RELATIONSHIPS BETWEEN TOXIC METAL FROM ZEBRA MUSSEL WASTES AND PROXIMITY TO SELECTED LAKE ERIE SHIPWRECKS

Andrew Ailen Brooks

A Thesis Submitted to the Faculty of Graduate Studies and Research through the Department of Geography in Partial Fdfilment of the Requirements for the Degree of Master of Arts at the University of Windsor

Windsor, , 1997 National Library BiMiathèque nationale du Canada

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This thesis is an examination of toxic metal concentrations around three shipwfecks in the Westem Basin of Lake Erie. These wrecks are densely populated with zebra mussels (Dreissem polymoqha). It was anticipaîed that the zebra mussels were a mechanism by which the toxic met& in the surrounding water were deposited on and around the shipwrecks. UtiliPng scuba divers, thirty-six samples (twelve hmeach site) were gathered and chemically analysed.

The results indicate that one of the shipwrecks under study, the Conemaugh,was statistically different fiom the other wrecks. This could be atfributed to dissimilar environmental conditions at this site. Statistical andysis of the remaining data set revealed that the toxic metals under study were in fact concentrated on the shipwrecks, and decreased in with increased distance hmthe wrecks. In several instances, available govemment standards for contaminiited soUsedirnent were exceeded by the observecl toxic metal concentrations. As a result of the observecl toxic metal concentrations, and the relevant literature, it could be concluded that the zebra mussels were the mechanism by which the toxic rnetals reached their obsewed elevated concentrations.

iii Many people deserve thanks for their contributions to this thesis. My advisor, Dr. Pete LaValIe is most responsible for my success as a university student, culmùiating with this project Without his expert tutelage, and innumerable hours of assistance and advice, 1 like1y would never have entered graduate school, or completed this thesis. Dr. Chais Lakhan, my second reader, aleoften filling my head with dreams of Guyana, South Amerka, has kept me focussed on the goal at hand, and helped me to achieve it. Dr. Don Wailen, my exterd reviewer, deserves credit for his ongoing advice.

Several people were Myresponsible for helping me get the field and laboratory work completed. Mr. Grant Meseck, and Mr. Mike Drexier deserve thanks for assisting me in sampfe collection Mr. Derek Nardini deserves recognition for help on shore, as well as in the geopphy department for his help with computer problems, and general advice dong the way. Mr. John Karry of Save Ontario Shipwrecks (Windsor Chapter), and Mr. Peter Engelbert of the Ontario Miaistry of Heritage and Culturr, deserve thanks for allowing me to gather some of my samples while accompanying them on meydives for ErieQuest. 1 am grateful to the stafïat Point Pelee National Park for permitting myselfand those assisting me access to the tip with vehicles and gear, so that 1 couid gather samples hmthe Conemmgh. Mr. J-C. Barrette of the Great Lakes Institute for Environmental Research was instrumental in actually performing the chernical anaiysis on my samples, and in adjushg the fee structure so that my iimited research fun& would dowfor the cornpletion of the needed tests. Jennifer Elcomb, of South Shore Scuba, supplied me with undenvater photographs for my thesis.

Last, but not least, my family deserves a great deal of credit for allowing me to complete this project. As anyone who knows me can attesf 1 prefer to work at odd hours. It has been a great advantage to be permitted to corne and go at my leisure and to work when motivated to do so. This was, I am sure, of considerable inconvenience to all concemed. There were times when they forgot what I looked like because 1 wasn't amund, just as there were times when 1 was hard at work in my room at ali hours of the night, bothering those who tried to sleep. To my girfiend, Jenuifer McLean, 1 know how hard this has been on you, and us. Hopefully now we cari get on with our Lives. TABLE OF CONTENTS

page... ABSWCT...... UI A-OWEDGEMENTS ...... iv TABLE OF CONTENTS...... v . LIST OF MAPS ...... ~11 L][ST OF FIGURES ...... *...... *...... vu .. LIST OF GRAPHS...... w.. LIST OF TABLES ...... wu...

2. REGION UNDER STUDY ...... 3 a Sm& Are&...... 3 22 ...... 6

3. LITERATURE REVLEW ...... 7 Introduction of Zebra h&& ...... *...... *.*.7 Bipptocess@ bv ZebMussels ...... 7 3J and Their T- ...... 9 24 Jlevelopment of ~~~~...... 9 4. A priori MODEL...... 11

6. OBSERVATIONS...... ,..,...... 22 6.1 General Fi- ...... *.*..*...... 22 6.1 .1 Pilot Study, Spemlar and Tioga...... A 6.1.2 Conemcrugh...... 22 6.1 .3 Northern hdia~...... ,...... 23 6.1.4. . MI Wilcox...... 23 6.2 S-cal ...... 24 7. CONCLUSION...... 48 7.1 Discm...... 48 ns of FmSw ...... 49 7.3-Final Cm...... , ...... +...... 50

8. APPENDICES ...... 52 ...... 33 ...... **.....*.*..*...... ~..*...*.. 54 t Smde Raw Da ta...... 55 8.3.1 Tioga and Spedm...... 55 8.3.2 Conempugh...... 56 8.3.3 Northern Indiana...... **..*...... *.*.*...**...*...*....**...*...... *..57 8.3.4 ML WiZcox...... 58 ...... 8.4 _GLTER Protocol ...... 59 8.5 photo-h of Zebra Mlysels on the Northem IrlQiang...... 60 8.6 Photo- . of. Fisso~~Axial Piasma Spectophotomem...... 61 8.7 Schemc Diperêms of ICP-OES ...... 62 LIST OF MAPS page MAP 1: THE STUDY AREA ...... 4

LIST OF FIGURES

FIGURE 1 :A priori MODEL ...... 13 FIGURE 2: SURVEY PATTERN AROUND SHIPWRECK SITES ...... 16 FIGURE 3: DMSION OF HEXAGONS INTO EQUAL AREAS...... 17 FIGURE 4: LOCATION OF SAMPLE SITES AROUND THE CONEMAUGH...... 19 FIGURE 5: LOCATION OF SAMPLE SITES ARUUND THE NORTHERN INDIANA...... -...... 20 FIGURE 6: LOCATION OF SAMPLE SITES AROUND THE M.1 . WILCOXII...... l.--..ir.i..-r...... *....-..*...... ea.*...... 21

LIST OF GRAPHS

GRAPH 1 :CONEMAUGH, LN ARSENIC vs .LN DISTANCE...... / GRAfH 2: CONEMAUGH. LN CADMTUM vs. LN DISTANCE...... , ...... 26 GWH3: CONEMAUGH,LN CHROMIUM vs . LN DISTANCE...... 27 GRAPH 4: CONEMAUGH,LN COPPER vs .LN DISTANCE ...... 27 GRAPH 5: CONEMAUGH. LN LEAD vs . LN DISTANCE ...... 28 GRAPH 6: CONEMAUGH.LN NICKEL vs .LN DISTANCE ...... *...... *28 GRAPH 7: CONEMAUGH,LN VANADIUM . vs . LN DISTANCE ...... -29 GRAPH 8: CONEMAUGH,LN ZINC vs . LN DISTANCE ...... 29 GRAPH 9: M.I. WLCOX AND NORTHERN INDIANA LN ARSENIC vs . LN DISTANCE...... 30 GRAPH 10: M.I. WILCOX AND NORTHERN INDIAN LN CADMIUM vs. LN DI STANCE...... 30 GRAPH 11: M.I. WLLCOX AND NORTHERN INDIANA LN CHROMIUM vs . LN DISTANCE ...... 31 GRAPH 12: M.I. UrLLCOX AND NORTHERN INDIANA LN COPPER vs. LN DISTANCE...... 3 I GRAPH 13: M.1 . WILCOX AND NORTHERN INDIANA LN LEAD vs .LN DISTANCE...... -32 GRAPH 14: M.I. WILCOX AND NORTHERN INDLANA LN NICKEL vs . LN DISTANCE ...... -32 GRAPH 15: M.I. WILCOX AND NORTHEICN INDIANA LN VANADIUM vs . LN DISTANCE...... -33 GRAPH 16: M.I. WILCOX AND NORTHERN INDIANA LN ZINC vs .LN DISTANCE...... 33

