Pergamon 0025-326X(95)00039-9 Marine Pollution Bulletin, Vol. 30, No. 10, pp. 646-654,1995

Copyright 0 1995 Elsevier Science Ltd Printed in Great Britain. All rights reserved

0025-326X/95 $9.50+0.00

Contaminants in Oysters in Kaneohe Bay, Hawaii CYNTHIA L. HUNTER*TI, MARK D. STEPHENSONt, RONALD S. TJEERDEMAS, DONALD G. CROSBY& GARY S. ICHIKAWA_F, JON D. GOETZLt, KIM S. PAULSON?, DAVID B. CRANEt, MICHAEL MARTINI_ and JOHN W. NEWMANS *Hawaii Institute of Marine Biology, University of Hawaii, Kaneohe, HI %744, USA j-Marine Pollution Studies Lab, California Department of Fish and Game, Moss Landing, CA 95930, USA $-Department of Chemistry and Biochemistry and Institute of Marine Sciences, University of California, Santa Cruz, CA 95064, USA SDepartment of Environmental Toxicology, University of California, Davis, CA 95616, USA llPresent address: Department of Botany, University of Hawaii, Honolulu, HI 96822, USA.

Despite past and present concerns about the toxicity and persistence of various environmental contaminants (heavy metals and pesticides), relatively few studies have documented their concentrations in tropical or sub-tropical marine ecosystems. In this investigation, a ‘mussel watch’ approach was applied in Kaneohe Bay, Hawaii, to assess the present levels of potential con- taminants in the Pacific oyster, Cmssostrea gigas. Geographical gradients of these contaminants were observed and related to what is known about past and present inputs. Concentrations of lead, copper, chromium and zinc were elevated in oyster tissues near stream mouths in the southern watersheds of Kaneohe Bay. Dieldrin and chlordane concentrations in oysters from one of these sites exceeded the US Environmental Protection Agency’s screening levels to protect human health, and were much higher than in oysters from the east and Gulf coasts of the temperate mainland USA.

Numerous studies have documented the accumulation of contaminants in benthic sediments and biota near industrialized areas or dense population centres at temperate latitudes (Goldberg et al., 1978; Stephenson et al., 1979; Phillips, 1980; NOAA, 1989). Studies in tropical and sub-tropical environments have been limited, but indicate similar elevations of contaminants in marine ecosystems receiving run-off from lands used for agricultural purposes or near heavily populated locations (Olafson, 1978; Menasveta & Cheevapara- napiwat, 1981; Brown & Holley, 1982; Glynn et al., 1984, 1989; Hallecher et al., 1985; Paez-Osuna et al., 1986; Dougherty, 1988; Hungspreugs, 1988; Phillips, 1991; Guzman & Jimenez, 1992). Although previous investigations demonstrate the presence of high con- centrations of toxicants in some tropical regions, the distributions of these toxicants are poorly understood in most areas.

Pesticide contamination in Hawaiian biota was first documented in 1969 (State of Hawaii, 1969). In a

nationwide survey of pesticides in freshwater fish, Hawaiian samples rated highest in dieldrin and chlordane concentrations between 1970 and 1974 and again between 1976 and 1979 (Schmitt et al., 1981, 1983). A more recent study indicated that bivalves (Ostrea spp.) collected within Hawaiian harbours and ports contained very high concentrations of a number of contaminants compared to bivalves from US main- land coasts (NOAA, 1989). However, accumulation of metals and organic pesticides in marine bivalves may be species-specific as shown by differential accumulations among species with overlapping ranges. Therefore, the high concentrations of contaminants in Hawaiian Ostrea were cautiously interpreted (NOAA, 1989). Because little information currently exists describing concentrations of toxic substances in tissues of Ostrea spp. from locations outside Hawaii, we analysed tissues from Crassostrea gigas for direct comparison with other studies and to determine if the trends in contaminants observed for Ostrea spp. may reflect those of other bivalves in other habitats in Hawaii.

