Trace metals and pesticides in sediments and organisms in John Pennekamp Coral Reef State Park and Key Largo National Marine Sanctuary report

[From the U.S. Government Printing Office, www.gpo.gov]

REPORT

TRACE METALS AND PESTICIDES IN SEDIMENTS
AND ORGANISMS IN JOHN PENNEKAMP
CORAL REEF STATE PARK AND KEY LARGO
NATIONAL MARINE SANCTUARY

Renate H. Skinner
Bureau of Biological and Interpretive Services

Walter C. Jaap
Bureau of Marine Research
Florida Department of Natural Resources

US Department of Commerce
NOAA Coastal Enterprise Center Library
2204 South Hobson Avenue
Charleston, SC 29405-2413

r- US Department of Commerce ---!
NOAA Conotal Q=jilcnes Ce mter Library
2234 Soultla E-C"=M Avonue
L_ Charleston, SC 2DZ105-2413 j

EXECUTIVE SUMMARY

Introduction

The study area is located in the Atlantic Ocean seaward, of

Key Largo, in the John Pennekamp Coral Reef State Park and the

Key Largo National Marine Sanctuary. Biscayne National Park is

immediately north of the area. Together, these three refuges contain

a major portion of the Florida reef tract, the only shallow-tropical

coral reef ecosystem on the north American continental shelf. The

coral reefs, seagrass meadows, and mangrove forests support highly

diverse tropical biological resources found nowhere else in the

continental United States.

This ecosystem supports a major tourist industry focused on

recreational activities of fishing, snorkling, and scuba diving.

There are also major finfish and lobster commercial fisheries in

the immediate area. Recent economic estimates of the coral reef

habitat report that larger reefs in the system (Molasses Reef)

are worth $400 million based on the entire spectrum of use; the

park and sanctuary reef resources are thus valued at $1.6 billion

(Mattson and DeFoor, 1985).

The recent rapid urbanization of upland and coastal areas

of Key Largo . and the adjacent Keys are a cause for concern.

Increased population density, boat usage, liquid and solid waste

disposal, channelization, dredging, marina construction and

activities threaten environmental quality through contamination

and physical degradation.

A number of large, coastal, urban developments are proposed

along the John Pennekamp Coral Reef State Park boundary. This

study,was conducted prior to the construction of these developments.

Purpose

The purpose of this two-year study was to establish a reliable

information base on the trace metal, pesticide, PCB, and pthalate

concentrations found in surface sediments and representative organism

tissues from 20 sites in John Pennekamp Coral Reef State Park and

adjoining Key Largo National Marine Sanctuary. other chemical

characteristics of the sediments and organisms were also collected.

The information will be used in support of monitoring environmental

quality and resource management.

Results

The information indicat@s that trace metals are present in

sediments and plant and animal tissues in part per million

concentrations. Copper appears to be relatively high. Filter

feeding. organisms concentrate aluminum and iron. Pesticides were

present at all stations in part per billion concentration. Some

of the compounds detected are currently banned or restricted. The

DDT and deterioration compounds were persistent in sediments and

tissues. There was considerable spatial and temporal variability

in the information. Contamination is not restricted to the coastal

area; offshore reef sites had similar contamination characteristics.

There is concern regarding the cummulative effect that the trace

metals, pesticides, PCBs, and pthalates have on the organisms.

Some tissue samples contain in excess of ten different high risk

compounds.

ACKNOWLEDGEMENT

The research resulting in this report was funded by grants CM 108
and CM 129 provided by the DER and by the Coastal Zone Management
Act of 1972, as amended, administered by the OCRM/NOAA.

INTRODUCTION

Purpose

Baseline data is required to evaluate current environmental quality in

John Pennekamp Coral Reef State Park and Key Largo National Marine

Sanctuary. This is accomplished by investigating the presence of certain

chemical parameters in the sediments and marine organisms. Based upon this

information, future monitoring will. make it possible to identify any

changes that may disclose degradation of the resource and indicate trends.

Although a long-term monitoring program should be developed, we must first

accomplish a short-term study to establish a data base before additional

onshore residential and commercial developments are completed.

Along with an on-going water quality monitoring program conducted by

the Department of Natural Resources for the past four years at John

Pennekamp Coral Reef State Park, this joint DER/DNR project is designed to

establish baseline levels in bottom sediments and tissue samples for

chemical parameters listed at stations located in John Pennekamp, Coral Reef

State Park. and Key Largo National Marine Sanctuary. This study will

complement present data by providing additional information beyond water

quality, and additional parameters and stations. Besides interacting with

the monitoring program in the park mentioned above, and monitoring in the

adjacent Key Largo National Marine Sanctuary and Biscayne Na tional Park,

the proposed study will interact with section- 205J water quality study in

Marathon. Results will also be provided to the Department of Community

Affairs and the Monroe County Planning Department, and federal agencies

involved.

Resource Historical Patterns

John Pennekamp Coral Reef State Park is a portion of the only living

coral reefs in the continental United States and was established on Key

Largo in 1959. Some 88 square miles of coral reefs, seagrass beds,

mangrove swamps, and hardwood hammocks are protected here as a

representative example of natural Florida, providing a wide range of

recreational and aesthetic opportunities. Extending seaward three nautical

miles, the park contains 2,290 upland and 53,722 submerged acres. From the

three-mile limit, the area extending seaward to the 300 foot depth contour

was established as the Key Largo National Marine Sanctuary in 1975. The

sanctuary administered by the National Oceanic and Atmospheric

Administration encompasses 100 square miles, for a total protected area of

188 square miles. The Park and Sanctuary are listed on the National

John Pennekamp Coral Reef State Park is located on Key Largo,

approximately 50 miles south of Miami, on U.S. Highway 1. It has a

north/south distance of approximately 20 nautical miles. It extends

eastward from Key Largo for three nautical miles to the State's territorial

limit (Figure 1). In 1975, the area of the three-mile limit to the 300

foot contour line in the Florida Straits was established as the Key Largo

National Marine Sanctuary. The Park and Sanctuary are separate entities.

The Park is a state-regulated resource, while the Sanctuary is governed by

the National Oceanic and Atmospheric Administration under Federal statutes

and administrative procedures. Biological and hydrological processes

functioning in the seaward portion of the Park are identical to those

occurring in the Sanctuary.

The location is at the northern geographic limit of the proper

environmental conditions necessary for reef development. Natural forces

such as hurricanes and the intrusion of cold water subject the reefs to

stressful conditions. In addition to such natural forces, the Park's and

Sanctuary's coral reefs are stressed by recreational and commercial

activities. Hundreds of thousands to over a million visitors are attracted

to the reefs annually. Many local businesses are tied to the existence of

healthy, thriving coral reefs, while others are dependent on the tourists.

Nonetheless, much coral damage occurs, caused by careless fishing, boating

and diving practices. Coral growth is so slow that it takes many years for

recovery of damaged portions.

Rapid development in the Keys during the last 10 years has made the

task of protecting the park waters and reefs more difficult and complex.

Pressure for more and higher density urbanization on North Key Largo which

borders the park has increased greatly. In order to protect the natural

resources, the cumulative effect of all development on park waters and

marine resources--especially the reef corals in both parks and sanctuary-

must be, carefully evaluated. Sixteen major developments are presently

planned for North Key Largo; together they would house more inhabitants

than all of Key West (Miami Herald, Sept. 1982). Most plans are for

condominium projects, many with marinas connected to the open water. The

demand for large marinas is increasing, compounding the problems.

Pollution and turbidity associated with this sort of development are

known causes of - stress in the marine environment. If North Key Largo is

developed according to plans, the resulting stressful conditions will not

be temporary, as in the case of an occasional oil spill or dredging, rather

they will be chronic. The previously undisturbed natural shoreline would

be destroyed by bulkheading, dredging and filling. Aside from terminating

the park visitor's aesthetic experience of an undisturbed coastline,

development will destroy adjacent mangroves and uplands, and will bring the

threat of man-made pollution to this relatively remote part of the park's

waters. Recent improvements in drinking water supply and access roads and

the technology of waste disposal have led to construction proposals for

nearly 7,000 housing units in this area. In the last ten years Monroe

County has approved the construction of 4,206 units on land bordering John

Pennekamp Coral Reef State Park, and the pressure to develop the Upper Keys

will continue.

As development on the uplands replaces the natural environment

adjacent to park waters, the marine resources will suffer degradation

through exposure to pollution caused by human activity. Pollutants include

silt, sewage, fertilizers, oils and greases, pesticides, PCBs,

plasticizers, and trace metals which can enter the marine environment

directly or through runoff. I Once in the water, pollutants are spread

through wind, wave, and tidal action.

Coral reefs cover only a small percentage of submerged bottom in the.

Park and Sanctuary. By far the largest areas are seagrass beds, sand, or

hard bottom (fossil reefs). Together with extensive coastal mangrove

forests, these areas are vital to the existence of the reefs because they

supply nutrients to all other plants and animals in the marine environment,

including food and game fish. Activities such as dredging and filling

cause siltation and clouded water (turbidity); housing developments,

marinas, and boating are sources of many pollutants. Besides having an

effect on inshore sea life, turbidity and pollution will eventually

decrease the reef's viability because the degraded water is transported to

the reefs via wind and tide.

The rationale for conservation and prudent stewardship of these

valuable resources can be divided into three categories. First, reefs are

an aesthetic natural wonder, a Florida treasure similar to the Everglades

and the Grand C anyon and should be conserved for the enjoyment and

enlightenment of future generations.. For example, Carysfort Reef is

approximately 5200 years old. It has weathered all forms of natural

climatic and oceanic stress; however, if it were destroyed by human

activity, it could not be restored or replaced.

Second, coral reefs in the Park and Sanctuary are economically

important to the surrounding human community. Monroe County's primary

industry, tourism, is highly dependent on pristine water, fishing, colorful

reefs, and a lush tropical setting. Fishing, diving, and lobstering

establishments, educational institutions, gift shops, motels, restaurants,

etc., all gain economic benefit from the coral reefs and other living

resources.

Thirdf ecologically, the natural processes that have created the.

biological diversity in these coral reefs must be allowed to continue

without undue interference from external human influences. While the basic

functioning of these processes may still be a mystery, a conservative

approach offers the best chance for maintaining the system.

Recent awareness of the increasing negative impact of onshore

development and associated resource and water usages in Key Largo has

prompted the Governor and Cabinet to request a report describing the

situation and recommend actions to enhance existing resource protection at

John Pennekamp Coral Reef State Park and the contiguous Key Largo National

Marine Sanctuary (Skinner and Jaap, 1984).