vii LIST OF TABLES

TABLE 1: COMPARXSON OF CCME STANDARDS WITH THE HIGHEST RECORDED TOXIC METAL CONCENTRATIONS FROM EACH WRECK...... 24 TABLE 2: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN ARSENIC ...... , ...... 35 TABLE 3: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN CADMIUM...... *.*..*.....*..*...... **...... *..**.,..3 5 TABLE 4: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN CHROMIUM...... ,...... 36 TABLE 5: 2-WAY ANOVA OF INTERACTIONS OF WEECK AND SECTOR FOR LN COPPER ...... 36 TABLE 6: 2-WAYANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN LEAD...... 37 TABLE 7: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN NICKEL...... 37 TABLE 8: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN VANADIUM...... 38 TABLE 9: 2-WAY ANOVA OF INIERACTIONS OF WRECK AND SECTOR FOR LN ZINC...... 38 TABLE 10: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN ARSENIC ON THE M.I. WILCOX AND NORTHERN INDIANA...39 TABLE 11: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN CADMIUM ON THE M.I. WILCOX AND NORTKERN INDIANA ...39 TABLE 12: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN CHROMIUM ON THE ML WILCOX AND NORTHERN lNDIANA..40 TABLE 13: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN COPPER ON THE M.I. WILCOX AND NORTHERN INDIANA.... 40 TABLE 14: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN LEAD ON THE M.I. WILCOX AND NORTHERN INDIANA...... 41 TABLE 15: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN NICKEL ON THE M.I. WILCOX AND NORTHERN INDIANA. ...41 TABLE 16: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN VANADIUM ON THE M.I. WILCOX AND NORTHERN INDIANA..42 TABLE 17: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN ZINC ON THE M.I. WCOX AND NORTHERN INDIANA...... 42 TABLE 18: REGRESSION ANALYSIS, M.I. WILCOX AND NORTHERN INDIANA LN ARSENIC vs. LN DISTANCE. ....*.*...... ,...... **...... *..*...... **43 TABLE 19: REGRESSION ANALYSIS, M.I. WILCOX AND NORTHERN INDIANA LN CADMIUM vs. LN DISTANCE...... 43 TABLE 20: REGRESSION ANALYSIS, M.I. WILCOX AND NORTHERN INDIANA LN CHROMWM vs. LN DISTANCE...... ,...... d viii TABLE 21 :REGRESSION ANALYSIS, M.I. WECOX AND NORTHERN INDIANA LN COPPER vs. LN DISTANCE...... 4 TABLE 22: REGRESSION ANALYSIS, M.I. WILCOX AND NORTHERN INDIANA LN LEAD vs. LN DISTANCE ...... -45 TABLE 23: REGRESSION ANALYSIS, Ml. WILCOX AND NORTWERN INDIANA LN NICKEL vs. LN DISTANCE...... 45 TABLE 24: REGRESSION ANALYSIS, M.I. WlLCOX AND NORTHERN INDIANA LN VANADIUM vs. LN DISTANCE ...... ,...... -46 TABLE 25: REGRESSION ANALYSIS, M.I. WILCOX AND NORTHERN INDIANA LN ZINC vs. LN DISTANCE ...... 46 TABLE 26: SUMMAlRY OF REGRESSION ANALYSIS FOR M.I. WILCOX AND NOR- INDLANA...... 48 1. INTRODUCTION

Since 1986, Dreissena polymorphu (zebni mussels) have invaded Lake Erie (Hebert et al.,

1991). Zebra mussels have been cited as agents which contribute to some pollution problems

(Reeders and Bij de Vaate, 1992) while ameliorating others on or near colonkation sites such as shipwrecks (Macke and Wright, 1994). Zebra mussels appear to be responsible for the increase in underwater visibility in Lake Erie, hmone-halfmetre in the mid 19801s,to in excess of ten metres presently. For over ten years, the Town of Leamington, Ontario has been attempting to develop a marine park known as ErieQuest (Town of Ldgton, 1995). The improved visibility enhances the economic viability of EneQuest but an increased pollution havud may offset this phenomenon. Thmefore, it itms advisable to examine possible relationships between zebra mussel coIonizafion, changes in the poilution hapud due to toxic metal bioamplinpation, and improved undemer visibility around some of these shipwreck sites.

Zebra mussels preferentidy fïiter and biodeposit fine particdate matter (4p), which tends to be more highly contnminated with toxic metals (Reeders and Bij de Vaate, 1992). In areas where zebra mussels are abundant, such as on shipwrecks, this process leads to correspondingiy high toxic metal concentrations in the sediments. Some consideration of this phenomenon is necessary prior to the exploitation of shipwrecks as a tourist attraction designated for scuba divers. In this investigation, an attempt will be made to examine the relationships between toxic metal concentrations hmzebra masel wastes and their proximity to some Lake

Erie shipwrecks.

WhiIe no guidelines are currently in place to deal with the exposure of scuba divers to chemical contamination, there are guidelines for human contact with contamhated soi1 and sediments (See 8.2 AppendUr B)(CCME, 1991). Chernical analysis of the sediments hmon and around shipwrecks within ErieQuest wiil expose any heightened toxic metal concentrations due to the activities of zebra rnussels. Subsequent cornparison of these data with available guidelines shouid provide an indication of potential nsk to diva who may corne in contact with these sediments while visiting the shipwrecks in question. 2. REGION UNDER STUDY

ZL-

The Western Basin of Lake Erie is located to the West of Point Pelee, and north of the international border between Canada and the United States of America (See Map 1). In historic times, the shipping channel passed between Point Pelee and Pelee Island, and into the Detroit

River. The numemus shoals and reds in this area were the site of hundreds of shipwrecks, and led to the creation of what are today shipwreck sites (Town of Leamington, 1995). Since 1988, the Wmdsor chapter of Save Ontario Shipwrecks (S.O.S.) has catalogueci the location of 48 shipwrecks and 26 wreckage sites, and meyed individual shipwreck sites (Town of Leamington,

1995).

The exact bomdaries of EneQuest have not as yet been specifically delineated. A potential approach, and that which was utilized for this shidy, will encompass that area extending from Leamington to the intemational boundary, stopping at Bar Point on the West and just beyond

Point Pelee to the east (See Map l)(Town of Learnington, 1995). This area indudes the vast majority of known shipwrecks. From these shipwrecks, two pilot, and three study sites were chosen at random. Each is slated for inclusion in the initial fifteen wrecks utibd for EneQuest when it fodyopens on 3 1 May 1997. The sites used for the pilot study were the Specufur and

Tioga, while the ML Wilcox, Conemaugh, and Northern Indiana were chosen for the study itself

(See MAP 1). The M.I. Wihxlies off of Colchester;Ontario, and the others are in the Pelee

Passage, between Point Pelee, and Pelee Island, Ontario.

The Tioga was a one himdred seventy-seven foot (nfty-four metre) propeller driven freighter. She was constructeci at Cleveland, Ohio in 1862, and following a fire, sank to a total

10son 5 October 1877 (Kohl, 1994). The wreck lies in approxhately forty téet (twelve me-) of water.

The Speculm was also built at Cleveland, Ohio. She measured two hundred sixty-three feet (eighty me-), and was launched on 7 September 1882. She was originally a schooner, but was changed to a propeller pnor to her sinking on 22 August 1900 (Kohl, 1988). Judged to be a menace to navigation, she was dynamited on 23 October 1900, and now lies in thirty-seven feet

(eleven metres) of water.

The Conemaugh was a wooden package fieighter. Built in Bay City, Michigan in 1880, the two hundred fi&-one fwt (seventy-six and one-haif me)ship ran agrouud on Point Pelee during a violent stom on 24 November 1906 (Kohl, 1988). Most of the cargo, and dl of the crew were rescued, but ice smashed the hull during the winter, and the wreck now lies scattered in nfteen - twenty feet (five - six metres) of water. Historically speaking, the Conemaugh was very important (Kohl, 1988). She was involved in an earlier sinking in 1898 with the New Ywk in the

Detroit River. As a result of this incident, the United States Supreme Court adopted wht ûMeto be known as the New York Rule, a fine point of the Great Lakes Rules of the Road that is dlin use today (Kohl, 1988).

