaS/Oil field located 32 mil es south of GalvestontTexas. Two active petroleum production platforms have been thecenter of this study. Resul ts from the second yeart 1977...1978t(Anderson and Schwarzer 1979) and the third yeart 1978-1979t(Tille~,2 1980) indicate that sediment concentrations of Ba,Cd, Cr, Cu, Mn, Pb, Sr and Zn decrease with di stance from theplatfonns and are not correlated to other geochemical parameters.It is believed these trace metals are coming from the platformstructure, produced brine discharges, previous dl"illing operations,and boating activities around the platfonn structures.

The thi rd study, which was a part of the MAFlAi nvesti gationsmentioned earlier, is the Rig Monitoring Study (White, Turgonand Blizzard 1977) which examined an offshore drilling site priorto, during, and after drilling operations. Sediments and biotawere analyzed for Cd, Cr, Cu, Fe, Pb, Ni and V. Bottomsedimentsshowed an increase in Ba concentl"ations both "during" and lIafter"

drilling operations. There were also increases in Fe concentrationin epifauna but this could not be connected to the drilling activities.StOl"mpassage, which increased 'the amount of resuspended sediments,may have been a causative factor.

3.3-4

Figure 1 shows the location of the West Hackberry disposalsite. It is located approximately six miles off the coast fromMud Lake at 29°40' Nand 93°28 'w witha bottom depth of approximately30 feet. This site is identified as site "A. I'

Figure 2 shows the location of the Weeks Island disposalsite. It;s approximately 26 mil es from the south poi nt offthe coast of Marsh Island andi s located at .29°04' Nand 91°45'Wwith a depth of 30 feet. This site is identified as site "B."

Figure 3 illustrates the sampling grid used at both sites.Station 8 is located over the center of the proposed diffuser.

The purpose of this project is to conduct an environmentalassessment of the West Hackberry and Weeks Island disposal sites.The objectives of the trace metal investigations are to characterizesurficial sediments, suspended particulate matter, selected epibenthicorganisms and macrocrustaceans, collected from the viCinity ofthe di ffuser sites, for 13 trace (or heavy) metal s (Al, Ba, Cd,Co, Cu, Cr, Fe, Hg,Mn, Ni, Pb, Sr, Zn) over four consecutiveseasons.

These data, along with other trace metal data on these sites,wi11 provide the ambient or "baseli ne" concentrations, seasonalvariability, and intraspecies variability to which future monitoringefforts can be c·ompared. This w;11 prov; de ; nformation on theamount and affect of trace metal pollution added to the marineecosystems at the bri ne diffusers once they become operational.

3.3-5

II. METHODANDMATERIALS

A. InstrumentationThe following atomic absorption spectrophotometers were

used for all metal analyses:

* a Perkin-Elmer Model 5000 Atomic Absorption Spectrophotometerwith a HGA-500Graphite Furnace and multigas flame capability.This system is completely automated and includes a Perkin-Elmer AS-3 Automatic Micro Sampler System for fl ame analysisand a Perkin-Elmer AS-l Auto Sampling System for flamelessanalysis.

* a Perkin-Elmer MOdel560 Atomic Absorption Spectrophotometerwith a HGA-500Graphite Furnace andmul ti gas fl ame capabi 1i ty.

* a Perkin-Elmer Model 403 with an Instrumentation Laborato~Il-455 Graphite Furnace.

* a Perkin-Elmer Model 306 with a HGA-2000Graphite Furnace.

B. Sample CollectionAll samples were col lected using noncontaminating techniques

and material s. Samples were pl acedinpre-aci d washed polyethylenecontainers and frozen immediately after collection. Samples

remained frozen until ready for analyses at the on-shore laboratory.C. Methodologies

1. Surficial Sediments

The "parti al" digestion was done on all sediment samples.On 25 percent of sediment samples, a "total" di gestion was performed.

a. Partial DigestionThe sediment subsample was removed from the freezer

and allowed to thaw completely and equilibrate with room temperature.An acid-cleaned glass rod was used to thoroughly mix the wets.ediments before 60-80 grams of the wet sediment waswei ghedinto a tared polyethylene beaker. Particles greater than, orequal to, 3 mmwere removed with Teflon-coated forceps. Thebeaker was then covered with a thin sheet of tissue paper and

3.3-6

placed in a drying oven (60°C) until sediment reached a constantdry weight. The sample was reweighed to determine water loss.The sample was then ground in a roortar and pest1 e and storedin an acid-cleaned polyethylene bottle.

A five-gram aliquot of the dried sediment was

weighed into a 250-mL polyethylene screw-cap Erlenmeyer flask.Twenty-fiveni. of 5N HN03was added to the sample. The flaskwas sealed and placed on a mechanical shaker at low speed fortwo hours. The leachate was quantitatively transferred to a50-mL polyethylene centrifuge tube using three distilled waterrinsings of the Erlenmeyer flask. The sample was then centrifugedat 2500-3000RPM' sfor 20 minutes to separate the suspendeds i 1ica materi a1 from the leach, thereby preventi ng an interferencein the flame and flameless AASdetermination of the analytemetal s. The leachate was quantitatively transferred to a 50-mL polyethylene volumetric flask and made to volume with distilledwater. This leachate was analyzed for all metal s (except Hg)using fl ame or fl ame1ess MS. Hg was determined on a one-gramaliquot of theori gf na1 sample by cold vapor AAS.

b. Total DigestionA ten-gram subsample of the dried sediment (as

prepared above for "parti al" df gesti on) was si eyed through a100 mesh stainless steel screen (ATMCorporation, Milwaukee,Wisconsin) using an ATMSonic Sifter. A five-gram subsampleof the preground, presieved sample was weighed into a 250-mLTeflon beaker. Twenty-five nt. of concentrated HC1was addedto the sample, and the beaker was covered with a Teflon watchglass.The sample was placed on a hot plate (90-100°C) for one hourto digest. Following the Hel digestion, the sample was allowedto coolon a clean bench and 15 mLof concentrated HN03wasadded. The beaker was then returned to the hot plate and heated

3.3-7

(90-l000e) for 45 minutes. The beaker was removed and all owedto cool before addi ng 25 ml of 48 percent HF to di srupt thecrystalline lattice of the sediment. The sample was returnedto the hot pl ate for a thi rd ti me and heated for two hours.After this final digestion, the sample was cooled and quantitativelytransferred to a 50-mL pOlyethylene volumetric flask. The beaker

was rinsed three times with distilled water and the flask broughtto volume with distilled water.

All metals (except Hg) were determined by flameor flameless MS. Mercury (Hg) was not determined on this totaldi ges.tate.

2. Suspended Particulate Mattera. leach Procedure for Adsorbed Elements

The Nucleopore filters (0.4 ~m, 47 mmpolycarbonatemembranes) were stored in a desiccator for at least 24 hoursto maintain a constant weigh1; and the Nucleopore Swin-lok membranefil ter holders were cl eaned in 8N ni tri c aci d for four hours,.rinsed with distilled water, and dried. Each filter was thenpreweighed on a clean bench using Teflon-coated forceps andloaded into the filter holder. The loaded filter holder wasthen sealed in a polyethylene bag for shipment to the collectionsite.

Upon arrival at the laboratory, each used Nucleoporefilter was removed from its filter holder on a clean bench usingTeflon-coated forceps. The filter was placed ina desiccator(over si 1i ca gel) for 48 hours to dry. Once it had dri ed toa constant weight, the filter was weighed on the microgram balance(four decimal places) so the mass of the suspended particulatematter could be determined.

On a clean bench, the dry Nucleopore filter wasplaced in a 125-ml polyethylene Erlenmeyer flask and 50 ml of

3.3-8

25 percent (v!v) acetic acid was added. The flask 'was sealedto prevent contam; nati on and then 1'1aced on a shaker for twohours at a low speed to continue leaching. Using Teflon-coatedforceps, the fi 1ter pad was removed from the Erl enmeyer f1askand positioned over a 100-mL Teflon beaker. The leach acidwas then poured through the Nuc1eopore fil ter and collectedin the Teflon beaker. The Erlenmeyer flask was rinsed threetimes with distilled water and poured through the filter. Thefilter was then rinsed twice with distilled water and the rinseadded to the Teflon beaker. The fi1 ter pad was then storedin a 2" x 611 "Zip-lock" polyethylene bag for later digestionby the ri gorousmethod (only 10 percent of samp1es underwentrigorous digestion). The Teflon beaker waS placed on a hot

1'1ate with low heat (approximately 100°C) and the sample concentratedto less than 10 ml, cooled and quantitatively transferred toa 10-ml volumetric flask. Distilled water was used to makethe f1ask to the· mark after 0.050 ml (50 lJL) of Suprapur HN03was added to maintain the elements in solution.

