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Estuaries Vol. 14, No. 3, p. 279-289 September 1991 Long Island Sound" Contamination Distributions, Trends, and Effects of Chemical DONNA D. TURGEON THOMAS P. O'CONNOR National Oceanic and Atmospheric Administration National Status and Trends Program NOAA N/OMA32 Ocean Assessments Division Office of Oceanography and Marine Assessment National Ocean Service Rockville, Maryland 20852 ABSTRACT: Trace metals and organic contaminants concentrations are monitored annually in surface sediments, blue mussel tissue, and winter flounder livers at multiple sites in Long Island Sound by National Oceanic and Atmospheric Administration's National Status and Trends (NS&T) program for Marine Environmental Quality. The NS&T program is also conducting various studies on the bioeffects of contaminants in the sound. Three years of monitoring results indicate organic and elemental contaminants concentrations in sediments and biota at sites in the western portion of the sound are high on a national scale. Possible decreasing trends in cadmium and chlordane in the sound are suggested by the 1986-1988 data for their concentrations in mussels. A comparison between NS&T Mussel Watch results and those of the Environmental Protection Agency's Mussel Watch, conducted from 1976 through 1978, indicated a decadal increase in copper concentrations and a decrease in lead in the sound. Bioeffects studies in the sound have revealed responses to contamination only in localized zones where contaminant levels are very high. Introduction The National Status and Trends (NS&T) Pro- gram of the National Oceanic and Atmospheric Administration monitors chemical contamination in the coastal and estuarine waters of the United States. The program consists primarily of two mon- itoring projects and intensive surveys of the bioef- fects of contaminants. The Benthic Surveillance Project, initiated in 1984, monitors the concentra- tions of organic and elemental contaminants in sur- face sediments and in livers of benthic fish at more than 75 sites nationwide. In addition, histopatho- logical measurements are made on livers of fish. The Mussel Watch Project, initiated in 1986, mon- itors concentrations of the same chemicals in mus- sels or oysters, and surface sediments at more than 200 sites nationwide. Monitoring sites occupied by the Benthic Surveillance and Mussel Watch Pro- jects through 1988 are listed and located on maps in two reports (National Oceanic and Atmospheric Administration (NOAA) 1988, 1989). On average, distances between sites are 20 km in estuaries and embayments and 100 km along open coastlines. The sites have been selected with the intention of collecting samples that are representative of their surroundings. Known point sources of waste dis- charge have been avoided. In Long Island Sound, there are two Benthic Surveillance sites and nine Mussel Watch sites (Fig. 1). Intensive surveys on the bioeffects of contam- inants are not spatially limited to the Benthic Sur- veillance or Mussel Watch sites and are underway in a number of areas. In Long Island Sound, sur- veys are being conducted on reproductive damage, genetic damage in blood cells, and prevalence of disease conditions in winter flounder; species rich- ness and abundance of benthic invertebrates; and sediment and water toxicity. This paper presents the findings for the first three years of the NS&T contaminant monitoring pro- gram in Long Island Sound. The geographic dis- tribution of surficial sediment contaminants among annual monitoring sites; temporal trends in mol- luscan tissue contaminants among NS&T sites and between two national Mussel Watch programs; and the results of several biological effects studies are discussed. Methods Four laboratories have provided NS&T chemical monitoring data for Long Island Sound: NOAA's National Marine Fisheries Service laboratories in Sandy Hook, New Jersey, and Gloucester, Massa- chusetts; and the Battelle Ocean Sciences labora- 9 1991 Estuarine Research Federation 279 0160-8347/91/030279-11 $01.50/0

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Estuaries Vol. 14, No. 3, p. 279-289 September 1991

Long Island Sound"

Contamination

Distributions, Trends, and Effects of Chemical

DONNA D. TURGEON

THOMAS P. O 'CONNOR

National Oceanic and Atmospheric Administration National Status and Trends Program NOAA N/OMA32 Ocean Assessments Division Office of Oceanography and Marine Assessment National Ocean Service Rockville, Maryland 20852

ABSTRACT: Trace metals and organic contaminants concentrations are monitored annually in surface sediments, blue mussel tissue, and winter flounder livers at multiple sites in Long Island Sound by National Oceanic and Atmospheric Administration's National Status and Trends (NS&T) program for Marine Environmental Quality. The NS&T program is also conducting various studies on the bioeffects of contaminants in the sound. Three years of monitoring results indicate organic and elemental contaminants concentrations in sediments and biota at sites in the western portion of the sound are high on a national scale. Possible decreasing trends in cadmium and chlordane in the sound are suggested by the 1986-1988 data for their concentrations in mussels. A comparison between NS&T Mussel Watch results and those of the Environmental Protection Agency's Mussel Watch, conducted from 1976 through 1978, indicated a decadal increase in copper concentrations and a decrease in lead in the sound. Bioeffects studies in the sound have revealed responses to contamination only in localized zones where contaminant levels are very high.