The MI. Wilcox was a three masted schooner, launched on 2 May 1868 at Toledo, Ohio

(Kohl, 1994). She was one hundred thirty-seven feet (forty-two metres) in length. This vesse1 was actuaily involved in two accidents prior to her eventual sinking on 9 May 1906, ak foundering. Today, she lies in twenty-six feet (eight me-) of water.

The Northern Idma was a wooden passenger steamer, only recently identifïed by S.O.S.

Windsor. Built in 1852 at Buffalo, New York, she was used to feny passengers between the rail iines at Bunalo, and those of Detroit, Michigan and Toledo, Ohio (Kohl, 1997). On 17 Juiy 1856,

only four years after her launch, a fire broke out on board, and she sank in the Pelee Passage. This

was the vessei's second mishap in the Passage, and resuited in the loss of twenty-eight lives, stiil the worst maritime accident in Western Lake Erie (Kohl, 1997). Today, the three hundrecî foot

(ninety-one and one-half metre) vesse1 lies collapsed in forty feet (twelve rnetres) of water (See

Appendix 8.5).

22- G~~Qa!

The Western Basin of Lake Erie is shallow, and is separateci hmthe waters to the east and noah by Point Pelee, and a chab of shoals and islands (Hough, 1958). These islands are indicative of the shdow nature of this region. The predobtrock -ta found in the area are

Upper Bass Island dolomite, overlaid by Detroit River dolomite, topped by Columbus limestone

(Hou&- 1958). These strata were laid domapproximately 41 0 million years ago, between

Siluria.and Devonian times.

During these times, much of the Great Lakes region was wvered by an inland sea. Within this sea could be found coral reefs which created the sedimentary deposits found today. One potential factor contributhg to the proliferation of zebra mussels in the study area may be these exposeci strata. The dolomite and limestone are an excellent source of calcium fiom which zebra mussels could fonn their shells (Neary and Leach, 1992). 3. LITERATURE REVIEW

ZL InkQdU~onad Sm of7:é:hmM~eIs

Dreissempoljmorpha is a member of a superfamily of bivalve moiiusca that are restricted to estuarine and fieshwater habitats (Morton, 1969). They i5rst colonked Lake St Clair ia 1986, as a resuit of khwater ballast discharge (Hebert et al., 1989). This mechanism has been implicated in the introduction of several other exotic species into the Great Lakes (Schomann et al., 1990) since the opening of the St Lawrence Seaway in 1959 (Hebert et al., 1989). Some invaning species have failed to establish themselves, such as the mitten crab (Nepszy and Leach,

1973), while others, such as the fish Gymnocepha2u.s cernua have becorne dominant members of the fatma (Hebert et al, 1989). It is quite probable that the rich diversity of the native unionid wmmunity in the Great Lakes codd be reduced, through extinctions, as a result of the of zebra mussels (Neary and Leach, 1992).

The date of introduction for Dreissena polymorpha has been estabiished through an extensive study of sheil length distribution in Lake St. Clair, by Gri£fiths et al. (1 99 1). Due to comprehensive benthic surveys of the Detroit River and Lake St. Clair in 1983, 1984, and 1986, with no sign of zebra miissels, it is fairly deto posit they were not introduced prior to 1986

(Wthset al., 199 1). The zebra mussel population had a potentiai for rapid growth when studied in August 1 988, as the ratio of juveniles to adults was 20 to 1 (Hebert et al., 1 989). As a result of this, and the number already present, it was too late to stop their spread.

22BipproceSsine~MW

Much of the concem about the introduction of zebra mussels lies in how they alter the nutrient levels in water due to their filtering action. Reeders et al. (19891, showed that aa individual L)reissenupoljmorpha is capable of filtering more than one litre of water per &y. The long-term effects of this constant tramfier of nutrients hm the pelagic to the benthic component of an ecosystem are of great concem (Leach, 1993).

Zebra mussels are indiscriminate filter feeders (Reeders et al.,1989). They simply füter all particles smaller than one micro-metre ( m) fiom the water column (Jmgensen et al., 1984).

Food items such as algae and bacteria are selected intemally (Ten Winkel and Davids, 1982), while inorganic silt and pollutants are coilided with mucus and expelled as pseudofeces (Reedem and Bij de Vaate, 1992). niis expelled pseudofeces accumulates on the lakebed with the feces

(Mackie and Wright, 1993). Over 90% of all fecal particles produced by zebra mussels are pseudofeces Qeeders and Bij de Vaate, 1992). Pseudofeces are more easily broken down and resuspended (Risk and Moff' 1977). while fdpellets are more mistant to erosion (Rhoads,

1974). Biodeposited muds are particularly prone to resuspension (Flemming and Delafontaine.

1994). Should the filtering capacity of the community be sunicient to exceed algal growth, increased transparency wiil lead to the recovery of aquatic vegetation (Reeders et al., l989), or vegetation may now flourish in areas where it was previously too dark due to high levels of . In experiments conducted by Mackie and Wright (1993), zebra mussels were fodto remove 95-1 00% of the available suspendeci materials.

Pseudofeces is not simply suspendeci matter deposited on the lake bottom. Pseudofeces tends to be more pohted than the parent water due to the fact that particles the size of organic pollutants are most poiluted with toxic metals (Reeders et al., 1989). Small particles are more polluted with toxic metals because adsorbency increases with decreasing particle size (Salomons and Wrstner, 1984). This concentration of toxic substances into pseudofeces could lead to massive quantities of polluted sediment on the lake bottom. As a result of their feeding, respiratory, and excremental activities, bivalves are known to play an important role in mediating both physical and chemical processes near the sediment-water inteditce (McCaU and Fisher,

1980).

i3u

The importance of Sediments to the biogeochemical cycling of materials is well hown

(Lee, 1970; Mortimer, 1971). Sediments act as bot-a source and a sink for biologically important materiais such as carbon, and phosphorous (Matisoff et al., 1985). Sediments are known to play an active role in regulating cycles of trace metals (Jones and Bowser, 1978). Due to this, Mer knowledge relating to the chernical diagenesis of sediments is essential (Matisoff et al., 1985).

Sediment resuspension plays a dominant role in downstrearn transport of sediment-bound, or 'in-place' poilutants (Young et al., 1992). The term "in-place polIutantsWrefers to the reservoir of contamhnts that accumulates in aquatic sediments during periods of active pollution. These contnminnnts can affect water quality long afkr initial sources of pollution are elllninated. Such contnminnrit sources are implicated in forty-one of forty-two Great Lakw Areas of Concem designated by the Intemational Joint Commission (GLWQB,1987).

uDeveloament of EIkQuest Situateci on the shores of the Western Basin of Lake Erie, the Town of Leamington,

Ontario has been investigating the feasibiiity of developing local deresources as a tourist attraction (Town of Leambgton, 1995). The waters near the Town (Pelee Passage) have been the site of over 275 'incidents' involving the sinking of a ship. It is unknown how many resuited in the creation of a permanent shipwreck site, but the number is Iikely greater than 100. Eighty have already been identined, and ErieQuest, as the marine heritage area has corne to be known, is set to begin operation with a concentration on meen sites (Town of Leamington, 1995). However, if the shipwrecks are covered by sediments which contain excessive concentrations of toxic metals, then the feasibiIity of developing these sites for 'submarine tourism' may be severely reduced. If such a situation exists, then what is the deof zebra mussels in the concentration or mobi-on of these toxic materials near shipwreck sites. A study of this problem shouid not only add to the litexature on zebra musse1 ecology but it should provide LeamUzgton, Ontario with valuable information needed to effectively develop a shipwreck park 4. A prion' MODEL

Previous work has indicated that zebra mussels are capable of acting as biological filters, bioprocessing polluted suspendeci matter fiom the water colum.and biodepositing it as pseudofeces (Mackie and Wright, 1994). Analysis of thü: matenai by Reeders and Bij de Vaate

(1992) established that it was more polluted with toxic metals than the parent nispended matter.