This solution was then used to determine thedifferent analyte metals using flame, nameless, or cold vapor(Hg) AAS. The concentration of the different elements determinedthe method of AASanalyses. A I-mL aliquot of sample was removedfor mercury determination.

b. Rigorous Digestion for Total MetalsAfter the above leaching procedure, the refractory

matter remaining on the Nucleopore filter was removed by placingthe filter pad (using Teflon-coated forceps) into an all-Teflonbomb, adding 750 lJL of concentrated Suprapur HCl and sealing.After digestion of the sample for two hours in a steam bath(90-l00°C), the sample was cooled and the bomb opened on a cleanbench and 250 lJL of concentrated Suprapur HN03was added. The

3.3-9

bomb was resealed and returned to the steam bath for 30 minutes.The bomb was again removed from the water bath, cooled, openedo.n the cl ean bench, and 50 J.lL of concentrated HF was added.The bomb was resealed and returned to the steam bath for onehour. After allowing the bomb to cool, the digestate was quantitativelytransferred to a 10-mL volumetric flask. The bomb (cap andcylinder) was rinsed three times with distilled water. Therinsings were added to the volumetric flask and distilled waterwas used to make it to 10 rnL.

The concentrations of analyte metals in thisdigestate were determined by flame or flameless MS. Hg wasnot to be determined on this aliquot.

3. Epibenthi c .

a. Microdi~estionDue to the varied number and small quantity of

some species collected, a microdigestion procedure using HN03/H202was developed.

One gram (when available) of the wet tissue was

wei ghed into a speci ally designed di gestion tube (28-mmx 135-mmglass tube with a 24/40 ground glass joint). On a cleanbench, three nt. of Suprapur HN03and one nt. of H202 (30 percent)was slowly added to the digestion tube to prevent foaming.

The tube was loosely sealed with a small polyethylene beakerto allow for escaping gases. The tube was placed in a waterbath (95°C) and digested for six hours. Care was taken not

to allow samples to evaporate to dryness by adding distilledwater or HN03as needed. The di gesti on tube was removed fromthe water bath and allowed to cool. Thedi gestate was filteredinto a 10-mL vol umetri c flask usinga preri nsed (1 percent HN03)glass fiber filter (Reeve Angel). The digestion tube was rinsedtwice with distilJed water and rinses added to the 10-mL volumetric

3.3-10

flask. The flask was brought to the mark using distilled .water.This solution was then used to determine the different analytemetals using flame~ flameless, or cold vapor (Hg) AAS. The

concentrati on of the di fferent el ements determi ned the methodof AASanalysis.

b. Macrodi~estionWhen a greater number of the same epibenthic

speci es was co11ected, a multiash~di gesti on procedure was fo11owed.Experience indicated that this procedure provided the optimumconditions for recovering both volatile (Cd, Pb, Zn) and nonvolatile(Fe, Cr, Ni. Ba,Cu) elements from biological tissues. Thelow temperature asher completely destroyed the sample matrixat temperatures «ISO°C) compatible with retention of the volatileelements. Digestion of the ash in a closed Teflon bomb ensuredthe complete solubi Hzati on of the more refractory elementswhile retaining the more volatile.

Approximately 10 to 20 grams of the thawed epibenthicsample was weighed into a tared freeze-drying fla.sk. The samplewas freeze-dried and reweighed to determine the weight loss.

The sample was then placed into a homogenizingfl,ask and homogenized using a Yirtis "45" Homogenizer (The YirtisCompany, Inc., Gardi ner, NewYork) to ensure complete mixi ngof the sample. Approximately 0.5 grams of the finely groundsample was weighed into a tared Pyrex ashing boat. The boatwas placed into the low temperature asher (LTA-505, LFE Corp.,Waltham,Massachusetts) and ashed for 16 hours at 500 wattsof forward power using an oxygen plasma. The ashing boats wereremoved from the asher and 1 mL of 70 percent Suprapur HN03was added to solubilize the ash and retain it in the ashingboat during transfer to a clean bench. After allowing the ashto dissolve, it was quantitatively transferred to a Teflon bomb

3.3-11

using distilled water. After adding three additional millilitersof Suprapur HN03to the Teflon bomb, it was sealed and placedin a steam bath at 90-100°C for two hours. Once the samplehad been completely solubilized, the Teflon bomb was removedto a clean bench and the contents quantitatively rinsed intoa 15-mL pOlyethylene centrifuge tube using two or three rinsings(both cap and cylinder) of distilled water. To remove suspendedsilica material that would seriously affect the atomic absorptionanalysis (flame or flameless), the sample was centrifuged at2500 to 3000 RPMfor 10 minutes. The supernatant was decantedinto a 25-mL polyethylene vol umetric fl ask without the precipitate.Then the precipitate was rinsed with 2 mLof distilled wa.terand centri fuged again. The rinse was added to the vol umetricflask and made up to volume with distilled water. This solutionwas used for all metal analyses except Hg.

c. Mercury in Epibenthic TissueA one-gram aliquot (when available) of the wet

tissue sample was accurately weighed into a reaction vessel.Five nL of HC104:HN03·(5:1) and one nL of KMn04(5 percent solution)were added to the vessel. The vessel was sealed, shaken fora few minutes, and placed in a water bath at 75°C overnight.After removing samples from the water bath, the samples areallowed to cool to room temperature. Nex~ 5 mL of Hg-free deionizedwater was added to the reaction vessel followed by one mLof50 percent hydroxylamine hydrochloride:. The sample was shaken,5 percent stannous chloride was added, and the reaction vesselwas connected to the cold vapor analytical train. The Hg waspurged (N2) out of the sample and into a chamber where the 11ghtabsorption occurs relative to the concentration of Hg present.Hg was quantitated by the method of additions using spiked samplesof the material being analyzed.

3.3-12

4. MacrocrustaceaBefore dissecting, the shrimp and crab samples were

weighed and measured. Only muscle tissue was used for the shrimpand crab samples. The tissue was removed with Teflon-coatedforceps and stainless steel surgical scissors after the specimenhad been thawed. The excised tissue was placed in a tared fre·eze-

dryi ng flask and weighed. The sample was then freeze-driedand reweighed to determine weight loss. The freeze-dried ti.ssuewas thoroughly ground in a Virtis homogenizer and stored ina polyethylene bottle. A 0.5-gram aliquot of the finely ground

homogenized sample was weighed into a Pyrex ashing boat. Fromthis point, the sample was aShed, di gested, and analyzed accordi ngto the procedure given for epibenthic analyses (macrodigestion).

Hg was determined on a separate tissue aliquot bythe cold vapor AASmethod used for epibenthic samples.

The remaining metals were determined by flame or flamelessAAS.

D. Analytical Parameters and Qual ity Assurance1. Sediments

A standard reference material was prepared by the5N HN03"parti al" di gestion procedure and analyzed for the 13

analyte metal s; National Bureau of Standards, Standard ReferenceMaterial 1645, River Sediment, was prepared and analyzed forthe 13 metals even though Al, Ba, and Sr concentrations werenot reported for the NBSSRMRiver Sediment.

Table 1 summarizes the results of the analyses ofNBSSRMRiver Sediment using the partial digestion procedure.

The NBSSRM,River Sediment, was used to calibratea homogeneous sediment sample that was prepared and routinelyanalyzed with the sediment samples as a quality control.

2. Suspended Particulate r~atter (SPM)

Standard reference samples are not available for thesesample matrices. Spiked membrane filters processed by the procedure

3.3-13

ReportedConcentrationDeterminedConcentration

n = 7

~ % Recovery(.oJI•....~

-xsd-xsd

TABLE 1TRACE METAL CONC ENTRAT IONS AND PERCENT RECOVERY IN NBS

SRM 1645 RIVER SED IMENT* (~g/g dry wt. )Al !!L Cd Cr** Co Cu Fe** ..1JL Mn !!L .J!L Sr -1!LNR NR 10.2 2.96 8*** 109 11.3 714 785 1.1 45.8 NR 1720

1.5 0.28 NR 19 1.2 28 97 0.5 2.9 1692624 20.2 7.23 2.26 11.1 84.2 3.94 710 398 0.69 23.7 586 1519

45 6.7 0.44 0.06 1.1 2.8 0.16 30 8 0.05 1.0 31 24

71 76 138 78 35 99 51 63 52 88

* by partial digestion procedure** weight percent***value not certifiedNR = not reported

described for SPMwere used to evaluate the procedure for SPMand as quality control samples.

3. BiotaNational Bureau of Standards, Standard Research Materi al

1577, Bovine Liver, was prepared and analyzed using the methodologiesdescribed for macrocrustacean and epibenthic analyses to eval uatethese procedures. A large homogeneous sample of shrimp tissuewas prepared and periodically analyzed (spiked and unspiked)as a means to quantitate the'macrocrustacean data (method ofadditions) and to act as a routine quality control.

Table 2 summarizes the results of the analyses ofNBSSRM1577, Bovine Liver.

3.3-15

*value not certifiedNR=not reported

TABLE 2TRACE METAL CONCENTRATIONS AND PERCENT RECOVERY IN NBS SRM 1577

BOVINE LIVER (1l9/9 Dry wt.)

III. RESULTSANDDISCUSSION

A. Surficial SedimentsWhenperfonning baseline surveys for environmental monitoring

to detect possible pollution events in the future, it is necessaryto consider an possible inputs to the study area. This willallow a consideration of the natural variability that must beconsidered during the monitoring effort. The inputs may be fromterri genous sources which would include both natural and anthropogenicinput (i.e., pollution of riverine inputs), or the inputs maybe strictly from anthropogenic sources (Le, offshore oilfields).