Introduct ion

The National Status and Trends (NS&T) Pro- gram of the National Oceanic and Atmospheric Administration monitors chemical contamination in the coastal and estuarine waters of the United States. The program consists primarily of two mon- itoring projects and intensive surveys of the bioef- fects of contaminants. The Benthic Surveillance Project, initiated in 1984, monitors the concentra- tions of organic and elemental contaminants in sur- face sediments and in livers of benthic fish at more than 75 sites nationwide. In addition, histopatho- logical measurements are made on livers of fish. The Mussel Watch Project, initiated in 1986, mon- itors concentrations of the same chemicals in mus- sels or oysters, and surface sediments at more than 200 sites nationwide. Monitoring sites occupied by the Benthic Surveillance and Mussel Watch Pro- jects through 1988 are listed and located on maps in two reports (National Oceanic and Atmospheric Administration (NOAA) 1988, 1989). On average, distances between sites are 20 km in estuaries and embayments and 100 km along open coastlines. The sites have been selected with the intention of collecting samples that a re representative of their surroundings. Known point sources of waste dis- charge have been avoided.

In Long Island Sound, there are two Benthic Surveillance sites and nine Mussel Watch sites (Fig. 1). Intensive surveys on the bioeffects of contam- inants are not spatially limited to the Benthic Sur- veillance or Mussel Watch sites and are underway in a number of areas. In Long Island Sound, sur- veys are being conducted on reproductive damage, genetic damage in blood cells, and prevalence of disease conditions in winter flounder; species rich- ness and abundance of benthic invertebrates; and sediment and water toxicity.

This paper presents the findings for the first three years of the NS&T contaminant monitoring pro- gram in Long Island Sound. The geographic dis- tribution of surficial sediment contaminants among annual monitoring sites; temporal trends in mol- luscan tissue contaminants among NS&T sites and between two national Mussel Watch programs; and the results of several biological effects studies are discussed.

Methods

Four laboratories have provided NS&T chemical monitoring data for Long Island Sound: NOAA's National Marine Fisheries Service laboratories in Sandy Hook, New Jersey, and Gloucester, Massa- chusetts; and the Battelle Ocean Sciences labora-

�9 1991 Estuarine Research Federation 279 0160-8347/91/030279-11 $01.50/0

280 O.D. Turgeon and T. P. O'Connor

NS&T Sites

Fig. 1. Locations of National Status and Trends monitoring sites in Long Island Sound. Sites 1 through 9 are Mussel Watch sites at Throgs Neck (1), Mamaroneck (2), Hempstead Harbor (3), Sheffield Island (4), Huntington Harbor (5), Housatonic River (6), Port Jefferson (7), New Haven (8), and the Connecticut River (9). Sites 10 and 11 are Benthic Surveillance sites in the western (10) and eastern (11) ends of Long Island Sound.

tories in Duxbury, Massachusetts, and Sequim, Washington. Methods by which chlorinated com- pounds and polycyclic aromat ic hydroca rbons (PAHs) have been extracted and subsequently an- alyzed are detailed by MacLeod et al. (1985) and Wade et al. (1988). Trace metal concentrations have been determined through X-ray fluorescence or by atomic absorption analysis of total digests of tissue in nitric acid or sediment in hydrofluoric acid. Intercalibration exercises among all labora- tories are performed under NOAA's Quality As- surance Program. Results of organic chemical in- tercal ibrat ions th rough 1986 are included in MacLeod et al. (1989).