As explained in the report, the coral reefs off Key Largo are a part

of the total marine environment based on and sustained through the

intricate interrelationships of biological communities and the delicate

balance of dynamic natural phenomena. Disruption of only one segment of

the ecosystem can initiate a chain reaction of events which will eventually

impact the whole system. The following points are important:

1. The reefs are at the northern geographic limit of environmental

conditions suitable for their survival. Thus, natural phenomena (such

as low temperatures) could place the reefs under stress and weaken

resistance to-additional stress imposed by human activities (such as

turbidity and pollution).

2. The marine environment may be stressed by the deterioration of water

quality caused by development of the uplands and nearshore areas.

The concern expressed for the survival of a healthy marine environment*

is based on real threats and is supported by documentation from the

Department of Natural Resources and the Department of Community Affairs.

Visitors to the park have increased approximately 25% in the last ten

years, with an approximate increase of 17% in 1983 alone. These figures

are based only on gate receipts at the state park; they do not account for

the many visitors who reached the reefs on boats originating elsewhere.

Many of the visitors to the park and sanctuary waters are non-resident

tourists, but an increasing number will be residents of the Upper Keys if

development of this area proceeds as currently pl anned.

Ecological Information

The Florida Park Service's and National Oceanic and Atmospheric

Administration's aim is to preserve a part of the Florida Keys' natural

environment, and to maintain the natural function and appearance of some of

the original Keys, surrounding waters, and reefs. Until recently,

protective State and Federal statutes assured that Park and Sanctuary

resources would exhibit a vitality superior to other areas in the Keys.

A number of plants and animals in the Park and Sanctuary and immediate

vicinity are on State and Federal lists of protected species. Among them

are marine animals such as manatees, whales, porpoises, and sea turtles, as

well as the endangered American crocodile, and land animals such as the Key

Largo woodrat, Key Largo cotton mouse, and the bald eagle.

The subtropical climate in the Keys supports a diverse biological

resource resembling more southerly Caribbean areas. This is the only

region in North America supporting such a tropical ecosystem.

In a progression from the upland terrestrial habitats seaward to the-

91 m (300 ft) depth boundary of the Sanctuary (13-7 km off the coast), a

succession of habitats forms a mosaic whose parts are interrelated and

interdependent for the success of resident species. The upland tropical

hardwood forest gives way to a coastal mangrove forest. At the land-sea

interface the mangroves are replaced by a limestone fossil reef rock

dominated by attached algae. Mud flats line the mangroves and rocky

shores. Seaward, a mixture of sand, seagrass, and rocky outcrops that

support hardy corals, sponges and algae occur. A few miles seaward, patch

reefs and seagrass-sand areas dominate. Beyond Hawk Channel (a natural

navigation passage between the Keys and major reefs further offshore),

there is an increasing abundance of living coral reefs. The most seaward

reef community, the bank reef (such as Molasses [Figure 2] or French

Reefs), is the most dramatic resource in the Sanctuary. Bank reef s

terminate at about 130-140 ft. depth. Beyond this depth, a sandy or rubble

bottom with a few sponges and occasional outcrops of rock occurs.

Florida's living coral reefs are 4000 to 7000 years old. They exist

in a precarious balance as the northernmost bastion of shallow water

tropical reefs in North America and are the most unique resource in the

Park and Sanctuary.

Reefs are complexes of corals and other animals and plants with the

ability to extract calcium from seawater to construct limestone skeletons

that form the reef framework. The bulk of reef mass is subsequently added

by the breakdown of the skeletons into sediments which are cemented to the

reef. Coral calcification is driven by solar energy derived through

photosynthesis: microscopic plants (zooxanthellae) within the coral tissue

J provide the energy and nutrients, recycle animal wastes, and provide oxygen.

for the coral animals. This process requires light; therefore, murky water

inhibits coral reef development.

Florida's reefs form a discontinuous chain of banks and inshore

patches, paralleling the Keys, from Fowey Rocks near Miami to Dry Tortugas.

Reef development occurs within a . very narrow range of environmental

parameters, controlled by type of available substrate (rocky or

consolidated), light penetration of the water column (low sedimentation

4; rate., clear water), and water temperature (650-90*F). Winter cold and

silmmer heat both stress the system, but potentially the most severe natural

impact to a coral reef is the hurricane. Storm-driven waves can devastate

shallow coral reefs, often dislodging large coral colonies. Storm waves

also resuspend silt, reducing light penetration and requiring the coral to

expell sediments from their surfaces. Chronic sediment fallout (as

associated with dredging) on coral surfaces causes stress which, if

unabated, leads to death.

Reefs exist in this region primarily because of 1) the Gulf Stream;

and 2) the Keys island archipelago. The Gulf Stream is a warm water

current that moderates winter temperatures while the island chain

(particularly Key Largo) forms a barrier against water movement from

Florida Bay into the Atlantic. During the winter, extreme cold fronts

chill shal low Florida Bay waters to as low as 9.4% (49*F) [the lower

thermal limit for reef corals is about 150C (59001. Cold Florida Bay

waters are transported to the Atlantic by winds and tidal flux. Key Largo

forms a barrier to water transport out of Florida Bay. Generally, coral

reef development does not occur where there are large channels connecting

Florida Bay and the Atlantic.

The mangrove and seagrass communities are also important, functioning

as nursery habitats for juvenile fish and lobsters, shoreline stabilizers,

sediment filters, food, and breeding grounds. The mangrove swamps of the

low coastal islands and shorelines are important to the integrity of the

nearshore and offshore ecosystems. Intertidal mud flats, lining the

mangroves, exposed during low tide and flooded at high tide, attract wading

birds which also feed on the marine organisms, extending the food chain to

Iand animals.

The marine environment is not a closed system; it is dependent on a

continuing supply of organic materials delivered by circulating water.

Mangrove leaf litter is a source of organics and the base for a food chain.

The leaf litter is broken down by bacterial and fungal action into detritus

which in turn serves as food for small organisms. .The detritus of

mangroves makes up 35-60% of suspended material in inshore waters. The

detritus-feeders, some of which are larval forms of important commercial

species (e.g. , pink shrimp), are preyed upon by larger organisms which

attract other predators. Among fish and shellfish using coastal mangroves

as nursery grounds are mullet, mangrove snapper, snook, tarpon, sea trout,

shrimp and blue crab. A close interdependence exists between mangroves and

seagrass beds because larval organisms move from the mangroves to continue

their development in the grass beds. These organisms may later move out

into the reefs or stay inshore, depending on the species.

Large areas of submerged bottom in the Park, such as the 10-15 ft.

deep Hawk Channel separating the Keys from the reef tract, are covered by

seagrasses. These seagrass beds are highly productive areas since they

serve as habitat for numerous organisms and as nursery and feeding grounds

for many species of fish and invertebrates migrating between the reefs,-

seagrass beds and mangroves on a daily or seasonal pattern. Among these

important species are mangrove snapper, black mullet, spiny lobster and

pink shrimp.

The grasses support attached flora and fauna which, in turn,

constitute a food source for other organisms grazing on seagrasses.

Endangered green and hawksbill turtles feed on the seagrasses. Grass beds

also trap suspended sediment, protecting the reefs by keeping the water

clear, a necessity for the existence of reef corals.

Spiny lobsters and mangrove snapper are examples of animals whose life

cycle pattern is dependent upon all three communities. Breeding occurs in

or above the reef; larvae hatch in waters near the reef; larvae remain in

the water column for a period of time growing to juvenile stages which

inhabit the coastal mangrove fringe; larger juveniles move seaward to live

in the patch reefs and rock outcrops; subadults move into the bank reefs

where they find refuge in the reefs during the day and venture to the

seagrass meadows to feed on shrimp, crabs, and small molluscs at night.

Survival of these species depends on the quality of the several different

habitats; the demise of any one habitat will impact the population and

abundance of both species.

Past Research

The historical data base dealing specifically with trace metals

chlorinated hydrocarbons, and pthalates for John Pennekamp Coral Reef State

Park and the Key Largo National Marine Sanctuary is not extensive. Manker

(1975) reported on some trace metal concentrations in suspended and bottom

sediments in the Key Largo region. Manker's work detailed elevated levels-

of several trace metals in the sediments adjacent to heavily urbanized

areas. Water quality from five stations in JPCRSP were collected since

1982. This ongoing project monitors nutrients, ammonia, coliform counts,

oils and greases, trace metals, pesticides, PCBs, and PAEs. Several

studies indicate that coral (Scleractinia) skeletons contain historical

information on the concentration of certain metals and chemicals (Dodge and

Gilbert, 1984; Dodge et al., 1984). Neoplasm tumors (calicoblastic

epithelioma) are reported from Acropora palmata colonies from Carysforti

Reef and Grecian Rocks Reef (Peters et al., 1986). The tumors may be

related to environmental contamination. Several papers have offered the

hypothesis that pollution is affecting reef vitality (Voss, 1973; Dustan,

1977). This work will examine the nature of contaminants that are possibly

affecting the vitality of the Park's and Sanctuary's biological resources.

Problem areas that are detected may be selected for monitoring and to seek

point sources so mitigative measu res may be taken. The Key Largo National

Marine Sanctuary and John Pennekamp Coral Reef State Park funded

research projects that deal with a variety of issues and subjects. Much of

the work was completed and the findings are available as technical reports.

These include the following, listed chronologically..

1972 - Reef sedimentation, Harbor Branch Foundation

1974 - Reef Biology, Florida Reef Foundation

1974 - Dredging in the Florida Keys, Harbor Branch Foundation

1974 - Effects of offshore oil drilling, U.S. Geological Survey

1979 - Effects of drilling muds on coral, Texas A&M University

1981 - Biological inventory, University of Miami

1982 - Water currents, General Oceanics

1982 - Water quality, Biscayne National Park

1981-85 - Quantitative reef monitoring, FDNR Bureau of Marine Research

1982 - Water quality and monitoring, Applied Biology

1982 - Tumors in the bicolor damselfish, University of Miami

1982 - Stromatolites at French Reef, Virginia Polytechnical Institute

1982 - Survey of Carysfort Reef, College of Charleston

1982 - Water quality monitoring, DNR Div. of Recreation and Parks

1983 - Transplanting seagrass, NOAA & Corps of Engineers

METHODS AND MATERIALS

Station Information

During 1985, collections were made at twenty stations (Figure 2).