Kaneohe Bay, Hawaii, has served as a model for identifying the impacts of urbanization on tropical Pacific ecosystems (Smith et al., 1973, 1981). The surrounding watersheds underwent a 2000% increase in population size between 1940 and 1990, and the south end of the bay received municipal sewage dis- charges from the mid-1960s through to the late 1970s. Since sewage discharge was diverted from the bay in 1977-1978, there have been only rare (accidental) point-source discharges into bay waters. The potential for introduction of contaminants through non-point source run-off from urbanized watersheds of the southern bay and from rural-agricultural areas of the central and northern bay was last evaluated in 1975 (Young et al., 1976). Fate and persistence of toxicants in bay biota have not been addressed previously. A recent workshop aimed at identifying research needs for coastal ecosystems in the bay concluded that very little was currently known about contaminants in Hawaii in general, and in Kaneohe Bay specifically.

646

Volume 30/Number lo/October 1995

We used a ‘mussel watch’ approach to assess the current concentrations of metals and pesticide residues in Kaneohe Bay. This approach has been used in Hong Kong (Phillips, 1980), Australia (Phillips, 1976) and the temperate USA (Goldberg et al, 1978, 1983; Farrington et al., 1983; Martin & Castle, 1984; Smith et al., 1986; NOAA, 1989) to assess contaminant con- centrations. Our study involved the collection of samples of Pacific oysters (C. gigas) along a north- south gradient reflecting the urbanization of watersheds surrounding the bay, analysis of the extracts for contaminants, and comparison of results to those from other areas. Crassostrea gigas, a bivalve mollusc intro- duced to Kaneohe Bay in 1939 (Kay, 1979) was chosen as a bioindicator because of its relative abundance throughout the bay and to allow direct comparison with published findings for this species at other tropical and temperate localities. Our goals were to establish a toxicant baseline for bay biota and to determine the potential for toxicant stress on the surrounding estuarine and coral reef environments of Kaneohe Bay.

Methods Collections and dissections

Sample sites were selected to bracket the range of

Map Of Kaneohe Bay

/! !

Kaneohe Stream

Arsenic

environmental gradients in Kaneohe Bay, with a focus on the southern (more urbanized) region of the bay. We collected Pacific oysters from five stations during the period of June to September, 1991 (Fig. 1): Makani Kai Marina, Kaneohe Stream and the Marine Base on 28 June 1991, Lilipuna Pier on 6 August 1991, and Waikane on 27 September 1991. Attempts were made to collect samples of similar size (5-10 cm shell length) and from the same tidal height (mean low water) at each site.

Oysters were pried from the substratum with stainless-steel diving knives, placed in polyethylene bags, and frozen at -10°C until dissection. Twenty-one oysters (three replicates of seven oysters each) were collected from each of four study areas: 18 oysters (three replicates of six oysters each) were collected from the Marine Base site. Samples were thawed and dis- sected with stainless steel scalpels in a positive-pressure clean-air room previously tested for contamination (Stephenson et al., 1979). Oysters were dissected into acid- and solvent-rinsed glass jars with Teflon-lined lids. Whole bodies (soft tissues) were homogenized individually with a Brinkman tissue homogenizer equipped with a titanium shaft cleaned with detergent, methanol, petroleum ether, and trace metal and trace organic-free Milli-Q deionized water before each homogenization.

_) Zinc

Copper Chromium

Fig. 1 Collection locations and relative concentrations of metals (pg g-l dry wt) in whole tissue extracts of Crussostrea gigas in Kaneohe Bay, Oahu, Hawaii.

647

Trace metal digestion and analysis TABLE 1

For each of the three replicates, 3 g of wet tissue was digested for 4 h in 3 ml of a 4:l mixture of ultra-pure nitric and perchloric acids (Fisher Ultima Grade) at 130°C in Teflon” digestion vessels. Samples were cooled, diluted to 20 ml, and transferred to acid- cleaned polyethylene bottles for analysis. We deter- mined Ag, As, Cd, Cr, Pb and Se concentrations by graphite furnace atomic absorption spectrophotometry (Perkin-Elmer Model 3030 with Zeaman background correction); Cu, Mn and Zn were determined by flame atomic absorption spectrophotometry (Perkin-Elmer 21280). All results were expressed on a dry weight basis.

Detection limits of synthetic organic compounds and trace elements analysed in this study on a dry weight basis.