The a priori model developed in this section is based on this literature, a pilot study, and observations made by the author d&g reconnaissance work in the field.

Zebra mussels were first introduced into the Great Lakes system in 1986 (Griffiths et al.,

1991). They quickly colonized solid objects such as rocky reefk (Leach, 1993), native unionids

(eg. clams), and shipwreck sites in the Western Basin of Lake Erie. The observed concentrations of Dreissenapolyrnorpha have exceeded 342,000 /m2in some instances (Leach, 1993). These massive colonies of musse1s, their filtration rates of 1L/mussel/day (Stancy kowska, 1977), and the daily toxic metai loadings entering Lake Erie fkom the Detroit River alone (RAP, 1994), are expected to produce hi& concentrations of toxic rnetals in the sumiunhg sediments. It is also possible that the shipwrecks themselves may be sources of toxic metals, and that these met& may be biodeposited by zebra mussels.

Sediment resuspension plays a dominant physical role in downstream transport of sediment-bound pollutants (Young et al., 1992). Therefore, contaminated paticulate matter that settles on its own, or is biodeposited, can be expected.to migrate due to sediment resuspension, and subsequent desorption of contamhnts. This process should lead to both imports and exports of toxic metals kmshipwreck sites, most noticeably in the direction of the prevailing curent.

On the basis of these considerations, an apriori model was constructed (See FIGURE l), and the following hypotheses put forward:

1. Toxïc metal concentrations in sediments around shipwrecks will decrease with increasing distance away f?om the shipwreck.

2. Zebra mussels bioprocess toxic metals fxom the surroundhg water colrmin and biodeposit them onto shipwrecks.

3. Some toxic metal concentrations on shipwrecks within ErieQuest will exceed Canadian government standards for contamination of sediments.

These hypotheses are supported by the literature review, and are logical progressions fiom it. Hypothesis 1 is based on the fact that zebra mussels are concentrateci on shipwrecks, and decrease in density with increased distance away fkom the wreck. As a result of this, the zebra mussels' wastes which are contaniinated, can be expected to be concentrateci on the shipwrecks, leading to elevated toxic metal concentrations on the wreck itseK It is also possible that some toxic metals can corne fiom the wreck itself, and these toxins can also be expected to decrease in concentration with increased distance hmthe wreck. It is possible that this can lead to toxic metal contamination of shipwrecks.

Hypothesis 2 is grounded in the understanding that zebra mussels do filter water, and biodeposit any indigestible residue near themselves. The water of Lake Erie is known to contai. toxic metals, and zebra mussels are found atîached to shipwrecks. Therefore, zebra mussel wastes can be expected to accumulate on shipwrecks, and lead to corresponding increases in toxic metal contamination of the surrormding sediments.

The finai hypothesis (3) is based upon the known bioprocessing activities of zebra mussels. These mussels have been well established in the study area for more than five years. FIGURE 1: A priori MODEL.

, Zebra Shipwreck Musse1 l i Colony L I I 1 i i l ! !

I I l . DepasitiMi l Dapositioci 0

I I v

Under Study

Source: Author, 1997. hiring tbis tirne, the mussels have been continuously filtering the water column. The likelihwd that this time period has permitteci the accumulation of toxic metals in excess of government standards (See 8.2 Appendix B) is considerable. 5. METHODOLOGY

This study required the savices of two scuba divers in order to gather sediment samples hmon and around the three shipwrecks within the study area From each wreck, twelve samples were collecteci, for a total of thirty-six samples. This produced enough data points to dow for infefential statisticai analysis. The shipwreck sites were surveyed using a @ submersible compas and a Lu£kin@ 50m meamiring tape, and a series of hexagonal grids were delineated (See

FIGURE 2). Each hexagon had sides of 50 metres in length. The use of a hexagonal grid pattern aiiowed for the creation of smaller diamond shaped quadrats of equal area (See FIGURE 3).

From this mey,cpdrats were created in rings around the shipwreck, and numbered

Once the quadrats were labelled, a =dom numbers table was used to locate sampling sites. The actual collection of sediment samples from the wreck sites involved the researcher (using scuba equipment) transporthg an empty, clean, one litre Nalgena bottle to the sampling site. The researcher then opened the bottle, dlowed it to fill with water, and then submerged it gently into the Sediment. Once the bottie was Wed with sediment, the cap was replaced on the bottle, and the bottle was retumed to the surface for destorage until it was retunied to the lab. Four samples fiom the 50 metre hexagon, and six samples fiom the 50-100 metre hexagons were taken.

Two samples were also collected fimm on the wreck itself (See FIGURES 4,5, and 6).

After collecting the sediment samples, they were taken to the soils laboratory in the

Department of Geography, University of Windsor. The samples were then dried over night in a

GalIenlcamp OV-160oven and then manually crushed and weighed using a Meîtld PC4400 scale. Approximately 50 gram of sediment fiom each sample was then submitted to the Great

Lakes InstiMe for Environmental Research (GLIER), at the University of Windsor. The method FIGURE 2: SURVEY PATTERN AROUND SHIPVRECK SITES. SOURCE: AHEDEO AND GOLLEDGE C1975), pp. 214.

-SURVEY LINES FIGURE 31 DIVISION OF HEXAGONS INTO EQUAL AREAS. SOURCE: AMEDED AND GOLLEDGE (19753, pp. 216. FIGURE 4: LOCATION OF SAHPLE SITES AROUND THE CONEHAUGH.

-- SURVEY LINES

-SURVEY LINES

$I SAMPLE POINT FIGURE 5: LOCATION OF SAMPLE SITES AROUND THE NORTHERN INDIANA.

-- SURVEY LSNES

-SURVEY LINES

SAMPLE POINT FIGURE 6: LOCATION OF SAMPLE SITES AROUND THE M.I. VILCOX.

-- SURVEY LINES

7SURVEY LINES

SAHPLE PQINT of dysisemployed was aquaregia, followed by inductively coupled plasma - optical emission spectroscopy (ICP-OES). This involveci the use of a Fissons@ Maxim Axial Plasma

Spectrophotometer (See Appendix 8 6).

Aquaregia is the process of preparing the sample for injection into the ICP-OES(See 8.4

GLIER Protocol). ICP-OESinvolves the injection of a sample into a Stream of argon gas, where it is carried into a plasma source that has been heated by a radio-fiequency generator (Baty and

Kerber, 1993)(See Appendix 8.7). The sample is exposed to ranging hm6000 -

8000 K for approximately 2 mec. The ultraviolet-visible spectnim of the sample is monitored to detect the observed wavelengths (Skoog, 1985). These wavelengtbs are then compared to hown wavelengths to determine the elements present in the sample, and their concentrations

(Skoog, 1985). 6, OBSERVATIONS

. O 6.1 Ge& F-

6.1.1 Pilot Study, Speculm and Tioga

In the pilot stuciy of July - August 1995, one sample was taken nom each of the Speculm, and Tioga shipurrecks. An examination of these samples supportecl hypothesis 3. The sample hmthe SpecuZar exceeded CCME standards (See 8.2 Appendix B) for lead, nickel, vanadium, and zinc (See TABLE 1). There were similar results hmthe Tioga sample. Concentrations of copper, lead, nickel, vanadium, and zinc all exceeded CCME standards (See TABLE 1). It was these resuits fichencouraged the completion of this full scale project.

6.1.2 Conernaugh

The analysis of the sediments fimm the Conemaugh did not reveal any metal concentrations in excess of CCME standards (See TABLE 1). At fkt, this would seem troubling, but the wreck of the Conemghexperiences a différent set of environmental interactions than do the other wrecks in this My.

The Conewgh is exposed to much stronger currents then any of the other shipvw9cs.

This serves to breakdom and resuspend the zebra mussel pseudofeces. Once resuspended, the strong can easily dissipate the toxic metals over a wide area. The Conentclugh is also in shallower water, and much closer to shore than the other wrecks. As a result, the wreck is subjected to more severe ice interaction during the winter. This leads to reduced toxic metal concentrations for several reasons. Firstly, the ice is directly responsible for moving and removing the pseudofeces fkom on and around the wreck Secondly, the impact of ice against the wreck itself reduces the number of zebra mussels living on the wreck by causing their deaths.