Because of budget constraints, we reduced the original number during 1986

first to fourteen, then to eight, but retained the same numerical

designations. Stations were distributed as follows:

Stations 1 through 12; and 18: nearshore stations

(1) Broad Creek (8) Garden Cove

(2) Ocean Reef north (9) Largo Sound

(3) Ocean Reef south (10) South Sound Creek west

(4) Carysfort Yacht Club (11) South Sound Creek east

(5) Harrison development (12) Hidden Harbor

(6) Post/Nichols development. (18) Navigation marker 32

(7) Valois development

Stations 13 through 15, offshore stations:

(13) Deep reef near Benwood wreck

(14) Grecian Rocks

(15) Carysfort Reef

Stations 16, 17, 18, 20, Hawk Channel/intermediate stations:

(16) Turtle Rocks

(17) Basin Hill Shoals

(19) Rodriquez Key

(20) Mosquito Banks

14
Distances from shore range from 10 to 1000 m for nearshore stations :3, from

7.2 to 10.2 km for offshore stations on the outer reefs, and from 1.5 to

7.0 km for the stations of intermediate locations.

STATION CHARACTERIZATIONS

(1) Broad Creek station (25020.4'N, 80*15.0'W) lies immediately adjacent.to

the north boundary between John Pennekamp Coral Reef State Park (JPCRSP)

and Biscayne National Park in Broad Creek. Depth varies from 1 to 2 m,

sediments range from fine to coarse calcium carbonate particles in a thin

layer over hard limestone bottom. The benthic flora consists mainly of

turtle grass (Thalassia testudinum) and the calcareous'green alga Halimeda

sp., the benthic fauna includes both soft and hard corals (Porites porites)

and sponges among a variety of species.

(2) Ocean Reef - north (25"18.9'N, 80*16.1'W) lies at the mouth of a

residential canal system north of marker 18. Depth of water and type of

sediment are similar to (1) above, but the sediment layer is thicker at

this location. This is an area of dense turtle grass beds (T. testudinum)

and a number of *species of algae, including Halimeda sp.

(3) Ocean Reef south .(25018.6'N, 80"16.4'W) is located at. the 'approach,

channel to the club's marina next to marker 12. It is similar to station

(2).

(4) Carysfort Yacht Club (25015.2'N, 80018.4'W) is located at the approach

channel north of marker 4. The substrate is hard bottom with pockets of

sediments and patches of turtle grass (T. testudinum) and algae, among them

Halimeda sp., as well as finger coral (Porites porites).

(5) Harrison development (25*12.2'N, 80*18.9'W) and

(6) Post/Nichols (25*14.1'N, 80*19.0'W) are very similar to station (4).

In both cases the location is next to a marked access channel; bottom

configuration, sediments, and benthic communities are similar.

(7) Valois development (25*11.7'N, 80*21.3'W) station is located very close

to shore in shallow water of .5 to 1.0 m. Sediments are fine to coarse,

>10cm deep in parts of this area.. Distribution of turtle grass (T.

testudinum) and the alga Halimeda sp. is patchy.

(8) Garden Cove (25"10.4'N, 80021.8'W) at the mouth of the entrance canal

to the Port Bougainville development is characterized by soft deep

sediments and deposits of flocculent material which become suspended above

the floor by even slight water movement: Divers collecting samples cause

clouds of turbidity which take some time to clear. Turtle grass (T.

testudinum) growth is lush, blades are 20 to 30cm long, creating a dense

carpet. A few patches of Halimeda sp. occur in the vicinity of marker 18B.

Several spots of hard bottom in the channel indicate recent propeller

scouring.

(9) Largo Sound (25007.6'N,' 80023.9'W) at marker 21 is the only station

located in the sound, an enclosed water body connected to the Atlantic

Ocean through an intricate system of tidal mangrove creeks. Depth ranges''-

from .7 to 1.0 m. sediment is coarse to medium calcium carbonate particles

in a layer of 10 to 15 cm thickness. Benthic flora consists of lush beds

of turtle grass (T. testudinum) and a number of algae, including Halimeda

sp. This station is located close to the wading beach at JPCRSP.

(10) South Soun@ Creek west (25006.0'N, 80024.6'W) at the exit of the creek

into the Atlantic is the shallowest station in the series. Many of the

mudbanks in the vicinity are exposed at low tide. Samples are from a depth

of 40 to 60 cm at the edge of the channel where turtle grass (T.

testudinum) and algal growth is denser than on the shallow banks. Besides

Halimeda sp., a species of the green alga Caulerpa occurs extensively in

this area.

(11) South Sound Creek east (25*05.9'N. 80*25.2'N) consists of a limestone

hard pan with few sediment deposits, depth ranges from 2-2.5 m. Sponges

and octocorals are attached to the limestone, algae and seagrass are found

in the sediments.

(12) Hidden Harbor (25004.9'N, 80026.2'W) is again located at development

access channel. Sediments are medium to coarse, 10 to 20 cm deep with

deeper pockets. In addition to a benthic flora of mixed algae (including

Halimeda sp.) and turtle grass (T. testudinum) in large patches, the

benthic fauna includes some octocorals and sponges, as well as shallow

water hard corals (Siderastrea radian,s).

(18) Marker 32 (25*08.9'N, 80*21.2'W) lies near the exit of the Garden

Cove channel into Hawk Channel north of Rattlesnake Key. Depth is

approximately 3 m. This station has lush seagrass with algae and sponges.

(19) Rodriguez Key station (25003.1'N, 80026.4'W) is located north of the

key.at the park boundary. Depth is shallow, ranging from .6 to 1.0 m, the-

sediment layer is thin except in depressions, covering limestone bottom.

Turtle grass (T. testudinum) occurs more sparsely than at nearshore

stations, and grass blades are short. In addition to Halimeda sp. and

turtle grass, samples included Porites porites.

(13) Deep reef: Between French Reef and the Benwood wreck (25002.08'N,

80019.9'W) the collection site is located at a reef outcropping, 28.9 m

depth. The sea floor is a fine carbonate sediment with scattered

buttresses of Montastraea annularis outcropping upwards 1 to 2 m in relief.

Other scleractinian corals include Agaricia agaricites,, Montastraea

cavernosa, Stephanocoenia michelinii, and Myc,etophyllia aliciae. Some of

these coral heads are undermined with tunnels and caves that provide

shelter to invertebrates and fish.

(14). Grecian. Rocks Reef is a shallow reef community intensively used by

snorklers. Our sampling was concentrated on the southwestern inshore

portion of the reef (25006.7'N, 80.018.4'W). The organism distribution

pattern ranges from dense seagrass meadows of Thalassia testudinum inshore

of the reef to a mosaic. of coarse carbonate . sediments and patches of

seagrass extending outward from the reef approximately 20 m. Close to the

reef, small thickets of staghorn coral (Acr pora cervicornis) are common.

At the reef fringe there are isolated large heads of star coral (.M.

annularis). One of these heads lies atop an old ship's cannon. At the

inshore reef face a wall of coral and limestone juts upward close to the

surface. Most of the wall was constructed by elkhorn coral (Acropora

Palmata). Corals and Halimeda algae were collected from this. area. The

reef becomes progressively shallower toward its interior. At.low tide much

of this region is unaccessible to snorklers due to its shallowness.

(15) Carysfort Reef is located in the northeastern portion of the Key Largo

National Marine Sanctuary. (25*13.4'N, 80012.5W). A prominent feature of

Carysfort reef is the old lighthouse that was built between 1848 and 1852.

The lighthouse sits on a shallow flat that is dominated by elkhorn coral

(A. palmata). Sampling was conducted in the shallow reef flat as well as

in a forereef habitat at 13.7 m depth. The deeper area is dominated by

large colonies of M. annularis and Colpophyllia natans. Sediments were

collected in channels (grooves) that seperate ridges of reef limestone and

coral at the deep collection site.

(16) Turtle Rocks site is near intracoastal local marker 3 and next to an

old daymarker piling (25006.7'N, 80018.4'W). The seafloor is hardpan

limestone with sparse benthos. Short octocorals (sea plumes, whips, and

fans) dominant. Diploria clivosa, a brain coral characteristic of

turbulent environments, is conspicuous. A strong current was always

experienced while sampling this station. Sediments were collected in

shallow depressions where sparse deposits accumulate.

(17) Basin Hill Shoals is a small patch reef east of intracoastal marker 31

(25012.9% 80017.3'W), was sampled. The reef is surrounded by a halo of
carbonate sediments and sparse seagrass and algae. The reef is very

shallow, it had been hit several times by boats. The principal framework

coral is Montas-t-ra-ea annularis. The water was turbid as the reef is very

close to Hawk Channel.

(20) Mosquito Bank patch reef is northeast of the light tower that marks

the Mosquito Bank area (25004.4'N, 80023.0'W). It has the same

general characteristics as the Basin Hill Shoals station. The reef surface

is very close to sealevel. Many corals are morbid and there are signs of

boat groundings on the reef. Seagrasses and sediments are found peripheral

to the reef.

Field Methods

Field physical data.

Stations were sampled 10-11 July 1985, 3-5 December 1985, 25-27

February 1986, and 10-12 June 1986.

Field data were -collected using the following techniques. Stations

were located using visual landmarks and a loran C navigational instrument

(Figures 1, 2). Tide level was determined from tide tables (NOAA, 1984,

1985). Station depth was determined from diver's depth gauge and/or a tape

measure. Hydrogen ion (pH) concentrations were measured from the water

column with an electronic pH meter. Salinities were determined with a

refractometer. Water temperature was measured with a thermometer.

Illumination at surface and depth was measured with a quantum scalar

irradiance meter. Sediment samples were collected by divers. Acid washed

16 and 32 oz jars were taken underwater and filled with sediments. Three

replicates were collected at each station. Based on an evaluation of

dominant organisms, two to four species were collected by divers at each

station (Table 1). Organisms were brought aboard the boat, sorted,

labelled, and wrapped in aluminum foil. Sediments and- organism samples

were kept cool in an ice chest until return to shore. Samples were placed

in a refrigerator for storage and then transported to Dr. Corcoran's

laboratory at the Rosenstiel School of Marine and Atmospheric Sciences for

analysis.

Quality Assurance:

Great care was taken during the sampling and subsampling process to

insure that contamination was kept to a minimum and chain of custody was

maintained. This was accomplished by adhering to strict clean procedures,

keeping all samples under lock and key and maintaining detailed field and

laboratory records.

Laboratory methods

A7,ialysis of petroleum hydrocarbon analyses were conducted by

subsampling from the center of the sediment sample. This was done by

removing a subsample with hexane-rinsed stainless steel spatulas, and

placing it on clean aluminum foil. An inner plug was removed by inserting

a cleaned, organic-free 50 ml glass beaker through the center of the

subsample. The sample was placed in an organic-free glass jar and covered

with a foil lined screw top. It was then transferred to a locked freezer

until extracted.