Compound

Detection limit

(ng g-9 Trace element

1 1 1 1 1 4 2 5 3 3 3

20 Organic extraction and analysis

For analysis of organic contaminants, aliquots of tissue from each of the three homogenized replicates were combined into a single sample for each site in order to minimize costs. Two different analytical procedures were used. Samples from Kaneohe Stream were analysed for selected pesticides and PCBs by the method described in MacLeod et al. (1985) at the University of California, Santa Cruz. After this initial screening, samples from the other four stations were analysed using the US Food and Drug Administration (USFDA, 1975) method by the California Department of Fish and Game. The USFDA method is specific for more pesticides than that of MacLeod et al. (1985). The method of MacLeod et al. (1985) pooled 3.3 g from each of the three replicates into one 10 g sample for extraction. The USFDA method utilized 13.3 g from each of the three replicates pooled into one 40 g sample. Since replicate analyses were not performed, concentrations of organic compounds were not sub- jected to statistical tests. Compounds analysed and the detection limits for both methods are presented in Table 1.

Aldrin cis-Chlordane truns-Chlordane a-Chlordene y-Chlordene Chlorpyrifos Dacthal o,p’-DDD p,p’-DDD o,p’-DDE p,p’-DDE p,p’-DDMS o,p’-DDMU o,p’-DDT p,b’-DDT Dieldrin Endosulphan sulphate Endrin a-HCH P-HCH y-HCH 8-HCH Heptachlor Heptachlor epoxide cis-Nonachlor trans-Nonachlor Oxychlordane Parathion, ethyl Parathion, methyl PCB 1248 PCB 1254 PCB 1260

4

50 6

0.8 2

10 4

50 10 10

Quality controUassurance The University of California, Santa Cruz, and

California Department of Fish and Game analytical laboratories are participants in the National Oceano- graphic and Atmospheric Administration National Status and Trends trace metal and trace organics intercalibration programme (Cantillo & Lauenstein, 1992). The two organic methods were compared for several pesticides, giving the following results for the MacLeod and USFDA methods, respectively: chlor- dane, 48.2 ng g-’ and 54.5 ng g-l; dieldrin, 45.0 ng g-’ and 36.5 ng g-l; DDE, 18 ng g-l and 23 ng g-l; and PCB-1254, 200 ng g-’ and 215 ng g-l. These results indicate that good agreement exists between these testing procedures. In addition, two separate analyses were conducted on the pooled sample from the Marine Base site as a within-method control (Marine Base- QC).

relative concentrations of these contaminants in the oyster samples from various parts of the bay (Tables 2 and 3; Fig. 1). Concentrations of metals and pesticides varied along the north-south urbanization gradient of the bay. Lead concentrations were ten-fold higher in oysters at the south end of the bay near Kaneohe Stream and Makani Kai Marina than at the station in the north near Waikane Stream (Fig. 1). Multiple comparison statistical tests (Tukey’s test; Wilkinson, 1989) indicated that concentrations of copper, chromium, lead and zinc were significantly higher at Makani Kai Marina than Waikane Stream.

Results

In general, concentrations of arsenic, copper, chromium and lead were moderate to high in Kaneohe Bay oysters, while cadmium, and zinc concentrations were low when compared with other studies of metals in C. gigas (Table 4). Although interspecies com- parisons should be cautiously interpreted because of the variability in accumulation rates of metals among some bivalve species (NOAA, 1989), Table 4 shows that concentrations of metals in C. gigas are generally similar to those reported from other species and genera from different geographic areas. The metal concentra- tions that we found in C. gigas from Kaneohe Bay were also remarkably similar to those reported from Ostrea spp. collected from three Hawaiian harbours (NOAA, 1989).

Levels of present or historical inputs of metals and pesticides into Kaneohe Bay waters are reflected by the

Concentrations of DDT, PCBs, and other organic pesticides assayed in this study were low or undetect- able (Table 3). However, chlordane and dieldrin

648

Marine Pollution Bulletin

Detection limit

(CLg g-9

Arsenic 0.57 Cadmium 0.008 Chromium 0.03 Copper 0.04 Lead 0.1 Manganese 0.08 Selenium 0.5 Silver 0.002 Zinc 0.4

Volume 30/Number lo/October 1995

TABLE 2 Oyster size (x* SE) and concentration of metals in whole body tissue (pg g-l dry wt, x* SE) of Crassostrea gigas from five sites in Kaneohe

Bay, Hawaii.