This Leads to a corresponding decrease in the amount of con-ted wastes produced in the area Thirdly, the ice breaks up and scatiers the shipwreck. This reduces the concentration of zebra mussels in any one central location, and exposes more of the wreck to the bhcurrents in the vicinity of Point Pelee. These two factors combine to further reduce the amount of pseudofeces produced and retained on and around the shipwreck.

6.1.3 Northern Indiana

The samples hmthe Northern Indima showed a pattern like those of the pilot study.

There were concentrations of catimiwn, lead, nickel, vanadium, and zinc which wodd result in the wreck king classifiecl as contamhated (See TABLE 1). Most of the high levels occurred in the samptes fiom the wreck itself. and fkom the fifty metre hexagon, but vanadium in particular had elevated levels throughouî the sampling field (See 8.3.3 Northem Indima).

6.1.4 MJ. Wilcox

The M.I. Wikox also has several high concentrations of toxic metals present in the sunounding sedimentS. Copper, cadmium, lead, nickel, vanadium, and zinc al1 were found at levels in excess of CCME standards (See TABLE 1). At this wreck, while high levels of toxic metals were found on the wreck itself, there were also high levels of contamination obserred in the fifty metre hexagon (See 8.3.4 M.I. Wilcox). TABLE 1: COMPARISON OF CCME STANDARDS W'l'I'H THE HIGHEST RECORDED TOXIC hET'AL, CONCENTRATIONS FROM EACH WRECK.

Metal CCME Tioga Specuiar ConemPugh Northern Ml. WiIcox Standards Indiana

As 5.0 331 3.48 1 4.47 4.90 4.92 Cd 0.5 da da 0.30 0.95 0.7 1

Cr 79.0 39.24 37.05 10.76 30.65 38.48

Cu 30.0 39.89 29.63 7.82 25.81 39.9 1

Pb 25.0 50.83 32.7 1 7.70 25.77 35.76

Ni 20.0 45.94 36.18 12.21 30.86 38.44

V 25.0 3254 32.46 13.84 35.9 1 44.47

Zn 1 60.0 1 151.6 I 135.0 1 22.40 1 103.00 1 132.10 t

NB: AU values are in pprn.

. . 6.2 Stattstical a

For this part of the thesis, SPSSQ version 7.5 for Wmdows@ 95 was used. The program was executed on a Pentiumm 120MHz cornputer. In order to explore the validity of hypotheses 1 and 2, regression analysis is required This will indicate whether or not the relationships between distance fiom the shipwreck, and the concentration of the individual metals under study are signifiant. Due to the fact tbat three separate shipwrecks are king used, an analysis of variance must fïrst be perfodon the data.

An analysis of variance (ANOVA) is one method used to ascertain if places merin tems of the phenornena present there (Johnston, 1989). In this shidy, it was employed in order to determuie if the concentration of the toxic metals under study behaved similarly at al1 three of the

24 shipwreck sites. Before an ANOVA cmbe perf'onned, the data must be examineci for nodty and heteroscedascity. This examination reveaied the data to be nomally disûibuted, however, heteroscedascity was found to exist in the variance patterns.

In order to deal with the heteroscedascity, and limit its bias on the regression coefficients, a natural log transfomation was appiied to the raw data values. This transformation resulted in the scatter plots of the data king changed from their characteristic crescentic shape into a linear relationship that can more easiIy be fit to a regression equation (See GRAPHS 1 - 16). For rasons described below, the Conemaugh data is presented separately fkom those of the MI.

Wilcox and Northern Indiana.

These scatter plots and superimposed regression lines represent the natural log of each metal under shidy on the y-axis, and the natural log of the distance of each sample ~omthe shipwreck on the x-axis. The transformation of the data using the natural log redts in the base e on the right side of the regression equation. The regression equation takes the form:

With the heteroscedascity and nonnality issues resolved, the ANOVA was performed.

This analysis revealed significant interactions between the variables fiom dBerent shipwrecks. GRAPH 1:

CONEMAUGH LN ARSENIC vs. LN DISTANCE

Rsq = 0,0940

LN.DlST

LN = NATURAL LOG

GRAPH 2:

CONEMAUGH LN CADMIUM vs. LN DISTANCE

LN = NATüRAL LOG

Page 26 GRAPH 3:

CONEMAUGH LN CHROMIUM vs. LN DISTANCE

Rsq = 0.0304 1

LNDIST

LN = NAWRAL LOG

GRAPH 4:

CONEMAUGH LN COPPER vs. LN DISTANCE 22- v 2.0 - 1.8 - t v 1.6- v

1.4-

1.2- v 3 0 1.0- i w A .8, Rsq = 0.0632 s . I v -.2 0.0 2 .4 -6 -8 1.0 1.2 1.4

IN = NATURAL LOG

Page 27 GRAPH 5:

CONEMAUGH LN LEAD vs. LN DISTANCE

Rsq = 0.3624

LN.DIST

LN = NATURAL LOG

GRAPH 6:

CONEMAUGH LN NICKEL vs. LN DISTANCE 2.6

Rsq = 0.0994 4

LN.DIST

LN = NATURAL LOG

Page 28 GRAPH 7:

CONEMAUGH LN VANADIUM vs. LN DISTANCE 2.8

2.6 v

2.4 * v v 22- v v v 2.0 - v v f 1.8 RS~= 0.0323 1 6 i -2 0.0 .2 .4 .6 .8 1.0 12 1.4

LN = NATüRAL LOG

GRAPH 8:

CONEMAUGH LN ZINC vs. LN DISTANCE 3.6

Rsq = 0.3516 4

LN = NATüRAL LOG

Page 29 GRAPH 9:

M.I. WILCOX AND NORTHERN INDIANA LN ARSENIC vs. LN DISTANCE

9.5 j \i, '-. v i 1. : WECK 1 .. I 9.0; '1 -. r 2.00 v 8.5 A f 1 1.00 , < '- 8.04 -y Total Population f 7.5 i ! Rsq = 0.7091 1 r 1 r -.2 0.0 .2 -4 .6 .8 1.0 1.2 1.4

LN.DIST

1.00 = M.I. WILCOX; 2.00 = NORTHERN INDIANA LN = NATURAL LOG; WRECK = SHIPWRECK

GRAPH 10:

M.I. WILCOX AND NORTHERN INDIANA LN CADMIUM vs. LN DISTANCE 0.0 , 1 w

! r 2.00 *.8 {

-1 .O: i v 1.00 1 - ;:: -1.2; ;:: Total Population -1.4 i , Rs~= 0.3882 -.2 0.0 .2 -4 -6 -8 1.0 1.2 1.4

LN-DIST

1.00 = M.I. WILCOX; 2.00 = NORTHERN INDIANA LN = NATURAL LOG; WRECK = SHIPWRECK

Page 30 GRAPH 11:

M.I. WILCOX AND NORTHERN INDIANA LN CHROMIUM vs. LN DISTANCE

v 3.6 -, l 3.4; v 3.2 T WRECK 3.0 4 v r 2.00 2.8: T v 2.6 - v 7.. r 1.00 T v : az: 2-44 *-. . - v . Total Population 2.2; - 4 5 2-04 T r . 1 Rsq = 0.6779 -.2 0I0 -2 -4 -6 .8 1.0 1.2 1.4

LN.DIST

1.O0 = M.I. WILCOX; 2.00 = NORTHERN INDIANA LN = NATURAL LOG; WRECK = SHIPWRECK

GRAPH 12:

M.I. WILCOX AND NORTHERN INDIANA LN COPPER vs. LN DISTANCE

WRECK

1.. I '. 2.00 2.5 -, i ----,'d I

I v 7 1 2.0: 7 Q T Total Population 3 1.5; , Rsq = 0.6665 -.2 0:0 .2 4 -6 .8 1.0 1.2 1.4

1.00 = M.I. WILCOX; 2.00 = NORTHERN INDIANA LN = NATURAL LOG; WRECK = SHlPWRECK

Page 31 GRAPH 13:

M.I. WILCOX AND NORTHERN INDIANA LN LEAD vs. LN DISTANCE 4.0,

1 i Rsq = 0.7491 1 I -.2 0.0 .2 .4 .6 .8 1.0 1.2 1.4

LN.DIST

1.00 = M.I. WILCOX; 2.00 = NORTHERN INDIANA LN = NATURAL LOG; WRECK = SHIPWRECK

GRAPH 14:

M.I. WILCOX AND NORTHERN INDIANA LN NICKEL vs. LN DISTANCE

j WRECK 3.0 4 --.. 2.8 4 2 ... t r 2.00 1 . 2.6 -! 'K, T ' r 1.00 f v -.--. - 2-44 . -..v 1- T, . Total Population >\ ..\ T Rsq = 0.7676 4 -.2 010 .2 4 -6 -8 1.0 1.2 1.4

LN-DIST

1.00 = M.I. WILCOX; 2.00 = NORTHERN INDIANA LN = NATURAL LOG; WRECK = SHIPWRECK

Page 32 GRAPH 15:

M.I. WILCOX AND NORTHERN INDIANA LN VANADIUM vs. LN DISTANCE 4.0 ,

3.8 j I

WRECK

3.2 1 r 2.00 3.0 j T > 2-84 + Total Population w 5 2.6 i v Rsq = 0.4504 . 1 -12 O:O -2 .4 .6 -8 1.0 1.2 1.4

1.00 = Ml. WILCOX; 2.00 = NORTHERN INDIANA LN = NATURAL LOG; WRECK = SHIPWRECK

GRAPH 16:

M. 1. WILCOX AND NORTHERN INDIANA LN ZINC vs. LN DISTANCE

5.0 1 7

-1 '1 '1 v--. t 4.5 1 1, t v 1. \ l.,v WRECK 7 -1 1 4.0 i \ >-y . 1 2.00 . I , : v 1 v z 3.5 j 'Y - 1-0° N , : Total Population f 3.0 1 1 Rsq = 0.5961 , 1 -.2 0.0 .2 -4 .6 .8 1.0 1.2 1.4

1.O0 = M.I. WLCOX; 2.00 = NORTHERN INDIANA LN = NATURAL LOG; WRECK = SHIPWRECK

Page 33 From the 2-way ANOVA of shipwreck and sector vs. toxic metais for dl 36 samples (See

TABLES 2 - 9), it was found that signincant interactions existed As, Cr, Cu, Ni, V, and Zn ail

have significant F values. For Cd, while there is no significant interaction, it should be no@ that

there were no reported concentrations above the detection bitof the ICP-OES,and a value

below this level was substituted. This resulted in a 'flat-line' scatter plot (See GRAPH 2). For

this reason, the Cd &ta fiom the Conemaugh was excluded fiom Meranalysis.

Due to the similarity of environmentai conditions, and an examination of the natural log

metal vs. natural log distance relations (See GRAPHS 1 - 16). the MX Wilcox and Northem

I&M data were combined. This new data set was then subjected to an ANOVA (See TABLES

10 - 17). No signifiant interactions were found for Cd, Pb, or V. Some signincant interactions

mnahed for the other metals, and are associateci with a difference in the slope of their regression lines. The impmvement in redts fkom this second senes of ANOVA tests over the first was

signincant. Three metals had all interaction removed, and the others experienced rnarked

improvements. In order to maintain as large a sample as possible, and therefore degrees of freedo4 the MI. Wilcox and Northem Indiana data were kept together for Meranalysis.

Finally, regression analysis was performed (See TABLES 4 - 11). For this analysis, the t, signincance, r, and 9 were used to determine the devance of the output. With twenty-four

data points, at the 0.05 level of significance, the t,, value is 2.5 1, and the cntical r value is 0.404.

Following th,al1 the variables under study have significant r values, and negative signifiant r values. The percent explaineci for each variable, fiom each regression equation are: 1. arsenic -

70.9; 2. cadmium - 38.8; 3. chrornium - 67.8; 4. copper - 66.7; 5. lead - 74.9; 6. nickel - 76.8; 7. vanadium - 45.0; and 8. zinc - 59.6. Any P value in excess of 0.1 60 is considered significant. TABLE 2: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN ARSENIC.

Unique Metrioci Sum of Mean Squares df Squafe F AS ~aintttects (c;ommeu) 12.859 4 3215 WRECK SECTOR 2-Way lnterad0cls WRECK SECTOR Madel Residual Total a- LNAS by WRECK, SECTOR

TABLE 3: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN CADMIUM.

nique Method Sum of Mean Square F Sig. LN.GD ~aintmus (r;ombinea) 339 4.938 004 WRECK .388 5.651 .O09 SECTOR 290 4224 .O25 2-Way Intetadons WRECK ' SECTOR Model Residual

1 Toîal 1 a. LN-CD by WRECK, SECTOR b. Ali effecEs entered simu~usly

Page 35 TABLE 4: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN CHROMIUM.

ANOVA..~

Sum of

GR ~alntneus (r;omonea) WRECK SECTOR 2-Way Interactions WRECK ' SECTOR Model Residual Total a. LN.CR by WRECK, SECTOR b. Ail effec& entered simuitaneoudy

TABLE 5: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN COPPER.

ANOVA*~

Jniaue Method Sum of Sig. J WRECK SECTOR 2-Way lnteracüons WRECK ' SECTOR Model Residual

Page 36 TABLE 6: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN LEAD.

Sum of ~aintrtects (~'omined) WRECK 14.558 SECTOR 3.533 2-Way Interadions WRECK ' SECTOR Model Residual Toial

b. All Meds enû3reâ simubneously

TABLE 7: 2-WAY ANOVA INTERACTIONS OF WRECK AND SECTOR FOR LN NICKEL.

unique mmoa Sumof 1 1 Mean 1 I 1 Squares df Square F NI ~a~ntttect~ (~tnblnw 6.m 4 1.130 32.339 WRECK SECTOR 2-y Interactions WRECK SECTOR Model Residual Total a. W.NI by WRECK, SECTOR b. AI1 effeds entered simultaneously

Page 37 TABLE 8: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN VANADIUM.

unque ~ema -- Sum of 1 Mean 1 I Squam 1 df Square F v am t;mcts (-na) a285 1 4 2.W6 WRECK SECTOR 2-Way Interadions WRECK ' SECTOR Modd Residual

a. LN.V by WRECK, SECTOR

TABLE 9: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN ZINC.

Unique Mehd Sum of Mean df square F Sig. sa) 4 214 5m-m WRECK SECTOR

2-Way Interactions WRECK + SECTOR Model 14.803 8 1.850 31.950 Residual 1-564 27 5.792E-02 Total - 16.367 35 .468 a. LNZN by WRECK, SECTOR b. Ail effeds entered simuftaneousîy

Page 38 TABLE IO: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR . FOR LN ARSENIC ON THE M.I. WILCOX AND NORTHERN INDIANA.

ANOVA&~

Sum of Squares AS ~aintttect~ (~ornbinecq 5.054 WRECK .803 SECTOR 4250 2-Way Interadions WRECK ' SECTOR -945 Modal 6.358 Residual 2211

Total- I 8.569 a. LNAS by WRECK,SECTOR b. An effeds entered simubneousiy

TABLE il:2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN CADMIUM ON THE M.I. WILCOX AND NORTHERN INDIANA.

ANOVA~~

nique Method Mean 1 1 Square F Sig. 317 3.0ff 054 WRECK 1 SECTOR 2 2-Way Interactions WRECK' 18.774E-02 1 I SECTOR 2 Model I Residual 1 Total 1 2.871 1 23 a. LN.CD by WRECK, SECTOR

Page 39 TABLE 12: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN CHROMIUM ON THE MwIm WILCOX AND NORTHERN INDIANA.

ANOVA*~

Sum of F Sig. 10.695 006 271 3.41 1 .O81 SECTOR 2282 14.336 .O00 2-Way Interactions WRECK * .693 SECTOR Model 3284 Residual 1.432 Total 4-717 a. LNCR by WRECK, SECTOR b. Aîi efïects entered simuitaneousiy

TABLE 13: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN COPPER ON THE Mol. WlLCOX AND NORTHERN INDIANA.