Sediment Grain Size Analysis

A representative subsample of the collected surface sediments was

analyzed for grain-size fractions and distribution. The samples were

freeze-dried- in a Virtis Model No. 10-146-MB-BA freeze dryer. A

representative subsample was obtained by recovering 35 + 5 g from a

Jones-type, H.W. Curtin sediment splitter. The samples were fractionated

into three size classes, >2000u (gravel), 2000 to >63u (sand) and <63u

(silt-clay) by mechanically dry sieving for 15 mins. through 2000u and 63u

sieves.

The >2000u fraction (gravel) was dried at 105*C to a constant weight,

cooled to room temperature in a desiccator, weighed and archived. The <63u-

fraction was transferred into a labeled one-liter cylinder. The 2000u to

>63u fraction was mixed with a 496 (w/v) solution of sodium hexameta-

phospate and placed in a Bransonic 12 sonic bath for 15 mins. After

sonification this fraction was rinsed onto a 63u sieve with one liter of

distilled water. The particles which passed through the 63u sieve were

combined with the <63u previously stored in the one liter labeled cylinder.

The <63u fraction was transferred to a labeled aluminum weighing dish,

dried to a constant weight at 1050C, cooled to room temperature in a

desiccator and weighed.

The weight of the <63u fraction was calculated by subtracting the sum

of the >2000u and the 2000u - >63u fraction weights from the total sample

weight. From this data., dry weight percentages for gravel 02000u), sand

(2000u to >63u), and silt-clay (<63u) fractions were calculated.

Organic Content Analysis

The determination of the total organic matter of the sediments was

performed by using a modified version of Gralle and Runnel's (1960)

weightloss on ignition process. The procedure uses a high temperature

muffle furnace to oxidize organic matter. This method has been proven to

be 100% efficient for the recovery of total organic matter in marine

sediments (Byers et al., 1978; Dean, 1974).

Freeze dried, representative quantitative subsamples were obtained by.

using a Jones-type, H.W. Curtin sediment splitter. The split samples were

stored in clean 25 ml Erlenmeyer flasks, oven dried at 1050C to a constant

weight and cooled to room temperature in a desiccator. A sample of

approximately 10 g was transferred into a ceramic crucible.of known weight-

The combined crucible and sediment was then weighed, and placed in a rack

for ignit ion.

The samples were placed in a muffle furnace and ignited for 2 hours at

500*C. They were then cooled in a desiccator to room temperature and

weighed. The difference (i.e. weight loss) between this weight (minus the

crucible weight) and the initial dry weight was the quantity of total

organic matter (TOM) in the sediment (equation 1).

1. Dry wt. sample wt. after ignition at 500*C = wt. TOM.

The percentage by weight of TOM in the sediment was calculated using

equation 2.

2. wt. TOM x100 % dry wt. TOM
dry wt.

The organic carbon was calculated as 55% of the TOM.

Hydrocarbon Analysis

Sediment

Wet sediment (25-75 g) was weighed into cellulose thimble preextracted

with 1:1 benzene: 0.5N ethanolic KOH solution. Five grams of sample were

weighed onto a watch glass and placed in an oven at 105% for 3 hours for

dry weight determination. Sediments were extracted and saponified by

refluxing for 48 hours with the 1:1 benzene: 0.5N ethanolic KOH solution.

A plug of clean, light copper turnings was placed beneath the cellulose

thimble to remove the elemental sulfur from the sample. A 0.5 ml volume of

androstane and o-terphenyl (I mg/ml) was added to each sample as an

internal standard. Blanks were run with each set of 6 samples.

After 48 hours, the solution containing the extracted hydrocarbons was

removed from the Soxhlet and poured into a 500 ml separatory funnel. Any-

residue left in the round bottom flask was washed with three small aliquots

of hexane and these washings were added to the extract.

Three successive 50 ml volumes of hexane were shaken vigorously with

the extracted ethanol:benzene mixture, separating the aqueous and organic

layer, the three successive hexane-benzene mixtures were then combined and

the methanol aqueous phase was discarded.

The hexane-benzene mixture was washed first with organic free water

(prepared by passing distilled water through a large XAD-2 resin column)

and then with a saturated sodium chloride solution to 'remove trace amounts

of ethanolic KOH. The combined extracts were dried over I g of anhydrous

sodium sulfate to remove residual water. The ethanol and water were

discarded. The extract was concentrated to 5 mi in a Kuderna-Danish

apparatus using a rotovapor. The benzene-hexane concentrate was

transferred into a 12 mi evaporator tube, then the concentrate was dried in

a block heater under a stream of pure nitrogen gas. The dry sample was

then diluted to 1 mi with hexane placed in a 5 mi vial with a foil-lined

screw top and stored under refrigeration at 4*C.

An alumina-silica gel column was pre-wet with 12 mls of hexane and the

sample was transferred onto a (10 x I cm) column packed with 1.25 cm of

alumina over 2.5 cm of silica gel. Both the alumina and silica gel had

been partially deactivated with 2% organic free water prior to packing.

The aliphatic fraction (fl) was eluted with 12 mi of hexane and a similar

volume of benzene was used to remove the aromatic fraction from the column.

Care was taken to allow the hexane level to go below the alumina layer

during aliphatic elution. The aliphatic fraction was reduced to 1 mi on a

block heater under a stream of pure nitrogen gas, while the aromatic

fraction (f2) was brought to almost dryness and then diluted to 0. 2 mi.

The resultant sample s were then refrigerated until they were analyzed by

gas chomatography.

Tissue

The procedure for tissue analysis was similar to those described for

the sediment and consisted essentially of saponification, separation into

aliphatic and aromatic fractions and quantitative determination. However,

it was found that more complete and faster extraction could be attained by

placing the homogenized tissue in a round bottom flask, adding 150 ml of

ethanolic KOH and extracting it for four hours under a reflux condenser.

Gas Chomatographic Analysis

A 1.0 to 2.0 ul volume of the concentrate was injected into a Tracor

model 565 gas chromatograph which was equipped with dual flame ionization

detectors and two fused quartz capillary columns. The columns used were

two 30 m J & W columns coated with SE 30 for better resolution. Hydrogen

was used as the carrier gas and a flow of 30 ml/min. was maintained. The

temperature programming was such that the injector and detector

temperatures were maintained at 3000C and the chromatograph was programmed

for oven temperatures of 100* to 300% at 8*C/min with no initial hold and

a final hold of 5 minutes. A full description of conditions is shown in

Table 2. All samples were injected in the splitless mode. Two Hewlett -

Packard integrators model 3390A were programmed to record the retention

time, areas under the peaks and to calculate the amounts of hydrocarbons

from C12-C30- The integrators were calibrated with a standard mixture.

The aliphatic mixture contained hydrocarbons from C12 through C30 including

phytane, pristane and androstane. The calibration mixture used for the

aromatics had naphthalene, phenanthrene, dibenzothiophene and pyrene as

well as the internal standards o-terphenyl and I-methylph enanthrene. The

standard mixtures were run daily and the integrators were recalibrated as

necessary.

The quantification of the chromatograms involved evaluating the known

and unknown peaks, the internal standards and the unresolved complex

mixture for their retention times and areas. Calibration mixtures were run

to determine response factors (concentration injected divided by the area

of peak). The integrators were programmed with time windows to detect all

reference peaks in the C12 to C30 range and label them. In addition, it

determined the area for all other peaks. The response factors for the

internal standards, androstane for the aliphatics and o-terphenyl for the

aromatics, were used to quantify the concentration of all unknown peaks and

the unresolved complex mixture.

The integrators were capable of integrating under only one set of

parameters, therefore, the unresolved complex mixture was quantified

separately. This involved tracing the unresolved area on a sheet of paper,

cutting it out, determining its area and correcting to units which were

comparable to the other data generated by the integrator. The areas of the

unresolved tracings were determined by a Hayashi Denko, Type AAM-5

Automatic Area Meter. This unit is a photoelectronic apparatus that

automatically determines the area of any opaque or semitransparent material

by the amount of light it reflects. The area was reported in cm2 by the

area meter and converted to integrator units by a conversion factor. This

information, the areas for the known and unknown peaks, the response

factors, sample number, dry weight, volume injected and final dilution

volume were all entered into a computer program written to calculate and

quantify this data. The program calculated the ug/g concentration for all

of the reference peaks, resolved (includes- reference peaks and resolved

unknown peaks) -'and unresolved (unresolved complex mixture) areas, total

hydrocarbons, the carbon preference index (CPI), the percent recovery, and

the following ratios: resolved /unresolved, pristane/phytane, C17/pristane,

C18/phytane.

Pesticides and Phthalates

Both the tissue samples and the sediment samples were extracted in the

Soxhlet extractor for four hours using 150 ml of hexane-acetone (1:1). For

the sediments a cellulose thimble was used, but the tissue samples were

placed in the 250 ml round bottom flask for extraction. The extracts were

washed free of acetone with organic-free water using large separatory

funnels. Hexane extract was concentrated with a rotovapor and

chromatogrammed on a column of Floricil topped with anhydrous sodium

sulfate. Three fractions were collected using 200 ml each of 6%

ether-hexane, 15% ether-hexane, and 50% ether-hexane. Each fraction was

then concentrated to 2 ml. A 5 ul aliquot was injected into a gas

chromatograph equipped with 6 foot glass columns and electron capture

detector. Columns were packed with 1.5% SP2250/1.95% SP2401 and 5% SP2401.

Fraction 1 (6% fraction) was saponified and checked for PCBs. The

integrators used in connection with the GCs were prograrmned for the

detection of 21 organochlorine pesticides and 4 plasticizers.

Oils and Grease

Sediments were extracted with lipid solvent (hexane-acetone mixture),

and the resultant lipid material was weighed.

Coliforms, Detergqnts Nutrients, and Trace Metals

For the determination of these parameters methods were followed as

described in Standard Methods for the Examination of Water and Wastewater,

14th edition, 1976, by the American Public Health Association, the American

Water Works Association, and the Water Pollution Control Federation.

Coliforms: Standard Total Coliform Membrane Filter Procedure, pg. 928,

909A.

Detergents: Methylene Blue Method for Methylene-Blue-Active Substances,

pg. 600, 512A.

Trace Metals: Metals by Atomic Absorption Spectrophotometry, pg. 144, 301A.

Mercury by cold vapor method, all others with use of graphite

furnance.

Nutrients: Technicon AutoAnalyzer, pp. 616-628, 604, 605, 606, according

to method developed by Grasshof.