Oyster Oyster Metals length weight

Sites (mm) (g) As Ag Cd cu Cr Mn Pb Se Zn

Marine Base 91.11 98.30 11.87 7.05 0.61 165.20 2.57 13.41 0.60 3.41 854.46 f 4.95 i? 7.65 f 1.84 f 1.51 f 0.05 f 13.86 f 0.49 f 2.62 +0.11 f 0.32 + 98.93

Kaneohe Stream 68.57 36.50 8.47 7.28 0.54 335.43 10.01 14.68 0.99 2.88 544.60 f 2.35 f2.16 f0.51 f0.53 f 0.04 zt 35.25 + 2.47 f 1.73 f 0.09 kO.14 It 43.03

Makani Kai Marina 55.24 27.80 8.54 5.68 0.61 522.33 6.47 14.68 1.76 3.06 1211.27 f3.13 f 2.69 * 1.45 * 1.00 f 0.03 k45.81 + 2.02 * 1.07 * 0.57 f0.21 !c 56.34

Lilipuna Pier 52.62 26.40 11.61 9.35 0.57 244.86 4.42 14.45 0.43 3.00 591.55 f2.17 f 1.13 * 0.44 f 1.36 f 0.02 f 33.41 + 1.22 f 0.97 f 0.02 f 0.54 * 74.53

Waikane Stream 73.00 52.40 13.70 6.32 0.69 333.75 2.03 12.06 0.10 3.26 600.94 * 3.5 f 4.60 f 0.35 f 0.09 fO.ll ? 87.02 * 0.21 zt5.12 + 0.06 f 0.22 f 155.14

TABLE 3 Levels (ng g-t dry wt) of organic toxicants in oysters from five sites in Kaneohe Bay.

Toxicants

cis-Chlordane trans-Chlordane Oxychlordane cis-Nonachlor rrans-Nonachlor a-Chlordene y-Chfordene Heptachlor Heptachlor epoxide Sum of chlordanes

Aldrin Chlorpyrifos Dacthal Dieldrin o,p’/p,p’-DDD o,p’/p,p’-DDE p,p’-DDMU o,p’/p,p’-DDT Endosulphan sulphate Endrin a-, 8-, y-, &HCH Parathion, ethyl Parathion, methyl PCB 1248 PCB 1254 PCB 1260

Waikane Lilipuna Stream Pier

ND 8 ND 5 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND 13

ND ND ND ND ND ND ND 17 ND ND ND ND ND ND ND ND ND ND ND ND ND ND 10 ND

ND ND ND ND ND ND ND ND

Makani Kai Marina

88 75

5 46 32

ND 15

ND 29

290

ND ND ND 200 ND ND ND ND ND ND ND ND ND ND ND ND

Kaneohe Stream

36 30

4.1 25 42 ND

2.2 7.4

ND 147

ND ND ND 92 ND ND ND ND ND ND ND ND ND ND 57 ND

Marine Base

7 5

ND ND ND ND ND ND ND 12

ND ND ND 7.6

ND ND ND ND ND ND ND ND ND ND 52 ND

Marine Base Q.C.

7 5.2

ND ND ND ND ND ND ND 12.2

ND ND ND 7.5

ND ND ND ND ND ND ND ND ND ND 57 ND

ND-Not detected.

300

Chlordane 1 J

Dieldrin

Fig. 2 Relative concentrations (ng g-l dry wt) of chlordane and dieldrin in Crussostreu gigas from Kaneohe Bay compared to NOAA (1989) National Status and Trends 90% limits (NS&T 90%) and highest levels (NS&T highest) reported from mainland US oyster samples.

concentrations represented the highest reported for these pesticides in any bivalve population sampled from the eastern or south-eastern US mainland by the National Status and Trends Program (Table 5; Fig. 2).

Mean lengths and weights were significantly smaller for oysters collected at Makani Kai and Lilipuna Pier than for the three other sites (Table 2; Tukey’s test; Wilkinson, 1989). The oysters with largest mean sizes (Marine Base) had generally lower concentrations of contaminants, indicating that high levels of toxins were not related to larger body sizes in these bivalves.

Discussion Over the past century, the watersheds surrounding

Kaneohe Bay have been utilized for a succession of agricultural activities (primarily taro, rice, pineapple,

649

TAB

LE 4

M

etal

con

cent

ratio

ns

(ug

g-r

dry

wt)

in b

ival

ves

repo

rted

from

var

ious

stu

dies

.