Unique Method

Sum of 1 1 Mean- .. - -- 1 1 Squares df Square F Sig. GU ~aintnects (mima) 3.6 f 4 3 1.2z5"--m WRECK SECTOR 2-Way Interactions WRECK ' SECTOR Model Residuaf Total a. LN.CU by WRECK, SECTOR b. AI1 effeds enbred sirnultaneously

Page 40 TABLE 14: NUAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LEAD ON THE M.I. WlLCOX AND NORTHERN INDIANA.

ANOVA*~

Surn of LNPB ~a~nmeus (mrnl>rnea) + WRECK .468 SECTOR 3.394 2-Way tnteradions WRECK ' SECTOR .6l4 Model 4.460 Residual 1.737 Total a. LN-PB by WRECK, SECTOR b. All effeds entered simuitaneousfy

TABLE 15: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN NICKEL ON THE M.I. WlLCOX AND NORTHERN INDIANA.

Unique Meaiod Sum of Mean Squares df Square F NI MM t:f~8~t8 (mminea) 2. 3 928 13.1 16 WECK -186 1 .186 2.624 .123 SECTOR 2.599 2 1.3W ( 18.362 .O00 2-Way Interactions WRECK ' SECTOR Model Residual Total a. LN.NI by WRECK, SECTOR

Page 41 TABLE 16: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN VANADIUM ON THE M.I. WILCOX AND NORTHERN INDIANA.

ANOVA~~

liquaMettK Mean Square LN.V ~mttteas (r;ornmnea) 292 WECK 3.1 5SE-03 SECTOR .436 2-Way Interadions WRECK ' SECTOR -105 Model -221 Residual 5244E-02 1 Tdal 8.91 2E62 a. LN.V by WRECK, SECTOR

TABLE 17: 2-WAY ANOVA OF INTERACTIONS OF WRECK AND SECTOR FOR LN ZINC ON THE M.I. WlLCOX AND NORTHERN INDIANA.

Unique Mettiod Surn of 1 1 Mean 1 1 df Square ) F ~ainttted~ (~ommnea) 3 88r ( 12-401 WRECK SECTOR 2-Way t ntefactions WRECK ' SECTOR Model Residual Total a. WZN by WRECK, SECTOR b. Ali effeds enterd simuttaneousiy

Page 42 TABLE 18: REGRESSION ANALYSlS Mol. WlLCOX AND NORTHERN INDIANA LN ARSENIC vs. LN DISTANCE

am. Error of AdjuW the Model R R Square R Square Estimate fU9 696 a. Predidors: (Constant), LN.DIST b. Dependent VariaMe: LN.AS

k Standardi zed Unstancfard'ied Coenicien Coefficients ts Model 8 Su- Error Beda t Sig.

1 (wnstant) 9.839 129 /4.657 000 I LN.DIST -1.200 -164 -.842 -7.322 p .O00 a. Dependent Variable: LNAS

TABLE 19: REGRESSION ANALYSlS Mol. WlLCOX AND NORTHERN INDIANA LN CADMIUM vs. LN DISTANCE

Acïusted the -- Model R R Square Rdquare Estimate 1 a. Predicîors: (Constant), LMDIST

Standard zed Unstandardaed Coefficien Coefficients ts Model B Std. Error Beta t Sig. 1 (wnstant) - 1OS O 000 LN-DIST 9.514 .138 w.623 -3.736 .O01 , a. Dependent VariaMe: LN.CD

Page 43 TABLE 20: REG1 :ESSIONANALYSE M.I. \ llLCOX AND NORTHERN INDIANA LN C +ROMIUM vs. LN DISTANCE

Std. Enor of 1 Adi~litsd 1 the Model R R Square R Square -mate 1 0m 618 663 a. ?redidors:~(~o~tant).LN.DIST b. Dependent Variable: LN.CR

aranaami zed Unstandardized Coeftïcien Coefiicients ts B Std. Error Beta t Sig. 33*~.00Q W.DIST œ.871 -128 -.823 -6.805 .O00 a. Dependent Variable: W.CR

TABLE 21: REGF !ESSION ANALYSE M.I. Y nLcox AND NORTHERN INDIANA LN C 3PPER vs. LN DISTANCE

Errer of Adustecl the Model R RÇqwre R&- Estimafe

1 816a 7 651 3Z/S -' a- Predidors: (Constant), LN-DIST

Standardi zed Unstandardized Coenicien Coefficifficients ts Model B SM- Em Beta t Sig. 1 (GOnStant) 3253.Izs-25.840- LN-OIST -1 .O58 .159 -.a16 -6.631 .O00 a. Dependent VanaMe: W.CU

Page 44 TABLE 22: REGRESSION ANALYSIS MwI.WlLCOX AND NORTHERN INDIANA LN LEAD vs. LN DISTANCE

Emr of Adjuaed the Madel R R Square R Square Estimate 1 a v /49 f38 2668- a- Predidors: (Constant), LN.DIST b. Dependent Variable: LN-PB

amnaami Zed Unstandardied Coefficien Coeffiaents ts Model B Std. Enor Beta 1 (mstant) 3.3-h LN-DIST -1 .O49 -129 0.866 -8.1 05 .O00 A a. Dependent Variable: LN-PB

TABLE 23: REGRESSION ANALYSIS MmIw WlLCOX AND NORTHERN INDIANA LN NICKEL vs. LN DISTANCE

Model Summaryb

Std. Errer of l i l I Model R Square Estimate f 131 a. Predidors: (Constant), LN-DIST b. Dependent Variabie: LN.NI

Standardi zed Unstandardized Coefficien Coefficients ts Model B Std. Emr _ Beta t Sig. 1 (wn=w 3.434 OU/ 39.4411 000 LN.DIST 0.941 -110 -. 876 -8.524 .O00 a. Dependent Variable: LN.NI

Page 45 TABLE 24: REGRESSION ANALYSIS M.I. WlLCOX AND NORTHERN lNDlANA LN VANADIUM vs. LN DISTANCE

R Square R Square 1 Esb'mate

a. Predidors: (Constant), LN-DIST b- Dependent Variable: LN.V

T Standardi 1 z8d Unstandardized CoefCicien CoafficienEs ts Mdel B SM. Emr Beta t 1 (Gmw 3.521 08$ 40.488 LN.DIST 9.468 .Il0 9.671 4.246 .O00 a. Dependent VariaMe: LN9

TABLEZ& REGRESSION ANALYSE M.I. WlLCOX AND NORTHERN INDIANA LN ZINC vs. LN DISTANCE

Model R R Square f R Square Esürnate r 128 I ~r8 2951 , a. Predictots: (Constant), LN.DIST b- Dependent VariaMe: LNZN

Standardi zed Unstandardized Coefficien Coeffiaents ts Modei 6 Std. Error Beta t Sig. 1 (~onstant) 41- 113 40a WI LN.DIST -.819 .144 -.772 -5.698 .O00 A a. Dependent Variable: LNZN

Page 46 All variables meet this requirement.

Oved, îhe fo!lowing metals on the MI. Wileox and Northern Indiana sites were fou& to exhibit moderate to strong, and significant inverse relationships with log distance: 1. arsenic; 2. caclmium; 3. chromium; 4. copper; 5. lead; 6. nickel; 7. vanadium; and 8. zinc. Also, an examination of the scatter diagrams (See GRAPHS 9 - 16) tend to support these statistical findings. On the Conemmrgh, no significant relationship between metal concentrations and log distance were observeci because of the following: 1. low zebra mussel concentration; 2. the presence of strong current action' and 3. more intense ice action due to the fact that this wreck lies in shallowcr water than the others. 7. CONCLUSION

7-1 Discussiog

This thesis set out to examine toxic metal concentrations fiom zebra musse1 wastes around selected shipwrecks in the Western Basin of Lake Erie. Specificaily, three hypotheses were put forward: a) that toxic metal concentrations in sediments around shipwrecks decrease with in-ing distance hmthe wreck; b) that zebra mussels bioprocess toxic metals and biodeposit them ont0 sbipwrecks; and c) that some toxic metal concentrations WUex& CCME standards.