The West Hackberry brine disposal site can be influencedby the outfalls of the Mennentau, Atchafalaya and MississippiRivers. Major offshore oil fields to the east and southeast can

. also impact the disposal site since the longshore current generallyflows from east to west in this area. The Weeks Island disposalsite will be influenced by th-e Atchafalaya and Mississippi Riversand the offshore oilfield to the south and east. Table 3 summarizesthe seasonal trace metal character of the surfici al sedimentsfor the West Hackberry and Weeks Island disposal sites. Datafrom the West Hackberry site in fall 1977 and winter 1978 {Shokes1978) are also included for comparison.

At the West Hackberry site, there are generally higher tracemetal concentrations in the summer, but these appear significantonly for Ba, Cd, and Hg. The higher Sa in the summer may resultfrom a redistribution of sediments from the oilfields where BaS04from dril1ingmuds is pres.ent in the sediments. CadmiumandHg may be from river pollution or from the proximity to Cameron,Louisiana with its sources of industrial pollution.

West Hackberry sediments appear to be relatively homogeneous(low coefficient of variation - CV) with respect to trace metals

3.3-17

TABLE 3. SEASONAL COMPARISON OF AVERAGE TRACE METAL CONCENTRATIONS IN SURFICIALSEDIMENTS FROM WEST HACKBERRY (A) AND WEEKS ISLAND (B) DISPOSAL SITES"g/g dry weight

AI Ba Cd Co Cr Cu Fe' Hg Mn NI Pb Sr Zn-Site A Summer X 2080 94 0.167 5.13 8.76 9.36 0.709 0.447 403 8.87 14.4 54 31

. (W. Hackberryl n-7 CV'J(, • 22 14 17 10 29 24 . 19 27 27 15 25 47 13w ,. Winter X 2532 39 0.060 4.67 6.35 7.45 0.816 0.059 441 9.06 15.1 42 38wf n=8 CV'J(, 23 8 28 6 24 34 16 21 31 18 24 20 16•....en X 0.012 306 6.19 5.74 27 22Site B Summer 819 37 0.052 4.74 6.01 1.98 0.463

(W.lslandt n-7 CV% 16 45 37 6 17 40 10 39 12 8 22 39 8

Winter X 1056 21 0.014 4.25 3.04 1.04 0.483 0.019 222 7.05 4.71 14 26n-8 CV'J(, 11 18 16 8 7 31 12 33 '3 9 21 17 6

Site Alii Fall 1917 X 1380 N/D 0.067 N/D 2.41 6.60 0.418 N/D 334 4.54 14.2 N/D 21.3W. Hackberry n =12 CV'J(, 15 13 17 . 23 13 19 11 16 10

Winter 1978 X 885 N/D 0.058 N/D 2.14 5.71 0.390 .0163 314 5.18 13.8 N/D 19.9n =13 CV'J(, 19 26 24 29 21 33 32 20 23 14

!concentration In 'tl> dry weight

(1) Shokes. 1978 Table 3.3-2, p 3-251

in both the summer and winter. However, Sr is more variablein the summer even though its concentration is similar in bothseasons. The higher concentratons of metals relative to theWeeks Island site are in line with the sediment texture. TheWest Hackberry site is mainly silt and clay with a high organiccarbon content. Clays and organic materials tend to adsorb andcomplex metal ions and would be expected to have higher metalconcentrations. Sediments from the Weeks Island site are predominatelysilty sand with a low organic carbon content. This is reflectedin the lower metal concentrations observed in these samples.

A compari son of the West Hackberry data with that from Shokesindicates there are generally higher metal concentrations inour data. These differences appear to be significant for Alin the summer and winterand Cd in the sunmer. The more concentrated'

leaching solution (SN HN03) used in our study may account forthe relatively high metal concentrations reported. However,this would not account for the higher Al and Cd concentrations.

Homogeneity of the sediment as measured by the XCVare very

similar for our winter data and Shokes' winter data. The summersediments appear to be sl i ghtly less homogeneous than what Shokesfound in his fall sediment samples. Sediments from the WeeksIsland disposal site do not show any significant seasonal variationsin their trace metal composition. There is less homogeneity(higher CV) for Ba, Cd, Mn and Sr in the summer than the winter.This could be the result of less mixing of bottom sediments duringthe summer months as opposed to the more dynamic system causedby winter storms.

Another technique for determining future abnormal tracemetal inputs to the brine disposal sites is to construct scatterplots of the ambient metal concentrations versus the Fe concentration

in the surficial sediments. Since Fe is in relatively high concentration

3.3-19

when compared to the other transition metals, any pollution eventwould not seriously alter the Fe content of the sediments. Itwould however cause a significant increase in the other metalconcentrations (i.e., pOllution) relative to the Fe. Shokes(1978) has used this technique with 95 percent confidence intervalsabout the best-fit linear regression line to detennine abnonnaltrace metal inputs to the proposed disposal areas.

Figures 4 through 15 are scatter plots for each of the metalconcentrations versus the Fe concentrations for the West Hackberrydisposal site during the summer and winter crui sese Figures16 through 27 are similar scatter plots for the Weeks Islanddisposal site. Shokes' linear regression lines for his winter1978 sampling have been included on some West Hackberry plotsfor comparison purposes.

Examination of Figures 4, 8, 9, 10, 11, 12, 13, and 15 forthe West Hackberry site show there is good correlation for Al,Cr, Cu, Hg, Mn, Ni, Pb, and Zn in both the summer and winterseasons. There is good correlation for Cd (Figure 6) in thewinter, but in the summer there is a group of samples whose Cd/Feratios are dissimilar to the other samples at this site. Eliminationof this group improves the correlation coefficient (I': Y =-0.21X-

0.02, r2 = 0.997). Elimination of 50 percent of the data paintsis justified because (1) a similar occurrence was noted at theoriginal Weeks Island site (Shokes 1978) and (2) the slope ofthe new regression line is similar to Shokes. Also, it is interestingthat the magnitude of this aberrant group is similar to thatin Shokes' report even though the locations are different.

Barium and Sr did not correlate with Fe in the summer, butSr had good correlation in the winter. These are Group ItA,alkaline earth metals, and would not necessarily be involvedin the same geochemical mechanisms or fluxes the transition metals

3.3-20

would be. Both of these metals would be present in calcareousshell materials and also as potential pollutants from offshorepetroleum drilling and production activities to the southeastof the West Hackberr-y disposal site. Longshore currents couldbe influxing contaminating sediment from the oilfield into theWest Hackberry site.

Compa rison wi th Shokes' sediment data from the wi nter of1978 indicates close similarities in Al, Cd, Cr, Cu, Ni, andZn (Figures 4, 6, 8, 9, 12, and 15, respectively). Lead (Figure13), however, appears to be dissimilar in the summer and winterseasons as there is a difference in the slope of the regressionlines compared to Shakes' data. This would suggest a differentsediment texture since there is still good correlation with Fe.

Figures 16 through 27 for the Weeks Island disposal siteshow good correlation for all metals except Hg and Ni duringthe winter season. Generally, the correlation with Fe was poorduring summer for all metals except Co and Cr. There were evennegative correlations for Cd and Hg. Elimination of two highvalues improved the correlation (r2 = 0.634) for Cd. Mercurycorrelation was not improved by selective removal of high values.These data suggest there are seasonal trace metal inputs to theWeeks Island site duri ng the summer thatdi sru.pt the naturalconcentrations present in surficial sediments. This input wouldprobably be from the Atchafalaya River, Mississippi River orthe offshore oil fiel ds to the south and east of the disposalsite.

It is interesting that other investigators (Trefry and Presley1976) have found significant inputs of Pb and Cd to the Gulfof Mexico by the Mississippi River but no significant increasesin Mn, Co, Ni, Zn, Cr, or Cu. This leaves the offshore oilfieldsas suspect in causing the perturbations in the sediment trace

3.3-21

metal burdens duri ng the summer.Concentration of trace metal s are related to the amount

of fine grain (i.e., clay) materials in the sediments. Claymateri al s have naturally higher trace metal concentrations thancourser sediment particles because the finer grain particleshave larger surface areas and, therefore, more adsorption sitesfor binding metals. Abnormal trace metal inputs (i.e., pOllution)to sediments also tend to be associated with the fine grain fractionof the sediments. The relationship between the grain size (ttClay)

and the trace metal content of the sediment can be used to determinethese abnormal trace metal inputs to the sediments. Figure 28is a scatter plot of Fe versus ttClay in the Weeks Island samplesduring the sununerseason.

Iron should be representative of the other transition metalswith respect to the rel ationship between metal content and %Clayin the sediment. Iron, being in relative higher concentrationin the sediments, -would not be i nfl uenced by anthropogenic inputs.

However, Fe is a transition element and should have similar chemicalbehavior in the sediments as the other transition metals.

The Fe versus ttClay correlation ts relatively weak (1'2 =0.322) at the West Hackberry site. This is thought to be causedby the limited number of samples (i .e., data points) used inconstructing the scatter plot and the homogeneity of the sedimentswith respect to the ambient Fe concentration. Other metals,except Ba, Cd and 51", correlated well (1'2 ~ 0.5) with %Clay.This would be further evidence that there is an abnormal inputof Ba, Cd, and 51" to the West Hackberry site during the summer.