RESULTS AND DISCUSSION

Salinities ranged from 31 to 38 O/oo during the study. Lowest

values were from Largo Sound station; highest values were from offshore

stations (Table 3).

Seawater temperatures ranged from 19.4 to 32.8 C. Lowest and highest

temperatures came from the inshore stations (Table 3).

Water column PH ranged from 7.9 to 8.3 (Table 3). The PH meter

malfunctioned during the June 1986 sampling, hence no data was acquired.

Solar illumination.

The -quanta cm2 sec-l 2 m above the sea surface ranged from 30.1 to

167.7 (Table 4). Highest values occurred close to midday. The sky was

often cloudy during portions of the sampling days, thus reducing the solar

radiation. The irradance meter malfunctioned during the final sampling,

hence there is no information on irradiance during that period. The quanta

CM2 sec-l at the seafloor at stations ranged from 2.6 to 108.7 (Table 4).

Percentage of surface- illumination impinging on the seafloor ranged from

5. 3 to 74.7% (Table 4). Grecian Rocks station consistantly had the

greatest percentage of light passing through the water column (49.9 to

74.7%).

Sediments

Grain Size Analysis

Seven particle size classes were listed for all stations, ranging from

<0. 05 mm (silt) to >2 mm (gravel) in diameter. In general, at all

stations, a high percentage of sediment particles fell in the middle size

ranges of 0.1 to 1 mm diameter throughout the sampling period. Samples

with higher percentages of gravel-size particles originated from nearshore

stations and were most often associated with dredged access channels

leading to onshore developments. The largest percentage of silt (47.94%)

occurred in a sample from a recently dredged access channel at the entrance

to the Port Bougainville development canal; the second largest (43.26%)

originated from the station at the Valois development where fill material

from dredge spoil onshore continually erodes into adjacent waters.

Coliform Counts

Colonies/lOg wet sediment ranged in numbers from <5 at several of

stations to 16700 at the Rodriguez Key station in December 1985. High

values (above 1000) were also found at the Broad Creek, Ocean Reef,

Carysfort Yacht Club, Largo Sound, Hidden Harbor, and Basin Hill Shoals

stations in July 1985. These stations are associated with developments

and/or intensive boating activities. Rodriguez Key is a boating anchorage

and lies a short distance offshore from the town of Key Largo, therefor

falls into the same category as the other stations.

29*

Detergents

Detergents ranged from 0.05 at Mosquito Banks to 1.48 ugMBAS/g wet

sediment at the nearshore station in Largo Sound. Both the Largo Sound and

Garden Cove samples contained amounts above 1.0 in June 1986; along with

the Broad Creek, Ocean Reef, and other nearshore stations they ranged above

.1 in every sample. There appears to be a gradual increase in a number of

nearshore stations over the two year sampling period. Values for station 8

(Garden Cove) rose from .52 in July 1985 to 1.27 in June 1986, for station

9 at Largo Sound from .37 to 1.32, for Ocean Reef from .22 to .74 in

February 1986. Throughout 1985, values did not reach 1.0; in February

1986, one sample exceeded 1.0, in June 1986 four samples (two replicates)

exceeded 1.0.

Kjeldahl Nitrogen

This is the sum of organic and ammonia nitrogen. Values ranged from

160 ug/g at Turtle Rocks in July 1985 to 13170 at Garden Cove in February

1986. Sediments from stations located near developed areas onshore

consistently showed higher values than offshore stations. Garden Cove,
which shows consistently high values, is a shallow cove with a mangrove

shoreline and some heavily used access channels leading to commercial and

residential developments. Largo Sound, another station with high values,

is an enclosed body of water connected to the ocean through a series of

mangrove creeks. It is shallow, and surrounded on three sides by mangroves

and a developed 'shore on the fourth side.

Total Phosphate Phosphorus

Values ranged from llug/g in June 1986 in Largo Sound to 230 ug/g at

the deep reef station in February 1986. Other high values were 212 at

Ocean Reef north in December 1985 and 228 at Hidden Harbor in June 1986.

Since phosphates are not naturally abundant in the marine environment,

sources may be fertilizers and detergents. The high value at the deep reef

station did not appear in December 1986. Additional data are required to

determine whether some discharge may occur at the site (Simmons, personal

communication) and affect phosphate contents of the sediments.

Total Organic Carbon

The samples contained from 9 to 148 mg/g dry sediment of organic

carbon. Samples with the highest TOC were associated with channels close

to developments. They were also in close proximity to mangrove swamps.

Oils and Greases

Values ranged from .2 ug/g dry sediment at Grecian Rocks in December

1986 to 6.58 at South Sound Creek east on the same date. The value for

Grecian Rocks in February 1986 was 3.86, however, and for South. Sound Creek

east it was .73 (.76) for the.replicate. On the whole, sediments from all

stations contained fairly high amounts of these contaminants, but values-

fluctuated throughout the study period.

Trace Metals

Among the parameters listed, arsenic, cadmium, copper, mercury, and

lead are of special interest because of their toxicity to marine life

(National Academy of Sciences, 1972). Arsenic ranged from <.l ppm in over

50% of samples in December 1986 which included both inshore and offshore

stations, to 9.9 ppm in February 1986 in Garden Cove, and 8.8 ppm in Largo

Sound. The highest levels occurred in samples from nearshore stations.

February 1986 values were the highest overall during the study period.

Arsenic is used in paints and insecticides among many industrial uses. It

tends to be accumulated by marine organisms. Cadmium levels were below .5

ppm in all sediments, ranging from <.05 at many stations in December, 1985

to .32 in Largo Sound in February 1986. In the majority of samples

concentrations were well below .1 ppm, which is of significance since the

compound is highly toxic to marine life. Copper ranged from <1 ppm at

Broad Creek to 20 ppm at Garden Cove in February 1986. Values at stations

located in the vicinity of large developments. tended to be higher which can

be explained by the extensive use of copper as an antifouling agent in

marinas and bottom paints. Mercury levels ranged from <.05 at many

stations in February, 1986 to .2 at Garden Cove and Largo Sound in June

1986. The level of mercury was low throughout the study period with the

exception of the high values mentioned. mercury is highly toxic to marine

organisms. Since it is used in agriculture and in the plastics and paper

industries, to name some, it may enter the marine environment through
runoff and outfalls. Lead content of' samples ranged from <0.2 at several.

stations in February 1986 at 8 ppm at the Harrison development in July

1985. Lead levels in the samples from inshore stations exceeded levels

found in offshore stations considerably. Natural concentrations of lead

are extremely low in the marine environment. Much of it is introduced

through urban runoff where the source is the internal combustion engine.

Boats and marinas are another important factor in lead pollution of the

marine environment.

Hydrocarbons

The three sources of hydrocarbons in the marine environment are

biogenic (produced by marine or terrestrial organisms), pyrogenic (produced

by fires or combustion), and petrogenic (produced by petroleum products).

The groups exhibit characteristic patterns which make their identification

possible (Corcoran, 1983 and pers. comm.). A widely accepted method for

separating biogenic and petrogenic hydrocarbons is to separate them into

aliphatic and aromatic fractions. Table 5 lists the characteristics useful

in interpreting aliphatic chromatograms. An extensive discussion of

criteria is given in a report by Corcoran (1983).

Pesticides, Pthalates, and PCBs

Pesticides and pthalates found in the sediments and their detection

limits are listed in Table 6. Although both pesticides and phthalates.

occurred in low amounts, none of the stations were free of the contaminants

for the entire study period. Concentrations were higher at inshore

stations, as expected; however, some comparatively high values of certain

compounds occurred in outer reef stations. For instance, Heptachlor in

sample's from Carysfort Reef and Turtle Rocks were 2.62 and 2.29 ng/g,

respectively, in December 1985. Values for this compound throughout the

study period for all stations ranged from <0.002 ng/g to 32.8 in July 1985

in Largo Sound. Also in July 1985, Dieldrin was 11.64 ng/g and Endrin

15.14 ng/g at the deep reef station. Of interest is the continued presence

in the samples of banned pesticides such as DDT throughout the study

period, and its occurrence at offshore stations. A number of contaminants

appeared at Ocean Reef north in fairly high amounts in December of 1985:

Lindane 41.60; Heptachlor 2.84; Aldrin 33.13; o,p DDE 1.62; Endosulfan I

8.64; pp' DDE 18.75; Dieldrin 13.88; Endrin 28.93; and Endosulfan 11 4.33.

These amounts are from the same sample. Sublethal effects of pesticides

and LC50s are investigated by the EPA and continuously updated. Most

pesticides are found to be more harmful than previously assumed (EPA, pers.

comm.). In a case such as the station above where many contaminants occur

in the sediment simultaneously, a synergistic effect may occur, enhancing

toxicity to marine organisms. Fas t degrading chemicals pose a lesser

threat to aquatic life than the stable ones. The latter are of serious

concern since they may become concentrated in body tissues, or persist in

the environment, exposing organisms to their toxic qualities (Turk et al.,

1972).

The PCBs Aroclor 1248/1254 were detected in all sediment samples

collected in February, 1986. Concentrations ranged from a low of 40.98,

58.88 ppb at Grecian Rocks to a high of 321.36, 135.64 ppb at Broad Creek.

High concentrations were also detected at Ocean Reef (267.80, 249.83 ppb),

Carysfort Yacht Club (261.53, 192.80 ppb), and Largo Sound (286.60, 194 .49

ppb). The Carysfort Reef station sediments contained concentrations of

184.46, 140.49 ppb. Stations at the deep reef -@station also exceeded 100,

ppb.

The Aroclor chromatograms peaks were superimposed on pesticide

signatures and therefore masked sediment pesticide and pthalate values

during the February sample analysis. To eliminate the possibility of

contamination, the laboratory cleaned and recalibrated their equipment and

made a second evaluation of the samples. Similar results were obtained

(Corcoran, pers. comm.).

Pthalates occurred in comparatively high concentrations in the July

1985 samples. They were found throughout the sampling sites during all

sampling dates with the exception of the February 1986 samples, when the

Aroclor apparently masked their signatures on the chromatograms.

Tissue

Trace Metal Concentrations

1 July 1985

Nearshore stations

Aluminum ranged from 31 ppm in T. testudinum to 990 ppm in Ascidia

nigrans; arsenic concentrations ranged from 0.5 ppm in T. testudinum to 3.9

ppm in Halimeda sp.; cadmium levels were all <3 ppm; copper levels ranged

from 6 to 33 ppm in T. testudinum; iron concentrations ranged 28 ppm in

Siderastrea radians to 2790 ppm. in the sponge Spheciospopgia vepparia;

mercury was. found to be below <0.1 ppm in all cases.; and lead

concentrations were'always <10 ppm.