The data, and analysis of it, supports aU three of these hypotheses.

The regression equations for each metal under study are sipniIiciilit, and negatively sloped.

TAf3LE 26: SUMMARY OF REGRESSION ANALYSIS FOR M.I. WILCOX AND NORTI%ERN lN.DL4NA.

- ---- NB: r,, = 0.404

This indicates that the concentration of toxic metals does in fact decrease with increasing distance hmthe shipwecks. The concentrations of the toxic metals under study were higher in close proximity t~ the zc5z niussel colonies (i.e. on the shipwrecks) than they were away fiom the cotonies. This would indicate, and is supported by the literature, that the zebra mussels are actively filtering the met& fiom the water column, and biodepositing them on the shipwfecks. If the toxic metals were merely settling ont0 the lakebed, their concentrations would be expected to be evenly distributeci. They are not.

Finaüy, a cornparison of the toxic metai concentrations from on and around the shipwrecks with CCME standards (See TABLE 1) reveals repeated violations. While this thesis does not examine the risks associated with exposure to these metals, it is certainly worth noting that the standards have been exceeded.

In order to more Myunderstand the mechanisms at work with respect to zebra mussels and their ability to biodeposit sediments which are contaminateci with toxic metals, several avenues for enquiry are avaiiable. Laboratory analysis of a wide spectrum of toxic metais shouid be pexfomed. Just as Reeders et aL(1989) showed that substances such as PCB's are not biodeposited by Dreissenapolymorpha, it is possible that not all toxic metals are. Knowing which metais to test for can gready reduce the expense associated with sediment analysis, and perhaps expose metabolic pathways utilized by zebra mussefs.

Ongoing analysis of the sediments around shipwrecks, particularly those which are used as tourist attractions, should be perfonned. If the concentrations of toxic metals increase over time due to the ongoing filtering activities of zebra musseb, as suspecte& the sedhnents will becorne more hazardous with passing the. The nurnber of shipwrecks uder study, as well as the number of sampling sites mund each wreck should increase. With the increase in samphg sites and wrecks undet study, the toxic metal concentrations around the shipwrecks can be accurateiy studied.

Sorne consideration as to the environmental conditions around the shipwrecks unda smdy should aiso be &en. In this study, the Conemuugh was fond to have significantIy different toxic metal concentration patterns than the other wrecks. This was most Likely the resuit of diBering environmental conditions at the site of the Conemaugh. Should these enWonmentd factors be quantüïed at each site, further insight into the accumulation of contamhated biodeposited sediments could be ascertained.

7.3 Co~

Weeach of the hypotheses put forth in this study have been supported by the data, severai new questions have arisen. How does the physical environment of the shipwreck site rnom the concentration of toxic metals around the wreck? Does the density of zebra mussels influence the concentration of toxic metais aromd the shipwreck? Are the concentrations of toxic metals increasing over time around the zebra mussel colonies, and therefore on the shipwrecks of the Western Basin of Lake Erie?

These are aii important questions th& need to be answered. As the waters of Lake Erie, and the Great Lakes in general, continue to increase Ili cl&@, more scuba divers are likely to venture in search of local shipwrecks. Should this reduced turbidity be linked to ever increasing toxic metal concentrations on shipwrecks, the two phenornena will interact to increase the relative dangers. Those in the diving community, and those who promote diving tourism need to be derted. It is not enough, however, to be aware of the situation. Further andysis is needded (

8. APPENDICES Metal

Arsenic (As) Lesions of the skin and mucus membranes, lesions may become cancerous. Increased mortality hmseved types of cancer.

Cadmium (Cd) Ingestion (>l Srng/L) can cause symptoms simi1a.r to food poisoning. Long-term exposure most damaging to kidneys.

Chromium (Cr) Hexavdent chromium is corrosive, and sensitipng. Skin ulcers, perforation and irritation of nasal septum are possible.

Some salts cm cause abdominal cramps, diarrhea, and vomiting.

Centrai nervous system is critical organ, chiidrai are more susceptible. Some compounds can cause nausea, vomiting, and dianliea.

Nickel (Ni) Allergic response. cancer, and respiratory tract disurders.

Varindium (V) Respiratory tract irritation, nausea, vomiting, and abdominal pain.

Zinc (Zn) A number of zinc salts may enter the body through the skin or by ingestion and pruduce intoxication. Zinc chloride has been found to cause skin dcers* Other arise in the presence of As, Cd, Pb, and Cr. 1 Metals Under Study 1 Government Standards' (ppm) 1

------Arsenic (As) 5.0 Cadmium (Cd) 0.5

Nickel (Ni) 20.0 Vanndiumo 25.0

1. Canadian Council of Ministers of the Environment. Interim Canadian Environmental Quaiity Criteria for Contammzted Sites, Report CCME EPC-CS34, September, 199 1. C: Sediment Sêmple Raw Data

8.3.1 Tioga and Spedm

Metal Under Smdy Tiogal (ppm) Speadar' (ppm)

Arsenic (As) 3.3 1 3.48 Cadmium (Cd) da da - Chromium (Cr) 3 9.24 37.05 COPF(CU) 39.89 29.63 Lead (Pb) 50.83 32.71 ------Nickel (Ni) 45.44 36.18 Vanadium (V) 32.54 32.46 151.6 135.0

1. Data hmAuîhor's Pilot Study of JUS, - August, 1995. Sample 3 Sample 5 +Sample 6

- -- Sample 8 Sample II Sample 12

NB: Al1 measurements given m ppm, and provided by Great Lakes Institute for Environmental Research (GLER), 1997. Metai Sarnple 1 Sample 2 Sampie 3 SampIe 4 Sample 5 Sample 6

Sample 7 Sample 8 Sample 10 Sample 12

NB: Ali measurements given in ppm, and provided by Great +es lnstitute for Environmental Research (GLIER), 1997. Sample 1 Sarnple 5 1 Sample 6

Sample 9 Sample 10 Sample 1 1 Sample 12

NB: AU measurements given in ppm, and provided by Great Lakes Institute for Environmental Rmh(GLIER), 1997. The following is an except hmGLIER (1996), and outlines the steps taken in the preparation of the sediment samples utilized in this study:

Weigh 1.0g of dry sample into a 125mL Erlenmeyer flask Add lOmL of Nitic Acid - ultra trace grade - and dow to stand at room for 0.5-1 hours. To control foaming, an ice bath may be necessary. Then add 20mL of Hydrochloric Acid - ultra trace grade - at mmtemperature and let stand for 1 .O hours. Again, to control foaming, an ice bath may be neces-. The samples are then heated graddy on a hot plate to 100 C for rernainder of day, approxïmately 5.0 hours. Continue heating ovemight at 50 C or until appmximately 5mL acid is left (most do not go to dryness). If so, add another 4mL of aqua-regia (ImL Nitric and 3mL Hydrochloric Aciûs) and heat for another hour. Tderto dry pre-weighed 125mL LDPE Nalgene@ bottles, filtering through WbatmanO #4 or #41 filter paper. Rinse Erlenmeyer 5 heswith P.W. during transfer. Make up to 1OOg by to 0.01 g. Exercise care to keep pre-weighed bottie dry during handling to avoid added error to solution final weight.

Quality Control Per Sample Sets Digested:

-Randomly place among set: - 3 meuiod blanks, - 2 samples in duplicate, - 1 sediment Certified Reference Matenal, - 24 sample~,and - 1 in house wntrol sample. h of Zebra Mussels on the Northern Indiana

Photo by Jennifer Elcomb, 1996. 8.6 Photom~hof Fissoris@ Maxim Axial Plasma Spectophotometer

Photo by Author, 1997. Inariaring shield

Sample aerorol or vapor in argon

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Name: Andrew Allen Brooks

Born: 14 October 1970 Windsor, Ontario

Education: Walkedle Collegiate institute Windsor, Ontario 1984 - 1989

University of Windsor Windsor, Ontario 1989 - 1994, Honours B.A. Geography; Environmentai Resource Management

University of Windsor Ontario 1995 - 1997, MA.

Geography; Environmental Resource ' Management