Correlation of Fe versus' %Clay at the Weeks Island siteis low (r2 = 0.173) but may be the result of a small samplingpopulation since the scatter is minimal (i.e., very homogeneous).Cadmium, Al, andMn have correlations similar to Fe. However,

3.3-22

COt Ni t and Zn were not correlated (i.e. t negative or weak correlations)with the clay fraction. The remaining metals (Ba, Crt Cu, Pb,Sr, and Hg) appear to have good (r2 ~ 0.5) correlation.

It was mentioned earlier that Co correlated well with thehydrous Fe fraction of the sediments (see Fi gure 19). This woul dleave Zn and Ni as being possible pollutants at the Weeks Islandsite during the summer.B. Suspended Particulate Matter (SPM)

Table 4 summarizes the SPM trace metal concentrations byseason.

The particulate loading (mg/L) appears to be similar inthe sunmert fal't and spring seasons. The winter season hasa slightly higher loading at both the Weeks Island and West Hackberrysites. This woul d be expected because of the more dynamic systemcaused by wi nter stann fronts.

This higher winter loading is also reflected in the higherAl and Fe concentrations for this season. This is the only detectabletrend noted in the SPM data. These higher Al and Fe concentrationswould be indicative of resuspended surficial sediments duringthe wi nter.

No significant differences in trace metal concentrati-onswere apparent for the West Hackberry and Weeks Island sites.C. Biota

1. MacrocrustaceansFive different species of shrimp were collected at

the West Hackberry and Weeks Island proposed disposal sites duringthe four sampling seasons. The trace metal concentrations inthe various species are summarized by season for the West Hackberryand Weeks Island disposal sites in Tables 5 and 6, respectively.

At the West Hackberry disposal site, there were adequatenumbers of Penaeus setiferus in all four seasons to describe

3.3-23

TABLE 4. MEAN TRACE METAL CONCENTRATIONS (lJ9/L) AND MEAN PARTICULATE ( mg/L _HOH ).BY SITE IN SUSPENDED PARTICULATE MATTER

PartlculataCruise Site T9/L HOH AI 8a Cd Co C, Cu Ffl Hg Mn Nl Pb 5r ZnI X 32 0.7 0.009 0.15 1.38 0.50 35.9 NO 12.8 3.5 0.84 NO 1.4Summe, A 6.86 CV" 102 65 265 55 96 125 130 52 193 102 98

N-7

X 36 0.2 0.011 0.17 0.95 0.111 3.9 NO 1.1 0.7 0.29 0.01 0.38 5.13 CV,," 103 109 178 60 108 138 123 87 100 228 17\ 265

N-7W ~ 18 0.2 NO 0.03 NO 0.64 30.2 0.39 8.9 0.3 . 0.2\ 0.23 NO.W A 5.01 CV" 215 101 138 135 220 190 62 211 114 761 II N-7N.po. Fall

~ 5 0.3 0.009 0.02 NO 0.65 5.9 . 0.35 8.5 0.2 0.51 0.32 30.8B 7.18 CV"" 30 83 265 78 162 147 70 28 77 98 57 231

N-7

X 63 0.5 0.046 0.12 0.65 0.19 127 NO 1t.5 1.3 0.52 0.84 NOA 20.78 CV'll. 109 220 178 182 108 129 122 120 151 12\ 88

III N-8Winta,

X 45 2.4 0.037 0.09 0.47 0.60 95.4 0.01 8.8 2.6 1.63 0.78 1.78 13.17 CV'll. 3J 120 75 123 146 163 68 265 40 83 155 39 265

N-7

~ 4 1.0 0.029 0.02 1.10 2.18 34.4 0.02 0.7 1.5 0.78 0.35 9.0A 7.00 CV'll. 124 151 96 185 IOS 196 209 100 1110 121 243 39 265

N-7IVSpring X 2 5.2 0.295 NO 1.66 2.15 19.3 0.02 0.3 1.3 1.25 0.35 33.4

8 9.20 CV"" 145 82 227 86 265 41 133 265 130 247 58 129N-7

N -' number 01 .amples averagedNO - Nona Detected

TABLE 5. SEASONAL TRACE METAL CONCENTRATIONS (Vg!g dry weight) IN MACROCRUSTACEAFROM WEST HACKBERRY (A) PROPOSED DISPOSAL SITESCruise Species AI Be Cd Cr Co Cu Fe Pb Mil tlg Nt Sr Zn--

Penaeus 8zlocus X 31 49 0.17 0.17 <0.30 26 48 <0.09 4.9 0.086 0.70 78 62CV'll> 62 75 33 66 18 67 60 21 38 24 20n ~ 5123'"

j

Summer P. selilerus X 21 1.6 0.11 0.17 0.37 34 41 0.10 4.9 0.109 1.30 50 70CV% 43 81 76 49 48 10 48 13 60 63 78 9 4o a 61111"

P. azlecus X 108 1.2 0.01 0.34 <0.30 21 148 <0.09 8.6 0.099 1.10 99 61CV%

" o a 116'"Fall

w P. sellferus X 37 62.1 0.05 0.34 <0.30 28 49 <0.09 4.1 0.084 0.78 62 63

" CV% 92 80 47 53 14 96 69 19 .,2 20 8w n a 4117'"IN X 40t11 P. seliferus 59 2.1 0.19 0.62 <0.30 36 45 0.61 1.7 0.093 0.85 128

CV% 34 25 72 114 10 45 35 54 44 55 12 3III 0-6163'"Wlnler

Tr8chypenaeus slmllis X 71 2.8 0.46 0.36 <0.30 22 47 3.19 2.7 0.018 1.62 198 43CV"'" 74 98 64 81 44 64 194 40 21 128 21 4n -7146'"

Xlphopen8eus "rovetl X 63 2.4 0.36 0.36 <0.30 28 31 0.91 2.9 0.000 0.47 215 41CV% 47 73 94 8.2 25 54 138 81 20 31 57 11o a 6116'"

P. ezlecus X 54 1.3 0.32 0.34 <0.30 26 23 <0.09 1.3 0.040 1.01 166 44CV%

IV 0- 1111"Spring

P. sollforus X 64 1.J 0.47 0.33 <0.30 25 45 0.24 1.9 0.019 1.13 135 50CV% 29 37 123 25 11 63 60 64 36 87 10 2n-51211"

" n - number 01 Samplos onalyzed I , a number of Individuals

TABLE 6, SEASONAL TRACE METAL CONCENTRATIONS (llg!g dry weight) IN MACROCRUSTACEAFROM WEEKS ISLAND (B) PROPOSED DISPOSAL SITES

Cruls. Specie, AI 8. Cd C, Co Cu f. •••• Mn ~ HI S. Zn---Ponaeu. __ztecul X 25 IU 0.11 0.11 <0.30 35 35 <0.00 4.9 0.012 0.94 15 82

CV% 69 221 31 46 12 68 61 32 63 21 3I n - Gllll'Summer

I'•••• eu ••• ," ••••• j( IS IS IS IS IS IS IS IS IS IS IS IS ISCV%n-te2l'

P .• z'ecu. X 19 22.3 0.03 0.19 <0.30 30 32 <0.00 4.4 0.081 1.<16 12 62CV'lIo 38 B9 24 40 12 25 42 14 60 10 •II n -61281'

f.nT,achypenaftU. consfrictul R 38 2.4 0.11 0.11 '0.30 18 13 0.12 1.5 IS 2.51 100 51

CV'lIon - 1131'

W P. adM;US 1I 58 1.2 2.01 0.68 <0.30 52 34 0.29 l.II IS 5.44 158 43•W CV'lIoI n-IIII'N ;rm 1'. nlll.lU. 42 2.0 0.31 0.69 <0.30 35 28 0.29 0.85 0.044 1.17 114 43

CV'llo 18 81 87 eo 15 35 91 74 20 85 14 3III n -11611'Winter

r. conlirleful R 113 2.8 0.02 0.13 <0.30 21 19 8.38 <0.30 IS <0.39 242 43.0CV'lIon -IIW

7•• 1mNl. X 390 '.4 0.80 3.19 <0.30 .2 122 5.84 <0.30 IS 2.98 315 41CV'lIon- 111I'

Xlphop••••• us k,oyerl ii 18 2.4 0.32 0.60 <0.30 31 21 2.49 0.9 IS 2.51 179 39CV'lIo 100 80 61 90 14 24 116 59 95 42 IIA-3131'

PenaeUlletUeru. X 52 1.3 0.13 . 0.50 <0.30 29 39 1.05 U 0.132 0.98 114 52CV% 28 42 69 38 8 32 III 43 38 <16 11 4n" 41131'

IV Tr.chypeneeus con •• rlctUI R. 68 2.8 1.30 0.35 <0.30 21 70 0.38 2.2 0.103 0.85 200 47Sp.lng CV'lIo 29 48 173 18 22 40 99 28 19 eo 21 5

n -1(811'

Trachypenl""" almHi. X 120 5.0 0.41 0.51 <0.30 11 94 0.88 2.6 <0.006 1.25 358 40CV'lIo 65 58 89 39 30 83 128 17 40 50 11n - 61131'

IS - In.ullk:lent aamp'.•.• numb., 01Nmptoa analy,ed I ) - number 0' individual.

the seasonal and intraspecies trace metal variability. Sufficientnumbers of Penaeus aztecus were collected in the sunmer seasonto descri be the intraspeci es variabi1ity but not the seasonal vari ability.Adequate samples of Trachypenaeus simil isand Xiphopenaeus kroyeriwere collected at West Hackberry during the wi nter season. Pivesamples of 1. similis were analyzed from the Weeks Island sitein the sprfn9...allowing for a seasonal comparison with those fromthe West Hackberry site in the winter. However, this would includeany site varfabili ty.