Shigenaka and Lauenstein (1988) provide a de- tailed listing of sampling protocols. Mytilus edulis (blue mussels) in the size range of 5 cm to 8 cm were collected each winter from nine sites in Long Island Sound, whereas Pseudopleuronectes american- us (winter flounder) were collected at two sites. Once per year at each site, three composites con- sisting of 30 mussels or 10 fish were collected. Sed- iments were collected within 2 km of the mussel sites and at the ends of trawl lines when fish were sampled. At each site, sediments were collected at three stations using specially constructed box cor-

ers, Smith-MacIntyre bot tom grabs, or Van Veen grab samplers. Subsamples for chemical analyses were taken from the top 1-2 cm of each grab or core. Composites for each station were made by combining surficial samples taken from three cores or grabs, and, in turn, three composites (one from each station) were analyzed per site per year.

Table 1 lists the elements and organic chemicals routinely measured in sediments in Long Island Sound. All those chemicals, except antimony, have been monitored in mussels, and all but antimony and PAHs have been monitored in livers of winter flounder. Since 1988, butyltins have been mea- sured annually in a single composite sam~ple of mus- sels from each site. Chemical data summarized in this paper come from two NS&T reports: NOAA (1988) contains means and standard deviations for contaminant concentrations in sediments collected at Benthic Surveillance sites in 1984-1985 and at Mussel Watch sites in 1986-1987, NOAA (1989) contains annual means and measures of difference among them for contaminant concentrations in mollusks collected in 1986-1988.

In this paper, concentrations are presented for aggregate classes of the organic chemicals listed in Table 1. Total polychlorinated biphenyls (tPCBs)

Contamination Distributions, Trends, Effects

TABLE 1. Chemicals and related parameters measured in the National Status and Trends Program.

281

DDT and its metabolites" Polycyclic aromatic hydrocarbons" Major elements

o,p'-DDD 2-ring AI Aluminum p,p'-DDD Fe Iron o,p'-DDE Biphenyl Mn Manganese p,p'-DDE Naphthalene Si Silicon o,p'-DDT l-Methylnaphthalene p,p'-DDT 2-Methylnaphthalene Trace elements

2,6-Dimethylnaphthalene Chlorinated hydrocarbons Acenaphthene Sb Antimony other than DDT and PCB As Arsenic

3-ring Cd Cadmium Aldrin Cr Chromium Alpha-Chlordane Fluorene Cu Copper Trans-Nonachlor Phenanthrene Pb Lead Dieldrin l-Methylphenanthrene Hg Mercury Heptachlor Anthracene Ni Nickel Heptachlor epoxide Se Selenium Hexachlorobenzene 4-ring Ag Silver Lindane (gamma-BHC) Fluoranthene Sn Tin Mirex Pyrene Zn Zinc

Benz(a)anthracene

Polychlorinated biphenyls b

5-ring

Chrysene Benzo(a)pyrene Benzo(e)pyrene Perylene Dibenz(a,h)anthracene

Dichlorobiphenyls Trichlorobiphenyls Tetrachlorobiphenyls Pentachlorobiphenyls Hexachlorobiphenyls Heptachlorobiphenyls Octachlorobiphenyls Nonachlorobiphenyls

Related parameters

Lipid in tissues Grain size in sediments Total organic carbon in sediments Coprostanol in sediments

�9 Dichlorodiphenyhrichloroethane (DDT), dichlorodiphenyldichloroethane (DDD), dichlorodiphenyldichloroethene (DDE). b PCBs quantified to level of chlorination in 1984 through 1987. Beginning with samples collected in 1988, 18 individual compounds

(congeners) have been quantified. " Five PAH compounds added to the list of analytes in 1988: acenaphthylene, 2,3,5-trimethyl naphthalene,benzo(b) and benzo(k)

fluoranthene, indeno(l,2,3-cd)pyrene, and benzo(g,h,i)perylene.

is the sum o f concent ra t ions o f PCBs at each level o f chlor inat ion or, equivalently (NOAA 1989), twice the sum of the concentra t ions o f 18 conge- ners . T o t a l d i c h l o r o d i p h e n y l t r i c h l o r o e t h a n e ( tDDT) is the sum of concent ra t ions o f D D T and its metabol i tes , d i ch lo rod ipheny ld i ch lo roe thane (DDD) and d i c h o l o r o d i p h e n y l d i c h l o r o e t h e n e (DDE). To ta l ch lo rdane ( tChlordane) is the sum of c o n c e n t r a t i o n s o f a lpha -ch lo rdane , t rans-nona- chlor, heptachlor , and hep tach lor epoxide. Tota l polycyclic aromat ic hydrocarbons (tPAHs) is the sum of concent ra t ions o f the individual polycyclic aromat ic hydrocarbons .