Met

als

Loca

tion

Spec

ies*

A

g A

s C

d cu

C

r Pb

Zn

R

efer

ence

Hel

ford

, U

K

cg

Hiro

shim

a B

ay, J

apan

cg

M

anuk

au H

arbo

ur,

New

Zea

land

cg

Ta

mar

Riv

er, T

asm

ania

cg

So

uthe

rn T

asm

ania

cg

D

eep

Bay

, Hon

g K

ong

cg

Ret

ail

mar

ket,

Hon

g K

ong

%

Kan

eohe

Bay

, Haw

aii

cg

Che

sape

ake

Bay

, Mar

ylan

d cv

Sa

vann

ah R

iver

, Geo

rgia

cv

B

isca

yne

Bay

, Flo

rida

cv

Tom

ales

Bay

, Cal

iforn

ia

me

San

Fran

cisc

o, C

alifo

rnia

m

e M

issi

on B

ay, C

alifo

rnia

m

e C

arib

bean

coa

st,

Col

ombi

a cr

Po

ll. g

radi

ent,

Ber

mud

a as

Po

ll. g

radi

ent,

Hon

g K

ong

Pv

Man

ila B

ay, P

hilip

pine

s ci

U

pper

Gul

f, Th

aila

nd

cc

Upp

er G

ulf,

Thai

land

cc

11

site

s, Fi

ji SC

B

arbe

rs P

oint

, H

awai

i O

S H

onol

ulu

Har

bor,

Haw

aii

OS

Kau

ai, H

awai

i O

S

5.3-

10.9

0.

3.5-

3.6

1.5

1.2

0.01

2 0.

58

0.12

1-18

8.2

12

0.5-

5.5

0.5-

22.5

1.

2-l

3.9

6.1-

14

27

15 6

5.8-

9.0

11

16

18 8

6 0.07

4-13

5 J-

23

2.0-

5.5

3.0-

27.0

0.

5-0.

8 1.

4-8.

4 2.

9 0.

36

5 46-6

2 2.

6 2.

0-15

.9

2.9-

4.1

0.75

-1.3

0.

5-2.

5 0.

4-2.

7 2.

1-3.

8

1.2

0.81

0.

35

273

140

178-

1219

20

0-17

00

lo-3

80

220-

1270

55

0-l

545

151-

525

30-2

50

64

90 5.4

1241

-168

0 5.

6 5.

9-91

.7

5.7-

9.8

17-1

58

20-1

00

6-27

6 lo

o-18

1 70

-160

12

00

1400

70

0

0.17

l-37

1.8-

11.5

0.

17-0

.67

0.51

0.

21

1.8

7.5-

9.3

0.87

0.15

-0.2

4 0.

24-0

.59

2.8-

4.0

1.9

2.3

8.2

2.1

o-13

5 O

-30

0.5-

2.0

OS-

O.4

0.

04-2

.4

0.28

-0.6

3 0.

22

0.28

0.

53

3.9-

7.1

1.3

0.6-

l 5.

6 1.

7-7.

3 6.

9-l

5.3

0.1-

1.0

0.5-

13.1

1640

74

0 97

0-41

46

2000

-140

00

200-

7800

12

00-3

310

1345

-311

0 42

2-12

68

1200

-450

0 14

00

2200

89

45

14-6

219

150

64-8

5 74

-96

1000

-400

0 83

-125

6 57

1-10

48

2.3

790

4.9

840

0.77

62

0

Thor

nton

et

al.

(197

5)

Hira

oka

(199

1)

Prid

mor

e et

al.

(199

0)

Ayl

ing

(197

4)

Thom

son

(198

2)

Phill

ips

et a

l. (1

982)

Ph

ihip

s et

al.

(198

2)

Pres

ent

stud

y N

OA

A (

1989

) N

OA

A

(198

9)

NO

AA

(19

89)

NO

AA

(1

989)

O

kaza

ki &

Pan

ietz

(19

81)

NO

AA

(19

89)

cam

pos

(198

8)

Leav

itt e

t al.