Table 5 shows an increase in Sa in!. setiferus duringthe fall season. This increase is an order of magnitude abovethe Sa concentration in the other three seasons and may be finegrain sediment contamination of the tissue. However, other metalconcentrations are not increased in these fall samples. Also,there appears to be a significant increase in tissue Pb and Srconcentrations during the winter and spring seasons.

Trace metal concentrations in P. aztecus from the WestHackberry site during the summer season have concentrations similarto!. setiferus. Other samples of !. aztecus from the fall andspring seasons are not of sufficient sample size for evaluationand can only suggest possible trends.

Samples of T. similis and!. kroyeri (Table 5) collectedin the winter at the West Hackberry site have similar trace metalconcentrations as !. aztecus and!. setiferus except for a higherconcentration of Pb and Hg in T. similis. The variability (%CV)of Pb in the T. similis is rather high (194 percent) and shouldbe considered when evaluating this higher Pb concentration.Comparing these Pb and Hg concentrations with T. similis fromthe Weeks Island site during the spring (see later) suggeststhese are seasonal highs.

Evaluation of Table 6 for P. setiferus trace metalvariability at the Weeks Island disposal site shows there are

3.3-27

significant seasonal variations with Cd and Hg. It should bekept in mind that both these el ements are perhaps the most di fficultto analyze in tissue samples; these seasonal differences maybe more a reflection of the methodology than any real seasonalvariation. Also, Pb appears to have a significant seasonal variation,but there is also high variability (%CV)within a season. Theoverall comparison with P. setiferus samples from Table 5 (WestHackberry) during the winter and spring indicates similar tracemetal concentrations.

The trace metal data for P. aztecus from the WeeksI slaM site (Table 6) showed no seasonal di fferences betweenthe summer and fall for any metal. Comparison with t. aztecusdata from West Hackberry site (Table 5) indicates an increasein Sa during the summer at the Weeks Island site. However, thevariability is high (CV = 221 percent) for this particular sample.

Trachypenaeus constrictus data at the Weeks Islandsite (Table 6) i·ndicate that the sample size is sufficient onlyduring the spring sea.son (N=7). The variability (%CV)is highfor Cd and Hg in this species.

A comparison of T. constrictus with t. setiferus showsthe fonner to have a higher Fe and Sr content. This would haveto be considered in using this species for monitoring tissuetrace metal burdens.

The number of T. similis collected at the Weeks Islandsite was sufficient only during the spring season. A comparisonof this data with T. similis data from the West Hackberry site(Table 5) was made earlier.

Table 7 is a comparison of trace metal concentrationsin T. constrictus and T. similis with other studies perfonnedin the Gulf of Mexico. There appears to be higher concentrationsof Cd, Ni and Pb in our samples (T. simil is) when compared to

3.3-28

I

TABLE 7. COMPARISON OF SEASONAL VARIATIONS IN AVERAGE TRACE I~ETAL CONCENTRATIONSIN TRACHYPENEUS SIMILIS (SUGAR SHRIMP) AND T. CONSTRICTUS (BROKEN NECK SHRIMP)MUSCLE TISSUES (~g/g DRY WT) ~llTH OTHER GULF STUDIESCrul •• A' e. I.d Co C. Cu -.!!... -!.!!.....- ~ Nl I'b S. Zn

SPRB,I"" fan R 3lI 2.4 0.11 <0.30 0.71 " 13 IS 1.5 1.51 0.12 100 51. Oi.po.aI T•• omel n- "3" tV'll.

C•••••••• F.n1978·Sp.InO 1979 Wltl •., Jl 113 2.' <0.02 <0.30 0.13 21 19 IS <0.30 <0.39 '.3lI 242 4J

n· mi' tV'll.It,lchJritn •• ,,.

cOfttIttk.ut' Sp.lno Jl •• 2.' 1.30 <0.30 0.35 21 10 0.10:1 U 0.85 0.30 200 41n·'Ie1· tV'll. 29 48 113 18 22 40 29 29 110 99 21 5

Wln,ef Jl 110 2.3 0.110 <0.30 0.110 11 58 0.011 2.4 1.99 3.52 212 44'T'achWttfl''''' n-814W cv" III 81 15 155 82 89 21 55 10:1 165 11 5

""'"",1Sp'lno R 120 '.0 0.41 <0.30 D.•• 11 !14 <0.006 U 1.25 0." J56 48n - 511:11" tV')f, 85 511 89 39 3tI OJ 11 40 129 50 II

W Ii. 8uCt;loem' Fan NO 2.9 2.48 0.35 0.43 28.7 53.8 0.119 4.41 1.13 0.21 30 51W n-III83I' tv", 19 III 28 J4 J4 33 19 48 40 47 24 5I RN lTr.chypeM •••• Wthlet' NO 1.1 0.84 0.61 0.59 21.2 49.2 0.129 3.90 2.ll 0.49 44 48

I.D .Im"'" n • 23\19"; tV'll> 27 211 511 71 20 19 14 72 118 118 25 I

Spring It NI> 4.3 2.03 0.31' 1.04 33.4 61.3 0.164 US 0.1108 0.23 24 114n - 111611' CV')f, • 211 23 55 " II 19 39 62 27 15 3

MAFlARlg" 8elore R NO NO 0.0:1 NO 1.0 23 31 NI> NO 0.4 0.8 NO NOMonUorlng CV')f, 100 60 13 110 15 22tT,.divpltnNuI Outing It NO NO 0.04 NO 0.7 25 51 NO NO D.• 0.8 NO NO...-1 tv", 150 51 12 42 110 11

Art_ Jl NO NO 0.03 NO 0.2 19 23 NO NO 0.5 0.1 NO NOeV'l(, 81 50 II 17 290 «I

SPR e,lne:l R 45 NO 0.017" NO 0.131 11.8 55.8 NO 5.011 0.212 0.28S NO 110.2~'sposaf fexom. eV')f, 82 24 19 42 24 44 42 8Group Fe, tl77·Win."" 1978tTllChypene ••.••"' .•

I. Tilt.,.,. 1919.2• .4Ue.lndet,1911. beforl. durlng and •••••• er., 1o d,lning opel,lIons: ',om lillie 13.

p 68.3. Sholl e•• 1918, lummary 0' d,,'. 'Ot'W",t Heckbetry Controt n. labtc 3.3-0, p 3-47.'''n'' te nurnbor o' pooled hmpfe.:number In .1••totallndlvldue" .empted.'-onIV one "a'u.glven, other. wer. "not detected."ND •• not detttffnined.IS -Inevllle"'" •••••••••.

the SPR fall 1977-winter 1978 data. The.intraspecies variabilityis similar except for Pb in our study, which is higher.

Our Cd concentrations are higher than what was foundin the MAFLARig Monitoring Study (White et al. 1977), but the

other metal concentrations agree reasonably well.Comparison with data from the third year Buccaneer

Oilfield (BOF) Study (Ti1lery2 1980) shows that Hg is lower inour samples but Pb and Sr are higher. Also, the overall Fe concentrationmay be sli ghtly higher in our 'samples.

The higher Cd concentration in our samples may be dueto spacial or seasonal differences or possible contaminants.The recoveries obtained from HBSBovine Liver (Table 2) and thedaily Quali ty assurance program followed would suggest contami nationis not the problem unless it occurred duri ng sampli ng.

2. EpibenthicTwo species of epibenthic organisms were to be sampled

at the West Hackberry and Weeks Island disposal sites. The seaonion, Paranthus rapiformis, and the sea worm, Chaetotterus sp.,were selected because of their availabili~ at the proposed disposalsites during previous sampling efforts.

Heither of these speci es nor any other epibenthic organi smswere found at the West Hackberry si te duri ng the summer season.At the Weeks Island site, five different epibenthic samples werecollected during the summer. However, the numbers of each speci escollected were low and none were sea onions or sea worms (seeTable 8 for epibenthic organisms collected by season).

Table 9 is a summary, by season, of the mean tracemetal burdens in the various epibenthic organisms collected atthe West Hackberry disposal site. Portunus gibbesii was theonly species commonto more than one season. Comparison of thesummer and winter data for this speci es shows higher concentrations

3.3-30

TABLE B. SPECIES OF EPIBEMTHIC ORGANISMS COLLECTED BY SEASON AT WEST HACKBERRYAND WEEKS ISLAND PROPOSED DISPOSAL SITES

w.WIW•.....