Contaminan t concent ra t ions in sediments have been adjusted for the sand conten t o f each sample (NOAA 1988). Ordinari ly , because contaminants are associated with the surfaces o f particles and

sand particles have lower surface areas per unit weight than do silt o r clay particles, one does not expect comparable levels of contaminat ion in sandy sediments. This effect o f sand has been counter - acted by dividing all concent ra t ions by the weight fract ion o f mud-sized particles in the sample (par- ticles smaller then 63 /~m in diameter) . For ex- ample, if a sample conta ined 60% mud and had a Zn concent ra t ion o f 100/~g g-~, its adjusted con- cent ra t ion would be 1 0 0 /0 .6 or 167 #g g-L Ad- jus ted concentra t ions are effectively those that samples would have if they consisted ent irely o f mud and provide a c o m m o n basis for comparisons among sites.

Care has been taken not to ove rex tend the as- sumption that sand-sized particles have no associ- ated contaminants and that they are only diluting

2 8 2 D.D. Turgeon and T. P. O'Connor

TABLE 2. Mean concentrations of contaminants in sediments and mussels from the National Status and Trends Mussel Watch site at Throgs Neck, New York. Means in sediments based on grain-size normalized concentrations in six samples (n = 6) collected in 1986 and 1987. Means in mussels based on nine samples (n = 9) collected in 1986 through 1988.

Sediment Mussel Tissue

Contaminant Mean Cone' (+_SD) Mean Cone" (_+SD)

tDDT 77 (19) 210 (71) tPCB 460 (92) 1,300 (300) tPAH 14,000 (3,300) 4,900 (3,000) tChlordane 13 (3.3) 86 (19) Dieldrin 2.5 (3.6) 20 (20) antimony 3.3 (2.2) - - arsenic 9.4 (6.0) 5.6 (0.9) cadmium 1.9 (0.59) 3.6 (1.0) chromium 200 (42) 2 (0.26) copper 190 (48) 15 ( 1.8) lead 190 (36) 8.8 (3.7) mercury 1.2 (0.32) .13 (0.03) nickel 56 (18) 3.1 (0.75) selenium 0.68 (0.36) 1.9 (0.4) silver 5.2 (2.3) .32 (0.04) zinc 310 (68) 120 (20)

�9 Concentrations of organic contaminants in units of ng per g-dry weight and concentrations of elements in units of ug per g-dry weight.

the mud in a sample of sediment. As the sand con- tent increases this assumption becomes increasing- ly critical. The NS&T data have not been adjusted whenever the sand content exceeds 80% (converse- ly, whenever the mud content is less than 20%). No concentrations have, therefore, been adjusted by more than a factor of 5 (divided by less than 0.2). This avoids distortions that could result when- ever a small amount of contamination in a mostly sandy sample would be adjusted to a high concen- tration simply by being divided by a small number.

Results

DISTRIBUTION OF CONTAMINANTS IN SEDIMENTS

Four Long Island Sound sites (6, 7, 8, and 11 in Fig. 1) yielded samples consisting only of sand, so comparisons among sites are limited to the seven other sites. For most contaminants, the highest concentrations are in the western end of the sound (sites 1, 2, and 3, Throgs Neck, Mamaroneck, and Hempstead Harbor, respectively). Contaminant concentrations in sediments at the Throgs Neck site are listed in Table 2, and concentrations for other sites are shown in figures as ratios relative to Throgs Neck. Figures 2a and b show those ratios for elemental (Ag, Cd, Hg, and Pb) and organic (tPCBs, tDDT, tChlordane, and tPAHs) contami- nants. Sites in those figures are listed from left to right in approximate west-to-east order. The four elements chosen for Fig. 2a are those with the larg-

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=g 3: 3:

Fig. 2. Ratios of mean concentrations of elements (a) and organic contaminants (b) in sediments at National Status and Trends sites to concentrations in sediment at the Throgs Neck site. Data from Benthic Surveillance in 1984 and 1985 and Mussel watch in 1986 and 1987 have been aggregated. For each sample, data have been adjusted to the fine particle size fraction of sediment (i.e., divided by the fraction of sediment in the <63 pm size category). All sediments from the Port Jefferson, Hou- satonic River, New Haven, and Eastern Sound sites were more than 80% sand and have been excluded from this comparison.

est differences between the highest and the lowest concentrations. Mean concentrations for six other elements (Cr, Cu, Ni, Sb, Se, and Zn) were also highest at the Throgs Neck site.