(198

9)

Cha

rt (1

989)

So

ria &

The

ede

(199

0)

Hun

gspr

eugs

(1

988)

Ph

illip

s &

Mut

tara

sin

(198

4)

Dou

gher

ty

(198

8)

NO

AA

(1

989)

N

OA

A (

1989

) N

OA

A

(198

9)

*Spe

cies

abb

revi

atio

ns:

cg, C

rass

ostr

ea

giga

s; c

v, C

rass

ostr

ea

virg

inic

a;

me,

Myt

ilus

edul

is;

cr,

Cra

ssos

trea

rh

izop

hora

e;

az,

Are

a ze

bra;

pv

, Pem

a vi

ridi

s;

ci,

Cra

ssos

trea

ir

edal

e;

cc,

Cra

ssos

trea

co

mm

erci

alis

; SC

, Sac

cost

rea

cucu

llata

; O

S, O

stre

a sp

p.

-, N

ot a

naly

sed.

Volume 30/Number lo/October 1995

TABLE 5

Location

Concentration of organic toxicants in bivalves reported in various studies.

Organic concentrations (ng g-‘)

* Speciest E Chlordane Dieldrin ZDDT PPCB Reference

Temperate sites Chesapeake Bay, Maryland Savannah River, Georgia Tomales Bay, California Mission Bay, California Baja California, Mexico Tamar River, New Zealand Manukau Harbour, New Zealand

* *

Tropical sites Malaysia *

Philippines *

Thailand *

India *

Benin Bight, Nigeria *

Biscayne Bay, Florida Mazatlan, Mexico Hawaii Kai Marina, Hawaii * Honolulu Harbor, Hawaii Barber’s Point, Hawaii Kauai, Hawaii Kaneohe Bay, Hawaii

cv 21-51 5-22 31-100 72-390 NOAA (1989) CV 12 5.9 13 46 NOAA (1989) me 3.3 3.5 15 34 NOAA (1989) me 20 3.2 70 310 NOAA (1989) cg _ 4-65 - Cajal-Medrona & Gutierrez-Galindo (198 1) cg _ 16-78 50-300 - Sumner (1978) cg 25-126 21-60 22-66 Pridmore et al. (1990)

‘Shellfish’ ‘Oysters’

Pv Pv ca cv cc

‘Oysters’ OS OS OS cg

28 _

12-288 26 19 13

12-261

5-25 130-2.50 135-220 13.5 _ _

50 120 50 14-200 3-36 91-138 122-387

17 45 210 _ 18-22 6-7

2-127 5-388 - 7.2 23 220 8.2 22 230 1.5 36 220

8-200 8-10 52-57

Hungspreugs (1988) Hungspreugs (1988) Hungspreugs (1988) Ramesh et al. (1990) Osibanjo & Bamgbose (1990) NOAA(1989) Martin & Gutierrez-Galindo (1989)

’ Tanita et al. (1976) NOAA (1989) NOAA j1989j NOAA(1989) Present study

*Conversion from wet to dry weight values; conversion factor = X 5. tSpecies abbreviations: cv, Crassostrea virginica; me, Myths edulis; cg, Crassostrea gigas; pv, Perna viridis; ca, Crassostrea gasar; cc, Crassostrea

corteziensis; os, Ostrea spp. -, Not analysed.

sugarcane, cattle grazing, truck farming and horti- culture), military operations (Kaneohe Marine Corps Air Station), and urban development (residential housing, golf courses, cemeteries, marinas, shopping centres and small businesses) (Devaney et al., 1982). The potential for contamination of Kaneohe Bay waters and associated marine life by toxic residues from these various land uses is reflected by the preliminary screening of metals and pesticides reported here.

Northern watersheds that drain into Waikane Stream are characterized primarily by rural and small-scale farming land uses. Oysters from this stream mouth showed detectable concentrations of parathion, but low concentrations of other contaminants. In contrast, oysters from the mouth of Kaneohe and Makani Kai Marina, the major outlets of drainages from the southern (urbanized) watersheds, had high tissue concentrations of lead, copper, chromium and zinc. These metals are common contaminants associated with automobiles (batteries and gasoline (Pb); plating (Cr); tyres (Zn)), residences in Hawaii (wood preserva- tion and banana fumigation (Cu)), and small boat marinas (Cu).