Offshore stations

Aluminum concentrations ranged from 42 ppmm. in T. testudinum to 620

ppm in a tunicate (not identified); arsenic levels ranged from <0.5 ppm T.

testudinum to 4.8 ppm in Acropora ceyvip_q@rnis; cadmium concentrations were

<3 ppm in all cases; copper levels ranged from 7 ppm. in T. testudinum to

110 ppm in Ralimeda sp.; iron concentrations ranged from 16 ppm in A.

cervicornis to 480 ppm in T. testudinum; mercury levels ranged from <0.1

ppm in several organisms to 0.2 ppm in Halimeda sp.; and lead levels were

always <10 ppm.

December 1985

Nearshore stations

Aluminum values expressed high variability, levels ranged from 100 ppm

in P. porites to 9000 ppm in T. testudinum; arsenic concentrations ranged

from 0.2 ppm in P. porites to 19.3 ppm in T. testudinum; cadmium levels

were <0.3 in most samples, the highest value was 1.3 ppm in S. vesparia;

copper concentrations ranged from 1.1 ppm 23 ppm in two S. vespari4; iron

levels ranged from 18 ppm in Halimeda sp. to 4800 in S. vesparia; lead

levels ranged from <1 ppm in many samples to 1.5 ppm in Halimeda sp.;

mercury levels were <0.05 ppm in all cases.

Offshore stations
Aluminum concentrations ranged from 60 ppm in M. annularis to 2800 ppm:

in T. testudinum; arsenic levels ranged from <0.2 ppm in several samples to

3.7 ppm in T. testudinum; cadmium .-conc entrat ions were all <0.3 ppm; copper

levels ranged from <4 ppm in several samples to 12 ppm in T. testudinum;

lead concentrations ranged from <1 ppm in most samples to 1.3 ppm in M.

annularis; all mercury levels were <0.05 ppm.

February 1986 sampling.

Nearshore stations

Aluminum concentrations ranged from 299 ppm to 2850 ppm in T.

testudinum; arsenic levels ranged from <0.5 ppm. in P. porites to 6.7 ppm in

T. testudin.um.; cadmium concentrations ranged from <.2 ppm in Halimeda sp.

to 0.4 ppm In T. testudinum; copper levels ranged from 4 ppm in T.

testudinum to 21 ppm in Halimeda sp.; iron concentrations ranged from 6 ppm

in Halimeda sp. to 385 ppm in T. testudinum; mercury levels were always

<0.1 ppm; and lead concentrations were always <1.0 ppm.

Offshore stations

Aluminum levels ranged from 85 ppm in M. annularis to 6000 ppm in T.

testud-inum; arsenic concentrations ranged from <0.5 ppm in A. cervicornis

to 7.2 ppm in T. testudinum; cadmium concentrations ranged from <0.3 ppm in

many samples to 0.7 ppm in the sponge Haliclona sp.; copper concentrations

ranged from 5 ppm in M. annularis to 12 ppm in two samples of P. porites;

iron levels ranged from 11 ppm in A. cervicornis to 100 ppm in T.

testudinum; mercury concentrations were <0.1 ppm in all cases; and lead

concentrations were <1.0 ppm in all cases.

June 1986 sampling.

Nearshore stations

Aluminum concentrations ranged from <100 ppm in T. testudinum to 460-

ppm in Halimeda sp.; arsenic levels ranged from <1 ppm in P. porites to 6.6

PPM in T. testudinum; cadmium concentrations ranged from <0.2 ppm in

Halimeda- sp. to .35 ppm in T. testudinum; copper ranged from 3 ppm in

Halimeda to 13 ppm in T. testudinum; iron levels ranged from 15 ppm in

Halimeda to 4400 ppm in S. vespari ; mercury concentrations ranged from

<0.1 ppm in most samples to 0.1 in S. vesparia; and lead levels were <1.0

ppm in all samples.

Offshore stations

Aluminum concentrations ranged from <100 ppm in M. annularis to 350

ppm in T. testudinum; arsenic levels ranged from <1 in several samples to

2.9 ppm in T. testudinum; cadmium concentrations ranged from <0.2 ppm. in

most samples to 0.25 ppm in T. testudinum; copper levels ranged from 2 ppm

in T. testudinum to 9.5 ppm in M. annularis; iron. concentrations ranged

from 10 ppm in P. poritps to 130 ppm in T. testudinum; mercury levels were

<0.1 in all samples; and lead concentrations were <1.0 ppm in all samples.

Inshore stations with higher concentrations of trace metals in

organisms were Garden Cove (5), Broad Creek (1), and South Sound Creek east

(11). These are located in areas with disturbance activities or where the

tidal flow transports materials from areas where disturbance does occur.

The offshore stations with higher trace metal concentrations included

Mosquito Bank (20), Basin Hill Shoal (17), and Grecian Rocks (14). These

are areas in close proximity to navigation lanes or receive intense user

activity.

Organisms that appear to concentrate certain trace metals include the
filter feeders, Iespecially the sponges and tunicates. The seagrass, T.

testudinum.also seems to concentrate. these metals under some circumstances-

There is a great deal of temporal and spatial variability. Most replicate

samples expressed similar concentrations of trace metals.

Tissue pesticide and pthalate compounds.

Pesticide compounds were found in parts per billion concentrations in

dried organism tissues. Concentrations ranged from not detected (ND) to

84.20 ng/gm (ppb). Pthalates (plastic agents) were detected in tissues in

concentrations ranging from .04 to 24.52 ug/gm (ppm). The PCBs were

detected in levels ranging from 137.83 to 780.58 ng/gm (ppb). Eighteen

different pesticide compounds were detected in organism tissues. Stations

that consistently had relatively higher concentrations of pesticides were

station 17 (Basin Hill Shoals), 20 (Mosquito Bank), I (Broad Creek), and 3

(south Ocean Reef channel). Stations with relatively higher pthalates and

PCB concentrations included 9 (Largo Sound), 14 (Grecian Rocks), I (Broad

Creek), and 17 (Basin Hill Shoals).

Nearly the entire spectrum of organisms sampled contained pesticides

in their tissues (Table 7). Algae, Plants, suspension feeders, and filter

feeders were included, indicating that the compounds are persistent in the

environment.-- Species with relatively higher levels of concentration

included Thalassia testudinum, Halimeda spp., -and Porites porites.

An unusual situation occurred during the February 1986. sampling. In

the sediment analysis, the PCB Aroclor 1248 was found to be present in all

samples, in tissue samples, Aroclor 1254 occurred in a number of the

organisms from offshore stations 13, 14, 15, 17, 19, and 20. . In samples

containing Aroclor 1254, pesticide compounds were not detected, but were

found in other tissue samples from the same station that did not contain-

Aroclor 1254. This situation will require further examination to evaluate

what happened.

Table 7 reports the highest concentrations found during respective

samplings. Detection limits are stated following each chemical (DW.

Specific organism concentration and station data are found in the appendix

tables. Other hydrocarbons detected during the program are also listed in

the appendix tables.

39
LITERATURE CITED

American Public Health Association, American Water Works Association, and
Water Pollution Control Federation.
1976
Standard methods for the examination of water and waste water, 14th
edition. Amer. Publ. Health Assn. 1193 pp.

Byers, S., E. Mills, and P. Stewart
1978
A comparison of methods of determining organic carbon in marine sediments
with suggestions for a standard method. Hydrobiologica 58(l): 43.

Corcoran, E.F., M.S. Brown, F.R. Baddour, S.A. Chasens, and A.D. Freay.
1983
Biscayne Bay hydrocarbon study, Final. report. Rosenstiel School of Marine
and Atmospheric Science, University of Miami. 326 pp.

Dean, W., Jr.
1974
Determination of carbonate and organic matter in calcareous sediments and
sedimentary rocks by loss of ignition: comparison with other methods. J.
Sed. Petrol. 44(l): 242-248.

Dodge, R.E., T.D. Jickells, A.H. Knap, S. Boyd, and R.P.M. Bak.
1984
Reef-building coral skeletons as chemical pollution (phosphorus)
indicators. Mar. Pollut. Bull. 15(5): 178-187.

Dustan, P.
1977
Besieged reefs of Florida's Keys. Nat. Hist. 86(4): 73-76.

Galle, 0. and R. Runnels
1960.
Determination Of C02 in carbonate rocks by controlled loss on ignition. J.
Sed. Petrol. 30:613.

Manker, J.P.
1975
Distribution and concentration of mercury, lead, cobalt, zinc, and chromium
in suspended particles and bottom sediments - upper Florida Keys, Florida
Bay, and Biscayne Bay. PhD dissertation, Rice University, Houston, Texas.
114 pp.

Mattson, J.S. and J.A. DeFoor, Il
1985
Natural resource damages: restitution as a mechanism to slow destruction of
Florida's natural resources. J. of Land Use and Envirn. Law 1(3):295-319.

National Academy of Sciences, National Academy of Engineering,
Environmental Studies Board
1972

Water Quality Criteria 1972. Environ. Prot. Agency, Wash., D.C., 594 pp.

Peters, E.C., J.C. Halas, and H.B. McCarty
1986
Calicoblastic neoplasms in Acropora palmata, with a review of reports on
anomalies of growth form in corals. "J. @rt- . Cancer Inst. 76(5): 895-912.

Turk, A., J. Turk, and J.T. Wittes.
1972
Ecology, pollution, environment. W.B. Sanders, Philadelphia. 217 pp.

Voss, G.L.
1973
Sickness and death in Florida's coral reefs. Nat. Hist. 82(7): 40-47.

"4 2 9 FLORIDA

BROWARD COUNTY

COLLIER COUNTY 4 MIAM

'MONROE COUNTY
DADECOUNTY

4 G1,

,P HOMESTEAD
GULFOF
MEXICO
7

SCALE OF MILES

0 5 10 20 30
JOHN PENN
CORAL REE
STATE PAR
ALLIGATOR
REEF

MARQUESAS SOMBRERO
KEY
LOOE KEY
SAND K Y KEY WEST NATIONAL MARINE SANCTUARY
20'1 10'' 8201 50' 1 40'1 30'1 20'1 1011 8101 50" 40'' 30" 20'1

Figure 1. Tropical coral reef communities off south Florida.