Summer (I)

(None collected)

SITE A - W. HACKBERRYFall (II) Winter (III)

Portunus gibbesii Portunus gibbesiiPolinicies duplicatus.Busycon contrariumThais haemostomaCantharus cancellarius

SITE B-WEEKS ISLAND

Spring (IV)

Callinectes sapidus

Dinocardium robustrumPersephona aquilonarisEchinodermata sp.Pagurus pollicarisPolinicies duplicatus

Portunus gibbesiiCallinectes similis

Portunus gibbesiiPersophona aquilonaris

Portunus gibbesiiCallinectes similisCallinectes sapidus

TABLE 9. TRACE METAL CONCENTRATIONS (~g/g wet weight) IN EPIBENTHIC ORGANISMSBY SEASON AT THE WEST HACKBERRY PROPOSED DISPOSAL SITESeason Species AI Ba Cd Co Cr Cu Fe Hg Mn Ni Pb Sr Zn

Summer (none collected) X(I) CV%

Portunus gibbesii X 347 115 0.46 2.57 1.12 6.00 182 IS 18.0 2.87 2.33 20.2 14n-2 (10)· CV% 15 66 11 90 29 23 34 72 60 76 141 8Polinicies duplicatus X 31.6 12.5 0.13 <0.14 0.27 10.6 37 0.011 3.6 0.45 0.14 0.37 19w n==1 (6)" CV%.

wI fall Busvcon contrarium X 80.6 12.1 0.70 0.30 0.39 4.98 88 <0.006 2.8 0.39 0.34 <0.12 28wN (III n=1 (21" CV%

Ibi!i.l> baemostoma X 93 19 .0.86 0.38 0.74 5.07 137 0.014 6.04 0.67 0.44 3.96 33n-4 (191· CV% 20 16 59 10 51 12 17 35 16 28 20 12 5Cantharlls cancellariusX 60 32 1.63 0.40 0.74 17.0 75 IS 8.54 0.52 0.33 <0.12 21n •• 2 /21· CV% 3 33 15 46 . 50 134 7 7 19 24 55

Winter Portunus gibbesii ~ 13 9.9 0.85 0.57 0.77 17.8 52 0.016 11.8 1.06 1.31 54 9.111I11 n-8 (1251· CV% 43 33 36 28 94 28 62 66 32 100 80 9 35

X \

Spring Callinectes sapidus·· 640 157 2.17 0.62 1.20 244 893 0.044 99.4 3.31 2.65 580 81IIVI 0=7 /31/* CV% 23 33 30 59 32 17 36 12 . 71 44 21 6 10

• n = number of samples analyzed ) •• number of individuals•• concentration in dry wllightIS - insufficient sample

of Al, Ba~ Co, and Fe during the summer. These differences maybe due to incorporation of fine grains of sediment into the tissuesrather than actual biochemical uptake.

Examination of the mean trace metal concentrationsin the other species listed in Table 9 indicates there are wideranges of various metals in these different species. Since thetotal number of individual species analyzed are low, these concentrationsonly suggest what the normal ambient levels should be. A largersample pool for each species is needed before statistical evaluations,that woul d adequately describe the burden and normal intraspeci esvariations of trace metals in these organisms, can be perfonned.

Table 10 isa seasonal summary of the trace metal concentrationsin the epibenthic organisms from the Weeks Island disposal site.The summer seasons did not produc.e large numbers of anyepibenthicorganisms suitable for ~nitori ng trace metal burdens. Fivedifferent organisms were sampled during this season, but thetotal number of individuals analyzed were insufficient for adequatestatistical treatment. The mean concentrations of the 13 analytetrace metals for each species are given in Table 10 as indicatingwhat levels can be expected in each species.

In the fall, winter and spring seasons, sufficientnumbers of 1:. gibbesii were collected at the Weeks Island siteto give some idea as to the suitability of this organism formonitoring trace metal burdens. There does not appear to beany large seasonal variations in the trace metal concentrationsin this species, but the variability (%CV) is higher for Al,Cu, Fe, Hg, Mn, Sr and Zn during the fall season.

Compari,son of the trace metal concentrations in 1:.gibbesi i from the wi nter crui se of the West Hackberry and WeeksIsland disposal sites (Tables 9 and 10) shows very similar valuesfor all trace metals analyzed. This is also true for Callinectessapidus at both sites in the spring.

3.3-33

Comparison of the trace metal concentrations in f..gibbesii from the winter cruise of the West Hackberry and WeeksIsland disposal sites (Tables 9 and 10) shows very similar valuesfor all trace metals analyzed. This is also true for Callinectessapidus at both sites in the spring.

The use of epibenthic organisms as monitors for tracemetal burdens at the disposal sites will be limited more by theiravail abil i ty than any i ntraspeci es variabil i ty in trace metalburdens. Intraspecies variability may be adjusted by increasingthe number of samples analyzed (but only if they are available).Mixing of different species will not be acceptable for makingup adequate sample sizes due to the high variability for certainmetals between species.

3.3-35

IV. CONCLUSIONS

A. West Hackberry Disposal SiteSurficial sediments from the West Hackberry site are relatively

homogeneous with respect to trace metals in both the summer andwinter seasons. There is an apparent input of Cd, Ba and Srduri ng the summer seaso~ that does not correl ate wi th the hydrousFe fraction (at three sampl ing stations for Cd) or the clay fractionof the sediments. Cadmium may be influxing from riverine orcoastal sources, whil e Ba and Sr are thought to be from the offshoreoil fields to the southeast of the proposed disposal site. Thesepossible sources of Ba, Cd, and Sr woul d have to be consideredin any future monitoring activities.

Comparison of our sediment data with previous sampling activitiesshows our results to be slightly higher for most analyte metals.This is thought to be caused by a strong leaching solution weused and not to any overall increase in sediment trace metalburdens. There does appear to be some changes in sediment texturesince the previous sampling program (winter1977~78) was conducted.

Suspended particulate matter loading was high in the winterbut lower in the other three seasons. Increased concentrationsof Al and Fe in the winter $PM suggest the increase is from resuspendedsediments. No other seasonal trends were apparent in the tracemetal SPM data.

Only!:. setiferus was collected in sufficient nurrtlersinall four seasons to describe both the intraspecies and seasonalvariabilities. There were increased concentrations of Ba inthe fall and Ph and Sr in the winter and spring. These seasonalvari ations woul d have to be cons idered in usi ng P. setiferusin a monitoring program.

Other speci es exami ned showed that T •.simil is had higherconcentrations of Pb and Hg than!:. setiferus. These may be

3.3-36

seasonally related. 1:. aztecus and!. kroyeri have trace metalconcentrations similar to P. setiferus.

No epibenthic samples were available at the West Hackberrysite during the summer. Five different speci es of epibenthicorganisms were collected in the fall but only,!:. gibbesii werecommon to another season sampling (winter). The number of samplesfrom these five species were not sufficient for adequate statisticaltreatment. 1:. gibbesii appears to contain higher concentrationsof Al, Ba, Co and Fe during the summer. This is based on onlytwo samples (10 individuals) collected during the summer season.These higher metal concentrations may be due to fine grain sedimentparticles in the tissues rather than biochemical uptake.

The availability of epibenthic organisms at this site willlimit their usefulness as organisms for monitoring trace metalaccumulations.B. Weeks Island Disposal Site

Surficial sediments from the Weeks Island site do not showany significant trace metal variation between the su.mmer andwinter seasons. However, there is less sediment homogeneityfor Ba, Cd, Mnand Sr in the summer season.

Correlation of metals with the hydrous Fe fractions in thesediments was good {r2 ~ 0.5) for all metals except Hg and Niin the winter. In the summer, correlation was poor for all metalsexcept Co and Cr. However, the correlation with the clay fractionof the sediments (summer) was good for all metals except Co,Ni and Zn. This would leave Zn and Ni as possible contaminantsin the sediments during the summer season. The offshore oil fieldsto the east and south of the proposed disposal site would bea possible source of this Zn and Ni influx.

Suspended particulate matter loading was higher in the winterthan the other seasons. Concentrations of Al and Fe were significantly

3.3-37

suggests the lncrease in SPMloadingNo other patterns in the trace

increased in the winter, whichis from resuspended sediments.metal data were noted.

There are seasonal variations in Cd, Pb and Hg concentrationsin P. setiferus, but high intraspecies variation for these metalsmakes seasonal vari ations suspect. Overall compari son of tracemetal burden for the winter and spri ng in f.. setiferus with theWest Hackberry. data shows the concentrations are similar.

Trace metal concentrations in P. aztecus showed no seasonaldifferences between the summer and fall seasons. These were

the only seasons adequate samples were collected.T. constrictus samples were adequate only in the spring

season. The intraspecies variability of Cd and Hg were highfor this species.

Comparison of T. constrictus with P. setiferus shows theformer to have higher Fe and Sr, which would have to be consideredwhen using T. constrictus in a monitoring program.

Comparison of T. simiUs and T. constrictus data from bothdisposal sites with data from other recent studies in the Gulfindicates our data are comparable with what other investigatorshave found in these species except for Cd, Hg, Pb and Sr. Concentrationsof Hg "are lower in our samples (T. similis) than other studieswhile concentrations of Cd, Pb and Sr are higher. These differencesare thought to be caused by spacial and/or seasonal differences.

The number of epibenthic organi sms collected duri ng thesummer were very minimal and dispersed over five different species -only one of which, Persephona aquilonariS, was sampled in anotherseason.

P. gibbesii were collected in sufficient numbers in thefall, winter and spri ng to determi ne its i ntraspeci es and seasonalvariability. There were no apparent seasonal variations in any

3.3-38

metal analyzed, but the intraspecies variability in the fallwas high for Al, Cu, Fe, Hg, Sr and Zn. This would limit theusefulness of this species for monitoring efforts unless larger

numbers were analyzed.