The high concentrations of chlordane and dieldrin found in oysters in the southern bay samples may be the result of long-term accumulation in tissues or sedi- ments, although recent (illegal) application of these banned pesticides cannot be ruled out. Tissue con- centrations of dieldrin in Kaneohe Bay were similar to those found in C. gigas in California near agricultural areas during the mid-1960s when dieldrin was still in use for agricultural purposes (Moden, 1969). Chlor- dane was banned in the USA in 1978, except for underground termite treatment; all uses were cancelled in 1988 (Eisler, 1990). Dieldrin usage was cancelled by

the USEPA in 1987. The most recent available usage levels in Hawaii were approximately 58 000 kg chlordane and 236 kg dieldrin in 1977, down from 64 000 kg and 7300 kg, respectively, in 1968 (State of Hawaii, 1969; Takahashi, 1982). The principal users of both compounds were pest control operators.

The half-life of chlordane is 350 days; that of dieldrin is approximately 3 years. However, isomers and breakdown products may be much more persistent (e.g. 3-14 years for chlordane in soils (Eisler, 1990)) because of low solubility in water, high solubility in lipids and low vapour pressure of these compounds. The USEPA (1993) has recently issued ‘screening values’ for various toxicants based on estimated human consumption rates. Concentrations in excess of these values ‘should be taken as an indication that more site- specific monitoring and/or evaluation of human health risk should be conducted’ (USEPA, 1993). For chlordane, screening values are 400, 205 and 19 ng g-i dry weight for adults, children, and subsistence fishermen, respectively. The Makani Kai Marina oysters (290 ng g-i) exceeded screening values for the latter two groups. Dieldrin screening values are 35, 18 and 1.5 ng g-i for adults, children, and subsistence fishermen, respectively; values for all groups were exceeded by the Makani Kai Marina dieldrin tissue concentrations of 200 ng g-l.

Concentrations of metals and pesticides were measured in Kaneohe Bay streams and bay waters in 1975 (Young et al., 1976). Metals concentrations in the bay were again analysed in 1989 (Hawaii Department of Health, unpublished data). Concentrations of dis- solved metals in seawater for various sites in Hawaii, including the two samplings of Kaneohe Bay, are presented for comparative purposes in Table 6. It is

651

clear that metal concentrations measured in Kaneohe Bay seawater in 1975 were extremely low. Whether these low values were due to low detection/recovery of the samples or lower absolute values of metals input to the bay is not clear, but the 1975 values were compar- able to those reported for other coastal waters near urbanized areas in Hawaii during that period (Young et al., 1976). More recent reports indicate that some metals in Kaneohe Bay seawater (e.g. Pb, TBT) may exceed Hawaii Department of Health limits.

Concentrations of metals in sediments in Kaneohe Bay showed an accumulation of approximately 0.5-2 orders of magnitude over concentrations in seawater (Tables 6 and 7). Relative concentrations of metals in bay oysters did not directly correspond with those in sediments. Arsenic and copper in C. gigus tissues from Kaneohe Bay were three to five times greater than the reported sediment concentrations; silver concentrations were more than two orders of magnitude greater. In contrast, chromium and lead were one to two orders of magnitude less concentrated in oyster tissues compared to their levels in sediments.

Of the organic pesticides measured in seawater in 1975 (Young et al., 1976), only chlordane, dieldrin and PCP were detected, and only at low (pg g-l) concentra- tions. Concentrations were somewhat higher in

Marine Pollution Bulletin

Kaneohe Stream (8.6 pg g-l chlordane and 9.0 pg g-l dieldrin) than in Waikane Stream (2.8 pg g-l chlordane and 1.1 pg g-l dieldrin), reflecting the impact of the termiticides in the urbanized vs rural watersheds. More recent published values for levels of pesticide input into Kaneohe Bay waters are not available, nor are there estimates of input of the dozens of pesticides in use but not analysed in the present study.

The toxicological or ecological impacts of metals and pesticides on the estuarine and coral reef communities of Kaneohe Bay have not been determined. Pridmore et al. (1991) found that low concentrations of chlordane added to natural sediments caused rapid and significant changes in the population structure and densities of two temperate bivalve species. High concentrations (pg g-l) of pesticides and metals were found in corals and octocorals in Florida (Glynn et al., 1989), but these reef populations showed no significant differences in health characteristics between ‘polluted and ‘non-polluted’ sites. Red Sea reef corals concentrated higher levels of heavy metals in soft tissue and skeleton in polluted areas relative to unpolluted areas (Harma & Muir, 1990). The larvae of a scleractinian coral (Pocilloporu dumicornis) are sensitive to very high levels of nickel, carbaryl, naphthol and chlorpyrifos, although larvae are surprisingly tolerant of lower concentrations (Acevedo,

TABLE 6 Concentrations of metals (ng 1-r) detected in seawater in Hawaii.