Key Largo Coral ,ef Marine Sanctuary
AA
0
ell 13
C
A
1 krn 7 os@ ago=-- <<' %
15 Q6 1 14 ZZ x1b.
Biscayne 16 0
@.ational Park

20
17 John Pennekarnp Coral Reef State Park
18 0 11
19
Hawk Channel 7
4 6 0
Ofd Rhodes 12
. .... ..... . .
90
Key Lar o:@!,
2
Key /1 3
0
IT,

Blackwat
r(
Barnes Sound
Sou d
Card Sound n Buttonwood
Sound
Park @20

Figure 2. Sampling stations

iable 1. Organisms collected at sampling stations

Station Number Organisms

1 Thalassia testudinum, HaVimeda spp.,
S_pecioq_pongia vesparia.

2 T. testudinum, Halimeda spp.

3 T. testudinum, Halimeda spp.

4 T. testudinum, Halimeda spp.

5 T. testudinum, Halimeda spp.

6 T. testudinum, Halimeda spp.

7 T. testudinum, Halimeda spp.

8. T. testudinum, Hallmeda spp.

9 T. testudinum, Halimeda spp.

10 T. testudinum, Halimeda spp,-

11 T. testudinum, S. vesparia
12 T. testudinum, Halimeda spp.

13 Montastraea annularis, Haliclona sp.

14,, Acropora palmata,.Acropora cervicornis,
@-Porites porites.

15 M. annularis, P. porites, A. palmata

16 T. testudinum, Diploria clivosa, A. cervicornis,
Gorgon@a ventalina

17 T. testudinum, M. annularis..P. porites,...
ffalir@eda spp7

18 T. testudinum, Halimeda spp.

19 T. testudinum, P. porites, Halimeda

20 T. testudinum, P. porites, M. annularis,
Halimeda spp.

@Table 2. Gas chromatograph operating.conditions.

Descriptor Column 1 Column 2

Column Type SE-30 SE-30

Column length W 30 30

Column velocity (cm/sec) 41.7 41.4

Detector gases
H2 (cc/min) 30 30
Air (SCHF) 1.0 1.0

Injection timer (sec) 30.5 30.5

Detector temperature UO 300 300

Injection port temperature (*C) 300 300

Temperature Program
Initial temperature 1000C
Final temperature 300*C
Program rate 8*c/min
Initial hold 0 min
Final hold 5 min

Table 3,v Field station data

Station' Date Time Depth Tide Temp Sal. pH
Lat. Long. (m) (C) (ppt)

1 2520.4 071085 1135-1201 0.9 low 30.8 31 8.1
1 8015.0 120385- 1116-1205 0.9 rising 25.5 35 8.1
1 022586 1140-1240 0.9 falling 22.7 36 8.0
1 061186 1421-1452 0.9 high 32.5 38 -
2 2518.9 071085 1231-1247 0.8 low 32 32 8.0
2 8016.1 120385 1220-1256 0.8 high 26.0 35 8.0
2 Station deleted following December sampling
3 2518.6 071085 1308-1324 1.4 rising 32.8 32 7.9
3 8016.4 020385 1220-1256 1.4 high 26.0 35 8.1
3 022586 1302-1348 1.4 falling 23.2 34 7.8
3 061186 1324-1410 1.4 high 32.0 38 -
4 2515.2 071085 1340-1355 1.2 rising 32.0 32 8.0
4 8018.4 120385 1420-1447 1.2 failing 26.8 36 8.1
4 022586 1527-1600 1.2 low 23.0 36 8.0
4 061186 1234-1304 1.2 high 31.0 38 -
5 2512.2 071085 1444-1450 0.9 high 32.6 33 8.0
5 8018.9 120385 1500-1540 0.9 falling 26.2 36 8.1
5 Station deleted following December sampling
6 2514.1 071085 1515-1530 1.0 high 32.0 34 8.2
6 8019.0 120385 1410-1440 1.0 falling 25.9 34 8.1
6 022686 1030-1118 1.0 falling 19.4 35 8.1
6 061186 1022-1101 1.0 rising 30.8 38 -
7 2511.7 071085 1540-1604 0.6 high 32.2 33 8.1
7 8021.3 120385 1252-1310 0.6 high 25.7 34 8.0
7 Station deleted following December sampling
8 2510.4 071085 1621-1630 1.5 high 32.0 34 8.0
8 8021.8 120385 1145-1220 1.5 rising 25.6 33 7.9
8 022686 1138-1203 1.5 falling 20.0 35 8.0
8 061186 1732-1807 1.5 falling 34.0 38 -
9 2507.6 071085 1645-1708 0.7 high 31.4 34 7.9
9 8623.9 .120385 1039-1111 1.2 rising 25.0 31 8.0
9 022686 1225-1252 0.7 falling 20.1 31 8.1
9 061086 1635-1712 0.7 failing 31.5 37
10 2506.0 071085 1722-1738 1.5 high 30.6 34 8.1
10 8024.6 120585 1428-1450 1.5 high 26.0 33 8.1
10 022686 1347-1429 0.6 low 19.6 35 8.1
10 061086 1510-1551 M falling 31.5 38
11 2505.9 071085 1738-1747 2.5 'high 31.0 34 8.0
11 8025.2 120585 1358-1416 2.5 high 26.0 34 8.0
11 Station deleted following December sampling
12 2504.9 071085 1759-1815 1.6 high 31.8 34 7.9
12 8026.2 120585 1140-1158 1.6 rising 25.8 34 8.0
12 022686 1500-1521 1.6 low 22.2 35 8.2
12 061086 1414-1437 1.6 falling 32.2 38 -
13 2503.0 071185 1040-1115 28.9 falling 30.5 32 8.1
13 8021.1 120485 1027-1040 28.9 rising 22.4 35 -
13 022786 1138-1215 28.9 high 22.9 36 8.2
13 161286 1055-1125 28.9 rising 29.5 38 -

Table 3.,:-Fllield station data (Continued)

Statiort Date Time Depth Tide Temp, Sal. pH
Lat. Long. W (C) (ppt)

14 2506.7 071185 1155-1215 1.8 falling 30.8 32 8.1
14 8019.3 120485 1110-1204 1.8 rising 23.2 34 8.0
14 022786 1250-1350 1.8 falling 21.8 36 8.2
14 061286 1150-1306 1.8 high 29.5 38 -
15 2517 * 0 071185 1305-1330 13.7 low 30.3 33 8.1
15 8024.4 120485 1430-1530 13.7 falling 26.0 34 8.0
15 022786 1425-1510 13.7 low 22.3 36 8.2
15 061186 1544-1632 13.7 falling 31.0 38 -
16 2520.6 071185 1420-1440 2.7 low 31.1 34 8.0
16 8013.0 120485 1605-1640 2.7 failing 26.0 33 8.0
16 Station deleted following December sampling
17 2512.9 071185 1455-1520 2.5 rising 31.1 33 8.1
17 8017.9 120485 1710-1730 2.5 falling 25.5 32 8.0
17 022786 1538-1615 2.5 low 21.6 36 8.3
17 061186 1126-1210 2.5 high 30.2 38 -
18 2509.3 071185 1545-1610 3.4 rising 31.1 32 8.1
18 8021.2 120585 0925-0950 3.4 rising 25.0 34 8.1
18 Station deleted following December sampling
19 2503.1 071185 1730-1745 0.9 high 30.6 33 8.1
19 8026.4 120585- 1100-1128 0.9 rising 25.5 33 8.1
19 022686 1540-1645 0.9 rising 22.2 35 8.2
19 061086 1318-1347 0.9 falling 32.0 38 -
20 2504.4 071185 1810-1850 2.2 high 31.2 32 8.2
20 8023.0 120585 1227-1249 2.2 rising 26.2 34 8.1
20 022786 1715-1745 2.2 low 21.3 34 8.2
20 061086 1501-1537 2.2 falling .32.5 38 -

Table 4. Solar illumination
10
Statioli Date Time Depth Sky Irradiation
(1m) cover (quanta cm2 sec-1
Surface Depth %

1 071085 1135-1210 0.9 clear 160.9 108.7 67.6
1 120385 1116-1205 0.9 overcast 80.2 58.2 72.4
1 022586 1140-1240 0.9 overcast 59.5 23.6 39.7
2 071085 1231-1247 0.8 clear 158.4 89.4 56.4
2 120385 1220-1256 0.8 overcast 56.8 2.6 4.6
2 Station deleted following December sampling
3 071085 1308-1324 1.4 clear 166.0 79.8 48.1
3 120385 1309-1350 1.4 overcast 150.5 39.7 26.4
3 022586 1302-1348 1.4 clear 154.2 41.8 27.1
4 071085 1340-1355 1.2 hazy 117.6 39.5 33.6
4 120385 1420-1447 1.2 part. cld. 143.7 47.2 32.9
4 022586 1527-1600 1.2 part. ,cld. 136.8 46.5 34.0
5 071085 1444-1450 0.9 hazy 129.6 47.2 36.4
5 120385 1500-1540 0.9 part. cld. 64.4 3.7 5.8
5 Station deleted following December sampling
6 071085 1515-1530 1.0 hazy 71.4 36.8 51.1
6 120385 1410-1440 1.0 instrument problem
6 022686 1030-1118 1.0 part. cld. 138.4 76.4 55.2
7 071085 1540-1604- 0.6 overcast 49.1- 24.6 50.1
7 120385 1252-1310 0.6 instrument problem
7 Station deleted following December sampling
8 071085 1621-1630 1.5 overcast 30.1 6.2 20.6
8 120385 1145-1220 1.5 instrument problem
8 022686 1138-1203 1.5 clear 145.8 17.7 12.1
9 071085 1645-1708 0.7 overcast 38.5 7.1 18.4
9 120385 1039-1111 1.2 instrument problem
9 022686 1225-1252 0.7 part. c1d. 147.6 58.8 39.8
10 071085 1738-1747 2.5 clear 144.4 19.1 13.2
10 120585 1428-1450 1.5 overcast 35.0 11.4 32.6
10 022686 1347-1429 1.5 part. cld. 147.8 19.1 12.9
11 071085 1738-1747 2.5 clear 144.4 10.1 13.2
11 120585 1358-1416 2.5 part. cld. 167.7 11.5 6.9
11 Station deleted following December sampling
12 071085 1759-1815 1.6 clear 121.2 28.4 23.4
12 120585 1140-1158 1.6 part. cld. 8.1 8.1 10.7
12 022686 1500-1521 1.6 part. cld. 145.0 20.8. 14.3
13 071185 1040-1115 15.2 hazy 121.5 24.7 20.3
13 120485 1027-1040 15.2 instrument problem
13 022786 1138-1215 15.2 instrument problem
14 071185 1155-1215 1.8 hazy 104.2 77.8 74.7
14 120485 1110-1204 1.8 overcast 33.4 16.5 49.4
14 022786 1250-1350 1.8 clear 145.4 101.6 69.9
15 071185 1305-1330 5.8 hazy 125.5 45.0 35.9
15 120485 1430-1530 instrument problem
15 022786 1425-1510 5.8 part. c1d. 140.0 40.3 28.8
16 071185 1420-1440 2.7 hazy 117.0 34.0 29.1
16 120485 1605-1630 instrument problem
16 Station deleted following December sampling