3.3-39

REFERENCES

Alexander, J. E., Program Manager, Baseline Monitoring Studies,Mississippi, Alabama, Florida, Outer Continental Shelf 1975-76, Vol. VI, Rig Monitoring. (Assessment of the EnvironmentalImpact of Exploratory Oil Drill; ng.) Bureau of Land Management,Contract 085SG-CT5-30, June 1977.

Anderson, J. B. and R. R. Schwarzer, Work Unit 2.3.2-2.4.2, Sedimentologyand Trace Metal Concentrations in Sediments and Organisms.In: W. B. Jackson. [Ed.] "1979 NOAA/NMFSAnnual Reportto EPA, Environmental Assessment of an Active Oilfield inthe Northwestern Gulf of Mexico, 1977-1979," Volume III,Physical and Chemical Investigations.

Bender, E., uNOAAAnalyses Brine Disposal at Gul f of Mexico Sites",Sea Technology, 19_, 44, 1978.

Berryhill, H. L. et ale In: "Environmental Studies, South Texas.Outer Continental Shelf, 1975"; Geology, prepared by U.S.Geological Survey for Bureau of Land Management, Contract085SQ..MY5-20, 1979.

Dames and Moore, liThe Mississippii, Alabama, Florida, Outer ContinentalShel f Basel i ne Envi ronmental Survey, 1977-1978", Fi-nal Report,Volume I-A, Program Synthesis Report, prepared for for Bureauof Land Management, Contract AA550-CT7-34, January 1979.

Montalva, J. G. and D. V. Brady, Part 1: Toxic Metal Determinationsin Timbalier Bay Water Samples. In: Offshore Ecology Investigations,Gulf University Research ConsortilUi, 1974.

Montalvo, J. G. and D. V. Brady, Part 2: Toxic Metal Determinationsin Offshor.e Water Samples. In: Offshore Ecology Investigations,Gulf University Research Consortium, 1974.

Shokes, F. F., "Characterization of Baseline Conditions at theWest Hackberry Offshore Brine Disposal Site - Texoma GroupStrategic Petroleum Reserve Program," Science Applications,Inc. Department of Energy, Contract EL-77-C-01.

1Tillery, J. B., Work Group 700-Trace Metals. 1!!..: C. A. Bedinger(Project Manager), "Ecological Investigations of PetroleumProduction Platforms in the Central Gul f of Mexico. II FinalReport, Bureau of Land Management, Contract AA551-CT8-17(in preparation).

2Tillery, J. B., Work Unit 2.4.2-Trace Metals. In: W. B. Jackson[Ed.], 1980, "NOAA/NMFSAnnual Report to En, EnvironmentalAsssessment of an Active Gas and Oilfield in the NorthwesternGulf of Mexico, 1978-1979", under Interagency AgreementEPA-IAG-DS-E693-EO.

3.3-40

Trefry, J. G. and B. J. Presley, "Heavy Metal Transport Fromthe MissisSippi River to the Gulf of Mexico. II In.: H. L.Windomand R. A. Duce (Eds.], Marine Pollutant Transfer,Lexington Books, Lexington, Massachusetts, 1976.

White, T. T., K. E. Turgon and A. W. Blizzard. In: "BaselineMonitoring Studies, Mississippi, Alabama, F'TO"rida,OuterContinental Shelf, 1975-1976", Volume VI, Rig Monitoring,Project Manager J. E. Alexander, prepared by State UniversitySystem of Florida Institute of Oceanography for the Bureauof Land Management, Contract 0855o..crS ••30, June 1977.

Williams, S. E. and J. J. Jones. liThe Distribution and Originof Bottom Sediments in Timbalier Bay, Louisiana." In:Offshore Ecology Investigations, Gulf University Re5e"archConsortium, 1974.

3.3-41

APPENDIX AFigures

3.3-42

w•W•~W

•• ,LA rfORMS•••. ..,.•··~··te·•••

0.1

""",.PELINI

Figure 1. Proposed Disposal Site at West Hackberry

GRAPHIC SCALE~,,"~..:.....rf~'-,·-~-4.1o 6 10n.m.

PROPOSEDPIPELINE

3 FATHOMS......................."..••.·.s ..J" ." "I l,III'- " , ' ••••• \ •••••••

••_.' J;./ ( 'i...•.•..... ",.,.••.•...••j";.

, till '\

\1 .:';""

iiI

TRINITY/SHOAL.: ••, ••••

•J•••• -oO ••••••••••••••••••••••• 6 FATHOMS .,..' ••.•~

•••••' • ", ••••••••• - ft°QuI' ••.1' .- •••••••••••• ~';,

.".1' ••••'"" .....,,' ",.,.....

w.WI~~

~f!.lure 2. Proposed DiSposal Site at Weeks Island····

I

10 miles

~ TOWARDS SHORE

,)1

"1w•WI..I;>.

V'I

,

O=SAMPLING STATIONS

f

IZ

CENTER OF DIFFUSER

5 miles

'''I

Figure 3. Sampling Grid Used at West Hackberry and Weeks Island ProposedDisposal Sites

w.WI~m

••

•

,S'

10

Al "ppm x10.2 ,"

,.•..

10

A A

I --C!). y • 2963x - 22r1• 0.180

I II -~--A. Y • 4300X - 914ra• 0.958

-- - - - :y. 3020X • 160 (Shokes, 1918)

o

••• I.SS o.u ,.u· 0. 71" ••• ,..,.Figure 4. Al versus Fe in Surficial Sediments from West Hackberry;

Summer (I) and Winter (III) Cruises

w.w,~'-J

,,.•

••

B. u(ppll)

.,. ------------- __ ol •••<. A ------.------------M

- - ------------ -66--•••

1-------' • 3•.• + 71.7r'• 0.101

III -----4-, • -15.11 + 51.5r'• 0.405.+---,---,---~---~--_r---r_--_r----___,r__--....., , I , , •• I •

,," ,.U (I.U •.,., •.'K •••.• , .• ~.,. (I)

Figure 5. Sa versus Fe in Surficial Sediments from West Hackberry;Summer (I) and Winter (III) Cruises

.UD

I' ---(!»" y • 0.21X • 0.02rl• 0.997

• ...• -- --.:::...------A

A __ 4---A_ --.---------- ---

.------' .-.---.---••

---

----

.----------- .-- ----

.-

.u.Cd

(P••• )w. .IMWI~00

.D.

I --e. Y • -0.079X • 0.223rl• 0.144

111----4. Y • 0.097X - 0.020rll• 0.622

.OW

o0.•

- - ------- - -_----4-----.- ---- -

4".,D IJ.1S

Fe I~)

IUD D.IS ur

Figure 6. Cd versus Fe in Surficial Sediments from West Hackberry;Summer (I) and Winter (III) Cruises

If

I. _

"

••

••

I ~.y. 2.441 • ).4ra• 0.)98

III ----A=y • -0. lilt • 4.8rl• 0.011

•+---,,---"r----.,-'-----r-l---r---'T'----r.---,,---I,r'"A'" .s.r I.U (US' 0.'" I.¥ tl.1IJ O.~ I.W .tr

Figure 7. Co versus Fe in Surficial Sediments from West Hackberry;Summer (I) and Winter (III) Cruises

"

lO

"

---- -- - 4- - - - - - - - ••..•••-A A•

- -T~· , • 18.411- 4.Jr'· 0.94'

11I----4. •• , • 11.111- 2.7r'· 0.'»-- ----I' .4.'11 + 0.155 (Shot••• 19781_

' , ,CUD A 7S 4. A. 4to •.•

F. (I)

•

A --., ..J --_------ A- - ---.[

I I

UfO 4.sr O.U ,.,~

Cr(ppn) Il

w•WIU'1o

Figure 8. Cr versus Fe in Surficial Sediments from West Hackberry;Summer (I) and Winter (III) Cruises

If

"

Cu I.w (P ••••).wI

l.11•.... ,

----

- -------A--- ..--- ..------•

CUI ,.U) ,.w '.70re (I.)

Figure 9. Cu versus Fe in Surficial Sediments from West Hackberry;Summer (I) and Winter (III) Cruises

.1"

.11

.110

•

1---..· , . 0.061 • 0.002,,'.0.4)511I----4= , • G.OQ • 0.001,,'. G.46t

•

•." .•.A _--------- .- -- - .•--!.-- - - - --- - - .~ .-- --------------- ._----- l

.'f _-----

.II

Hg(ppm)w.

w,01N

A'S •• •• 11" ••••

Figure 10. Hg versus Fe in Surficial Sediments from West Hackberry;Summer (I) and Winter (III) Cruises

w.WIc.nW

fQI

Hn .Ito(ppm)

/H

I ----.., • 7221 -no,I. 0.772

III----A- , • Mil - 343,'. 0.151

-- - -- I'· IICIlIl • 12 (SIloket. 1171.

tASS I.U 4'" fl.1$'

f. (S)••• AM

Figure 11. Mn versus Fe in Surficial Sediments from West Hackberry;Summer (I) and Winter (III) Cruises

,I,

"

" -

4.•,

AU AU

A

I ---0 = , • 8.751• 2.66r'• 0.7'1

III----A-'" 10.81.0.25r·· 0.7'2

-- - -. -. - ~, • 8.'1 • I." (Shotts•• '78), ••• f

•••• A ••• AW

Figure 12. Ni versus Fe in Surficial Sediments from West Hackberry;Summer (I) and Winter (III) Cruises

w•WIU1U1

Pb(pplll)

"

It

• --"-•...... - .__ 4

/..