The tPAHs concentration at the Sheffield Island site appears anomalously elevated in the geograph- ic sequence (Fig. 2b). The variance around the mean concentration for that site is high because of a ten-fold difference between 1986 and 1987 sam- ples. That difference may have been due to a zone of sediment with high tPAHs concentration having been sampled in 1986 and the high mean may not be representative of the site.

Contamination Distributions, Trends, Effects 283

"~ 1.75 ]- l "~

2 ~.2s 2 ~ . o - ] l m l m . g ,i I ~- 1.oo-1,= I [ ] . [] Cd = ~ [] Pb

o ~176 I >= o.75 >= , o_. o.2s , ~

... ~, .n ~ oo 8 o o o ~ 8 " ' . . . . . . . .

"~ 1.s -~ 1 . 7 5 T ~ ~" "= 1.so-] b [] tPc , ~, r 1 25 t �9 tOOT o o " "] I [ ] tCh lo rdane I ~ 1.o

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Fig. 3. Same as Fig. 2a and b except that data have not been adjusted for sand con ten t and no data have been excluded. Ratios o f mean concentra t ions for e lements (a) and organic contaminants (b) in sediments at National Status and T rends sites to concent ra t ions in sediment at the Throgs Neck site.

Fig. 4. Ratios o f mean concentra t ions for e lements (a) and organic contaminants (lo) in mussels at National Status and Trends sites to concentra t ions in mussels at the Th rogs Neck site. Data f rom all samples collected in 1986 th rough 1988 have been aggregated.

Greig et al. (1977) described an enhancement of Cd, Cu, Cr, Pb, Hg, Ni, Ag, and Zn in sediments west of the Hempstead sill relative to the rest of the sound. Turekian et al. (1980) compared the Greig et al. (1977) data with maps of particle size distribution in Long Island Sound sediments. They concluded that, while grain size was the primary factor controlling the trace element concentra- tions, the sediments around Throgs Neck, the Housatonic River, and New Haven were being con- taminated by human activity.

The sediment at the NS&T Housatonic River site contained more than 80% sand and, by the NS&T criterion, chemical data would not be ad-

justed for comparison with other sites. Figures 3a and b are similar to Figs. 2a and b except that raw, unadjusted data have been used to calculate means for each site. On that basis the Housatonic River site contains as much organic contamination as sites in the western sound. It also displays more trace metal contamination than do the other sandy sites at New Haven, Port Jefferson, and Eastern Long Island Sound. These latter sites, like almost all of the 28 NS&T sites yielding only sand (NOAA 1988), appear uncontaminated. The fact that they are sandy, however, confounds their comparison with other sites. The Housatonic River site is being pointed out because, although its sand content ex- cludes rigorous comparisons, it does have chemical

284 D.D. Turgeon ancl T. P. O'Connor

concentrations that, in agreement with Turekian et al. (1980), indicate contamination.

DISTRIBUTION OF CONTAMINANTS IN TISSUES

Mean concentrations based on all nine analyses (three per year) for each chemical in mussels from the Throgs Neck site are listed in Table 2. In Figs. 4a and b those data for four trace elements and four classes of organic compounds are compared with mean concentrations in mussels at the eight other Mussel Watch sites in the sound. As with sediments, concentrations were generally higher west of Hempstead sill (sites 1-3). Ag and Cd con- centrations in mussels at the Housatonic site were as high as in the western end of the sound. Among the elements not shown in Fig. 4, Zn was highest at Throgs Neck, Cu was equally high at Throgs Neck and the Housatonic River sites, Ni was equal- ly high at Throgs Neck and the Connecticut River sites, and Cr was nearly as high at both the Hou- satonic and Connecticut river sites as at Throgs Neck.

LONG ISLAND SOUND CONTAMINATION IN WIDER CONTEXT

The Long Island Sound data have been con- veyed in Figs. 2 through 4 as being generally high- est at the Throgs Neck site. On a broader scale, however, the concentrations in sediments and mus- sels at Throgs Neck are generally lower than those at NS&T sites in the Hudson-Raritan Estuary. The large number of people in New York City and its environs is the primary reason for the high con- taminant levels in that area. The tendency for con- taminants in the sound to be at their highest levels in the west may simply reflect the approach to the megalopolis. It should be noted that while sedi- ment contamination does increase further toward New York City, the levels of several contaminants in the western end of the sound are already among the highest 10% over the national distribution of NS&T sites (NOAA 1988).