S. Kaneohe Bay Hilo Keehi Kahana

Element Common sources Bay* Lagoon* Bay* 19751_ 1989*$

As Pesticides 0.940 0.890 1.190 _ 0.960 Ag Home, photography § 9 § - § Cd Rubber 0.133 0.019 0.021 0.007 0.007 Cr Plating 0.324 0.239 0.528 0.032 0.324 cu Wood preservative 0.509 1.330 0.430 0.012 0.856 Hg Health service 0.001 0.001 0.001 0.003 0.001 Ni Plating 1.650 0.680 3.390 0.003 4.180 Pb Batteries, gasoline 0.028 0.042 0.056 0.003 < 0.014 Se Electrical, shampoo lI n n ll Zn Rubber, plating 0.560 - 0.006 0.210 TBT Anti-fouling paints 0.195

*Source: Hawaii Department of Health, Draft Report, samples collected November 1989. $Source: Young et al. (1976). $(TBT) Source: Naval Oceans Systems Center, J. Grovhaug, pers. comm., 1991. $Non-detectable (< 0.001 pg 1-r). ITNon-detectable (< 0.004 ng 1-r). -, Not analysed.

Kaneohe MCAS*

0 - - -

0.001 -

6.150

- -

Pearl Hawaii DOH Harbor* Limits*

1.400 36.000 § No standard

0.016 9.300 0.290 50.000 2.331 2.900 0.001 0.025 2.970 8.300 0.028 5.600

!I 71.000 86.000

0.010

TABLE 7 Concentrations of metals (pg g-l dry wt) in Kaneohe Bay sediments.*

Marine base sites

Element Common sources 1 2

As Pesticides 4.700 7.100 Ag Home, photography 0.036 0.028 Cd Rubber t t Cr Plating 55.000 90.000 CU Wood preservative 14.000 23.000 Hg Health service 0.038 0.003 Ni Plating 35.000 42.000 Pb Batteries, gasoline 12.000 20.000

*Source: Naval Oceans Systems Center, R. S. Henderson, pers. comm., 1992. TNon-detectable (< 0.003 ng g-l).

3 4 5

0.120 0.830 4.720 < 0.015 co.015 co.015

t t 28.000 17.;00 21.000

4.500 1.500 5.400 0.006 < 0.002 < 0.002

20.000 59.000 67.000 6.500 1.600 3.300

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1991; Goh, 1991). Some coral species may be able to tolerate or detoxify trace metals, although growth rates may be affected and community structures will show responses from differential species sensitivities (Howard & Brown, 1984; Brown & Howard, 1985). The coral Porites futeci exhibits a bleaching response on exposure to iron but appears to develop a tolerance over time (Harland & Brown, 1989). In general, although high concentrations of toxicants have been documented, almost nothing is known about the short- term or long-term effects of toxic compounds on tropical and sub-tropical marine organisms.

Despite past and current concerns about the toxicity and persistence of various environmental contaminants (heavy metals and pesticides), few studies have documented their concentrations in tropical or sub- tropical marine biota. Over the past three decades, there has been a growing trend toward a greater usage of persistent contaminants (such as DDT and chlor- dane) in tropical areas with a corresponding decrease in many temperate countries where such usage has been banned (Greenpeace, 1992). A similar trend has been noted for lead, for which inputs from industrialized nations have been reduced but countered by a corresponding increase in Asian countries (Flegal & Stukas, 1987). The present study shows that organic pesticides such as chlordane and dieldrin may be present at human health-threatening concentrations in bivalve tissues for years after their usage has been restricted, and suggests the need for similar screening studies in other tropical and sub-tropical marine ecosystems.

The authors wish to thank P. Helfrich, M. McCartney and other financial supporters of the Kaneohe Bay Environmental Fund, and participants in the 1991 Kaneohe Bay Environmental Workshop. C. L. Hunter was supported in part by the Office of Naval Research Grant No. N00014-92-J-1852. This paper is dedicated to the memory of Dr Carl H. Honig, whose insightful questioning encouraged the initiation of this research. This is contribution No. 975 from the Hawaii Institute of Marine Biology.

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