Table 4'. Solar illumination (continued)

Station Date Time Depth Sky Irradiation
W cover (quanta cm2 sec-l
Surface Depth %

17 071185 1455-1520 2.5 hazy 115.3 62.1 53.9
17 120485 1710-1730 2.5 dusk
17 022786 1538-1615 2.5 clear 137.0 36.0 27.3
18 071185 1545-1610 3.4 overcast 71.2 22.5 31.6
18 120585 0925-0950 3.4 overcast 35.4 3.1 8.8
18 Station deleted following December sampling
19 071185 1730-1745 0.9 overcast 54.0 90.0 60.0
19 120585 1100-1128 0.9 part. c1d. 162.4 8.6 5.3
19 022686 1540-1645 0.9 part. cld. 112.4 56.4 50.2
20 071185 1810-1850 2.2 overcast 48.4 13.3 27.5
20 120585 1227-1249 2.2 part. ' cld. 61.5 15.4 25.0
20 022786-- 1715-1745 2.2 part. c1d. 87.0 8.5 9.8

Note, the instrument was non-functional duri.ng the June 1986 sampling.

Table 5:' Criteria for distinguishing petrogenic from biogenic hydrocarbons
(from Corcoran, 1983).

CRITERION PETROGENIC BIOGENIC

1) Homologous Series Wide boiling range (Cl to C60) Narrow boiling range
Several series (C15 to C35)
Few series (2 or 3)

2) Odd-carbon predominance Absent (CP1 1) Usually present over a
narrow range (C15, C17
and/or C19 often prominent

3) Unresolved Complex Present, often dominant Absent or barely detect-
Mixture (UCM) able

4) Isoprenoid distribution Appreciable pristane (Clq), Pristane often abundant,
phytane (C20),'Cl6, C18 no others detected

5) Pristane/Phytane ratio 1.5 to 2.5 100 or greater

6) Resolved/Unresolved Complex 1 but not zero infinite
Mixture (Res/UCM)

7) Total hydrocarbon as carbon/ Larger ratio Smaller ratio
total organic matter
(HCC/TOM)

Table 6. Pesticides and phthalat es in sediments collected in 1985 and'1986
and detection limits for pesticides and pthalates (labelled as
N.D.)

PESTICIDES (ng/gm)
0.004
Lindane 0.002
Heptachlor 0.004
Aldrin 0.004
o,p DDE 0.004
Heptachlor epoxide 0.004
Endosulfan 1 0.014
p,p DDE 0.004
Dieldrin 0.002
o,p DDD 0.011
Endrin 0.006
o,p DDT 0.002.
p,p DDD 0.011
Mirex 0.001
p,p DDT 0.012
Endosulfan 11 0.004
Methoxychlor 0.002
alpha chlordane 0.002
Endosulfan sulphate 0.01

PTHALATES (ug/g_m)

Diethyl pthalate 0.01
Dibutyl pthalate 0.01
Butyl benzyl pthalate 0.01
Diethyl hexyl pthalate 0.01

Table 7. Pesticide Compounds

Date Concentration Organism Station
(ng/gm, ppb)

LINDANE (DL .004 ng/gm, ppb)

July 85 .095 P. porites, 4
December 85 30.88 T. testudinum 11
February 86 12.87 Y. tudinum 17
June 86 9.62 testudinum I

HEPTACHLOR (DL .002 ng/gm, ppb)

July 85 0.70 T. testudinum. 14
December 85 84.20 ffaliclona sp. 13
February 86 20.23 T. testudinum 4
June 86 38.60 T testudfnujn 4

ALDRIN (DL .004 ng/gm, ppb)

July 85 ND
December 85 26.96 P. porites I
February 86 27.62 T. testudinum 17
June 86 38.10 Halimeda sp. - 8

0, P DDE (DL .004 ng/gm, ppb)

July 85 0.42 T. testudinum 5
December 85 26.33 f_. p9rites 1
February 86 21.04 Halimeda sp. 20
June 86 30.38 Ta'13meda sp. 3

HEPTACRLOR EPOXIDE (DL = .004 ng/gm, ppb)

July 85 0.12 Halimeda sp. .10
December 85 15.45 S. vesparia 18
February 86 31.46 T. tesru-di"n-um 17
June 86 3.01 -T. T'e@studinum 17

ENDOSULFAN I (DL .014 ng/gm, ppb)

July 85 ND
December 85 29.59 P. porites 1
February 86 20.76 Hal'iclona sp. 13
June 86 24.89 T. tres"tudinum 12

P,P DDE (DL .004 ng/gm, pbb)

July 85 0.30 T. testudinu'm 16
December 85 17.05 F. porites 20
February 86 20.23 T. testudinum 17
June 86 13.53 -9a 1 i@p, La 3

@ablpo 7. Pesticide Compounds (Continued)

Date Concentration organism Station
(ng/gm, ppb)

DIELDRIN (DL .002 ng/gm,ppb)

July 85 1.04 T. testudinum 20
December 85 15.01 -X.-@-e-rvicornis 14
February 86 20.13 A. palmata 14
T . -Ce -s
June 86 32.34 tudinum 4

O,P DDD (DL .011 ng/gm,ppb)

July 85 0.06 P. porites 4
December 85 15.69 T. testudinum 9
February 86 40.72 T. testudinum 17
June 86 0.91 testudinum 3

ENDRIN (DL .006 ng/gm,ppb)

July 85 0.23 T. testudinum 2
December 85 20.69 F. porites I
February 86 20.58 T. tesFu-d-i'-'num 17
June 86 -21.24 T. testudinum 8

O,P DDT (DL .002 ng/gm, ppb)

July 85 0.49 T. testudinum 5
December 85 46.22 Halimeda sp. 9
February 86 28.96 T. testudinum 17
June 86 29.66 T. testudigum I

PI,P DDD (DL .011 ng/gm,, ppb)

July 85 0.02 S. radians 4
December 85 ND
February 86 14.28 A. palmata 14
June 86 ND

ENDOSULFAN II (DL .004 ng/gm, ppb)

July 85 0.03 S. vesparia 18
December 85 14.13 T. porites 20
February 86 ND
June 86 20.21 Halimeda sp. 4

PI, P DDT (DL .012 ng/gm, ppb)

July 85 0.17 T. testudinum I
December 85 20.70 F. porites 20
February 86 6.47 T. testudinum 9
June 86 4.91 Iffallm-eda sp. 17

Ifat I d' 7 Pesticide Compounds (Continued)

Date Concentration Organism Station
(ng/gm, ppb)

MIREX (DL .001 ng/gm, ppb)

July 85 0.02 T. testudinum
December 85 22.05 P. porites 20
February 86 15.74 -ffalimeda 19
June 86 36.42 Halimeda. 3

METHOXYCHLOR (DL .002 ng/gm, ppb)

July 85 0.31 Halimeda sp. 12
December 85 16.45 P. p0YjTPS 1
February 86 9.22 Y. testudinum 14
June 86 21.84 Ifaiimeda sp. 3

ALPHA CHLORDANE (DL = .002 ng/gm, ppb)

July 85 ND
December 85 ND
February 86 ND
June 86 40.53 Halimeda sp. 20

ENDOSULFAN SULFATE (DL = .01 ng/gm, ppb)

July 85 ND
December 85 ND
February 86 ND
June 86 2.18 Halimeda sp. 20

AROCLOR 1254 (DL not given)

July 85 ND
December 85 ND@
February 86 780.58 A. palmata 15
June 86 ND

PTHALATES AND PCB COMPOUNDS

DIETHYL PTHALATE (DL = .01 ug/gm, ppm)

July 85 24.52 G. ventalina 17
December 85 0.55 Y. testudtnum 14
February 86 21.23 T. testudinum 6
June 86 14.6 2 testudinum' 9

DIBUTYL PTHALATE (DL = .01 ug/gm, ppm)

July 85 6.82 T. testudinum 20
December 85 0.28 Halimeda sp. 9
February 86 2.54 T. testudinum 14
June 86 7.31 Y. testudinum 17

F- US Department of Commerce -I
.WOAA Ccnct-@2 'I'--i - -@@ -3 U'c--a@cr Library
i 22241 C@ctul-'TIA Z'-vc----ue
L_ Char'lesto'nt -S& 2.94,05-2413 j

Pesticide Compounds (Continued)

Date Concentration organism Station
(ng/gm, ppb)

BUTYL BENZYL PTHALATE (DL = .01 ug/gm, ppm)

July 85 5.99 T. testudinum 10
December 85 0.04 Halimeda sp. 1,12
February 86 0.14 T. testudinum 14
June 86 0.76 Y. testudinum 9

DIETHYL HEXYL PTHALATE (DL = .01 ug/gm, ppm)

July 85 3.20 Halimeda sp. 7
December 85 1.40 T. testudinum 2
February 86 3.01 T. testudinum 1
June 86 2.49 testudinum 9

DIETHYL PTHALATE (DL = .01 ug/gm, ppm)

July 85 24.52 G. ventalina 17
December 85 0.55 Y. testudinum 14
February 86 21.23 Y. testudirtum 6
June 86 14.62 T. testudinum 9

DIBUTYL HALATE (DL = .01 ug/gm, ppm)

July 85 6.82 T. testudinum 20
December 85 0.28 Taimeda sp. 9
February 86 2.54 T. testudinum 14
June 86 7.31 T. testudinum 17

BUTYL BENZYL PTHALATE (DL = .01 ug/gm, ppm)

July 85 5.99 T. testudinum 10
December 85 0.04 Halimeda sp. 1,12
February 86 0.14 T. testudinum 14
June 86 0.76 Y. testudinum 9

DIETHYL HEM PT0RALATE (DL = .01 ug/gm,ppm)

July 85 3.20 Halimeda sp. 7
December 85 1.40 T. testudinum 2
T. testudinum I
February 86 3.01
June 86 2.49 T. testudinum 9

AROCLOR 1254 (DL not given)
(Concentration given in ng/gm, ppb)

July 85 ND
December 85 ND
February 86 780.58 A. palmata 15
June 86 ND

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3 6668 14111442 3