BUTYLTIN CONCENTRATIONS IN MUSSELS

Mono-, di-, and tributyltin were measured in Long Island Sound mussels during 1988. Concen- trations were highest at Mamaroneck, followed by Port Jefferson (Fig. 5). The lack of a west-to-east trend in Fig. 4 is probably due to the butyltin con- centrations being highest in the vicinity of marinas. Until recently, anti-fouling paints based on tribu- tyltin (TBT) were popular on recreational vessels. That use of T B T in the United States was effec- tively banned with passage of the Organo Anti- fouling Paint Control Act of 1988 (P.L. 100-333). Therefore, a decreasing trend is expected in mol-

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- I m

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600

500

400

300

200

100

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Fig. 5. Concentrations of mono-, di-, and tributyltin in mus- sels at National Status and Trends sites in 1988. Concentrations are given in terms of ng of tin per g of dry tissue regardless of the number of butyl groups.

luscan concentrations of T B T and its breakdown products, di- and monobutyltin. The total butyltin concentration of 550 ng g-i dry weight (as Sn) at the Mamaroneck site, the highest concentration among the East Coast sites sampled in 1988, can be compared with values in the range of 1,000- 3,000 ng g-I found in oysters or mussels at sites near marinas in Naples, Florida, San Diego, Cali- fornia, Los Angeles, California, Bellingham, Wash- ington, and Honolulu, Hawaii (Wade et al. 1988).

TRENDS

Trends are correlations between concentrations and time. With only three years of Mussel Watch data, however, simple correlations were not con- sidered sufficient evidence of trends. Trends were indicated as possible only when two conditions were met: 1) a statistically significant difference existed among the years (Kruskal-Wallis test at 0.05 level), and 2) the concentration means were monoton- ically increasing or decreasing. When these con- ditions were applied to all contaminants at all 132 sites throughout the United States for which there are data for 1986, 1987, and 1988, no trends were indicated at most sites for most contaminants (NOAA 1989).

However, two possible trends were apparent among groups of sites in the sound. Cadmium con- centrations appeared to be decreasing at all nine sites (Fig. 6) and at five of those sites there were significant differences and monotonic decreases.

Contamination Distributions, Trends, Effects 285

6 �9 Cd 86 T

i [] c.8, i / 5

4

E �9 2

?_, 1

0

o ~ =* '= z

Fig. 6. Cadmium concentrations (means and standard de- viations) in mussels at National Status and Trends sites in 1986, 1987, and 1988. At seven sites (all except Huntington Harbor and Port Jefferson) there was a statistically significant difference among the three years (Kruskal-Wallis, 0.05 level) and at five of those sites there was a monotonic decrease.

Throughout the 132 sites nationwide, there were only 17 with significant and monotonic decreases in Cd. Similarly with chlordane, nationwide there were only six sites where concentrations were de- creasing and significantly different among the years, and three of those were sites in Long Island Sound. If the possible trends suggested by three years of data are real, they will be verified with data from subsequent years.

Two Long Island Sound sites (Housatonic River and Hempstead Harbor) are each within 5 km of sites occupied from 1976 through 1978 by a pre- vious mussel watch program (Goldberg et al. 1983) sponsored by the United States Environmental Protection Agency (EPA). For these sites, changes can be estimated over a ten-year period for the six elements measured in both programs. In Figs. 7 and 8, the annual mean concentrations for the three years of NS&T data are compared with the annual values measured in the three-year EPA program. Figure 7 shows concentration ratios for Cd, Cu, Ni, Pb, a n d Z n relative to 1976 values. All those ratios are on a scale of 0.3 to 2.0. The ratios for Ag (presented separately in Fig. 8) extend from 0 to 9.

Differences between the sets of concentrations separated by ten years have been sought by com- paring the 1976-1978 values with the 1986-1988 mean concentrations. The Mann-Whitney test of two sets of three numbers will effectively find a 95% probability of difference when all three num-

bers in one set are outside the range of the numbers in the other. The only significant decadal differ- ences in the Long Island Sound data are for in- creased Cu at the Hempstead Harbor site (Fig. 7a) and increased Ag at the Housatonic River site (Fig. 8b). On a nationwide basis, comparison is possible at 50 pairs of EPA and NOAA sites (Lauenstein et al. 1990), and the most common result, as it was for Long Island Sound, is a lack of significant dif- ference (Mann-Whitney test).