•

,.

•••.~----- .• '" .•.A----- ...-,....••.•.•..6,,--6

•••

I --e- y••1.71.1.15r'. O•.,J11I-----4= Y • 24.71 - 5.01r·· 0.7"

-- -. --. Y • 40.11 - J.14 (SIlo" ••ml)

D.S$' IUS A~ An'

Fe (I)

Figure 13. Pb versus Fe Surficial Sediments from West Hackberry;Summer (I) and Winter (III) Cruises

,.IU

e

__ - - - - - .- ;1"-e--:--A

1 --._ Y • -58.9X • 96ra• 0.098

4

e __ ----4----.----- .•-- - _e_ - - - -----A-----

-------- A

e

Sr U(PpIlI)

w.w•01Ol

111----.8- Y • 49.IX • ZrZ' 0.591

tI

D•• ••••Fe (X)

Figure 14. Sr versus Fe in Surficial Sediments from West Hackberry;Summer (I) and Winter (III) Cruises

••

-- .• -6,-.\ --------.\_...••---i ---- _. ------ , ------ - - -- --- -- _.-------

- - - --=----=::::;...=-- -' --:..:-:.:-------.-- ------,..----. -.. ---~-____ --A

- - - =.:::-::- - -::::-- --

"10.

In(ppll) .,w.

W,U1..•...•

I --4!) = Y• 21.41 • 16. r&· 0.538

1/1 ----.11.= Y • 43.31 • 3ra• 0.940

- - - - I Y • 3S.91 • 5.81 (Shot.s, 1918)

(I -t----rr------rl----,Tr-----y--r----.T----T..------.-'----.---- .•..,0.,0 41,Q'" AU A" A,. •. 7S 4ft) O.• S 4- at(

h ($)

Figure 15. Zn versus Fe in Surficial Sediments from West Hackberry;Summer (I) and Winter (III) Cruises

,.'",,,,

"A'",

A ","A'"

•

1--0= Y• 571•• 560ra. 0.042

•

•••

"'"'".'".\ "'~

'". "/

'""'",

'"'"/

""'"//

"'"/

"

••

Alppm x10-1 ••

w.WIc.n

(X)

•111----8= Y • 185Z•• 160

r2• 0.811

1.11•

•••• •. W 0.10 •••• 0." I.•

Figure 16. Al versus Fe in Surficial Sediments from Weeks Island;Summer (I) and Winter (III) Cruises

--

w II. ~Ow (ppm)I

U'I\0

lO

I•

•

•

••

•

I ---(j). y. 23.9X + 26.5r~' 0.004

III - - - -ct. = Y • 51.5X - 5.5,.a. 0.606

..""""o+----r-f---~'----,lr-----,'----~,---..--,---,.------,,----,--

0." 0.• (J.MI CU' cU'O 0.••• D. iV 0.. 0.to /.'ft (I)

Figure 17. Ba versus Fe in Surficial Sediment from Weeks Island;Summer (I) and Winter (III) Cruises

••

.,.,

.11

./0

.01

W Cd •D6. (ppn)WI

O'l0

.~

.(11 •" ,," ---

A_ - -:i. -,,- - -"- - - - - - 4-------

1 ~., - -0.1931 t O.U'r'- 0.205

III ----4-, - 0.020 t 0.003r'- 0.295 '

-------------- --oo.~ o.zo 0." 0.• 0.60

Fe (I)

cuo •• to

Figure 18. Cd versus Fe in Surficial Sediments from Weeks Island;Summer (I) and Winter (III) Cruises

II

III

,

111---- ..• • Y • 1.48X + 2.6r'· O.:sal

---I --e- Y • :S.Ul + :S.:S

r'· 0.U4

. ----I- __A_._ - - -- --.__ A- ,..-A-A--------------

•

,

Co(ppm)

w.Wt0'1•....

o11.11I O.lI 0.• 0•• •.•• 0."

f. (I)•••

Figure 19. Co versus Fe in Surficial Sediments from Weeks Island.Summer (I) and Winter (Ill) Cruises

I.•cuo

III ---8= Y • 2.5X + 1.9rl.o 0.412

tUO0.•..'"

---- ----------.4 ---A-- - -A1l.-"-_---.4-- M I ~= Y. 15.9X _ 2.2

rl.· 0.135

•••'.M

---

··If

•

Cr(PpIll) 6

w.WI0'1N

. Fe (I)

Figure 20. Cr versus Fe in Surficial Sediments from Weeks Island;Summer {I} and Winter {III} ·Cruises

''I

"

,I --G=y. 5.4X .0.5

r2• 0.094

w.WI0-.W

Cu 6(pJlIII)

I" - - - -A = Y • 5. 4X - I. 6rZ' 0.922

'.0

.-

0."0."

---

O. :1lJ0.600.60Fe (,,)

•

0.<10

A - 4.- -• A-- Ay-_-4- .-

0.:100./0

f

Figure 21. Cu versus Fe in Surficial Sediments from Weeks Island;Summer (I) and Winter (III) Cruises

~ ..•. "'".•..•..•..•..•.•• I --4i). Y• -O.05X + 0.03........ r'· 0.235

w.WIO'l.J::oo

.DS'

.,'"

Hg .,»(ppm)

.'10

.M

0.1f) (Ull 0.:10

•

0••

•• •

0.•re (s)

III ----8= Y• 0.05X • 0.003r'· 0.172

••• ••• I••

Figure 22. Hg versus Fe in Surficial Sediments from Weeks Island;Summer (I) and Winter (III) Cruises

III---~ •• , • 1131.16'r'• 0.408

I --..,. 44JX. 105r'• 0.276

••

••

•

---- ---A A _A-----------__ --,,--~---- A

100

(.oJ ••• fin(.oJ (PPRl)I0'1(J1

lDO

o0.10 0.10 '.WI •••

Fe (X)

•.a ••• 0." '"

Figure 23. Mn versus Fe in Surficial Sediments from Weeks Island;Summer (I) and Winter (III) Cruises

,,,

IA

"

,

I ~= Y • 4.lX + 4.2r2• 0.155

.to .to.to .to 6-

- - - - - - - - - - - - -li.- - - -.- -- -- - -- - --..'w ,.W Nt• (p •• )

0'10'1

f

III &= Y • -O.08X + 7.1r2.. 0.000

•

0." 0.11I 0.• 0•••••

re (II•.'0 0.", O.t!) I.•

Figure 24. Ni versus Fe in Surficial Sediments from Weeks Island;Summer (I) and Winter (II) Cruises.

If

"

,

w Pb,.

W (,.-)•0'1-...,J

.,

I

.•., .•.,..

••

...'" ,A..,.. ' .

...."

......,..

,.•.

I ----41 •• Y - IO.6X. 0.1Irl. O. Illl

III __ u&::: y. H.lIX - 1.1rl·O.481

II.• •• ••f. (I)

Figure 25. Pb versus Fe in Surficial Sediments from Weeks Island;Summer (I) and Winter (III) Cruises

'0

•

I -e- y.40.51 • 1.2r'· 0.011

III --- -£- y. 21.OX • I.tr'· 0.316

••.•..•..•.-.••..-....•.- .•..•.------I • A •• -1"'-~-_ .....--

_----. I A-----

HSr

(pplll)

w•w•0'1co

o0•• 11.1.0 0.310 0.. 0..-

Fe (I)AID

Figure 26. Sr versus Fe in Surficial Sediments from Weeks Island;Summer (I) and Winter (III) Cruises

w•WI

0'1l.O

2n(ppm) •

,.

------

--------• A _-------

A _ -JAA•. - -.- -A---- .-- ••••I -----.- Y· 2.3l • 21

,.'. O.OOJ

111----6=- y. 171. 171". 0.415

• -I----"----.,r----..,,r-----r--,---,-.---,-,---,.,----,,---..,.I'"fl." ••••.• '.W , .• '.11I ••••••••• ".

Fe (1)

Figure 27. Zn versus Fe in Surficial Sediments from Weeks Island;Summer (I) and Winter (III) Cruises

Sitt A--0 I Y • 0.003X + 0.611"1. 0.332

w.WI.....,o

Fe(S)

•• '4

---------.--• .9-----••.1>._----_.----a.-- - --- ---

'.&

•• "

% Clay

Sitt 8----.£ I Y • 0.003X + 0.441'"1. 0.030

Figure 28 .. Fe versus % ClayinSurfic1al Sediments from ~lestHackberry (A)aM Weeks Island (8) Site for Summer (1) Cruise

APPENDIX BSample and Data Inventories

Sample and Data Inventories

Sample Type Number Contracted Number Collected Number Analyzed

Epibenthic 56 56 56Macrocrustacean 56 56 56Suspended Particulate 56 56 56

Matterw.w Surficial Sediments 36 36 36I-JN