Although the Mann-Whitney test found no dif- ference in Pb, the average concentrations are low- er at both Long Island Sound sites in the more recent data set. In the national context, the average of the more recent Pb concentrations is lower in 39 of 50 sites. So, the small Pb decrease in Long Island Sound is part of a national trend that can be attributed to the decreasing use of alkyl-lead additives in gasoline (Trefrey et al. 1985; Shen and Boyle 1987).

The Cu increase at the Hempstead Harbor site may also be part of a national picture. The more recent Cu concentrations were higher than in the 1970s at 25 of the 30 common sites at which mus- sels (as opposed to oysters) were collected. More- over, by the Mann-Whitney test, 15 of those dif- ferences were statistically significant. An increasing trend for Cu is harder to explain than the decreas- ing trend for Pb. Seasonal differences might be suspected: the EPA collections were made in the summer while the NS&T collections were in the winter. Mussels collected in summer could have spawned just before collection. I f the gametes con- tain proportionally less metal than do other tissues, mussels will lose body mass without losing metal and metal concentrations will increase (Phillips 1980). However, this does not explain the Cu re- sults, because the Cu levels in the summer-collected animals are lower, not higher. Furthermore, al- though decadal differences for Cu concentrations in mussels are in a consistent direction and statis- tically significant, the differences for other metals are either non-existent, in the opposite direction, or not significant. Moreover, no seasonal trends of metal concentrations in mussel tissue were found in a study in Long Island Sound (Freitas et al. 1988). Figure 9 shows the Cu concentrations mea- sured in mussels at three Mussel Watch sites on four occasions over a year. Because the variances are small, differences can be found among the mean concentrations, but there is no consistent tendency for concentrations to be at their highest or lowest values in any particular month. These observations lead us to conclude that there may, in fact, have been a national increase in Cu contamination. Among the six metals measured by both Mussel Watch programs, copper is the only one that was

286 D.D. Turgeon and T. P. O'Connor

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� 9 � 9

1 .

0

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o [ ] Cd

[ ] Hi

8 0

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Fig. 7. Comparison of National Status and Trends data (1986-1988) for Cu, Cd, Ni, Pb, and Zn in mussels with EPA Mussel Watch data (1977-1978, Goldberg et al. 1983) for two sites in Long Island Sound. All data are shown as ratios to the 1976 concentration. The Hempstead Harbor and Housatonic River National Status and Trends s i t e s a r e compared with the Manhasset Neck and New Haven EPA sites, respectively. Within each pair, the sites a r e s e p a r a t e d by 5.3 km to 5.5 km.

being consumed in the United States in higher amounts in the late 1980s than in the late 1970s (Lauenstein et al. 1990).

The Ag increase at the Housatonic River site is not part of a national trend. Although Ag concen- trations at the Housatonic site are higher in the 1980s than in the 1970s, the three 1980 concen- trations themselves suggest a decreasing trend.

D i s c u s s i o n

MONITORING SPATIAL AND TEMPORAL

TRENDS

The enhancement of contamination in western Long Island Sound is evident in both sediment and

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8"~ b 7'! Housat0nic River

6" 5: 4" �9 Ag 3: 2-" 1

0 to I~ a~ to I',,. to

Fig. 8. Comparison of National Status and Trends data (1986-1988) for Ag in mussels with EPA Mussel Watch data (1976-1978, Goldberg et al. 1983) for two sites in Long Island Sound. All data shown as ratios to the 1976 concentration. The Hempstead Harbor and Housatonic River National Status and Trends sites are compared with the Manhasset Neck and New Haven EPA sites, respectively. Within each pair, the sites are separated by 5.3 km to 5.5 km. The "n.d." for the 1978 ratio indicates that Ag was not detected in the composite for that year.

mussel tissue analyses from the NS&T program. If spatial distributions were all that were sought through, the monitoring program, sediment anal- yses would be sufficient. On a national scale, results of tissue analyses cannot readily be compared be- cause different species are collected in different regions. For example, at NS&T sites south of New Jersey and through the Gulf of Mexico oysters are sampled rather than mussels. At the Housatonic River site, both species have been collected and the concentrations of Ag, Cu, and Zn in oysters ex- ceeded those in mussels by at least a factor of 10 (NOAA 1989). Such species differences are obvi- ously avoided when sediment is used for monitor- ing spatial trends but, even here, as demonstrated by the Long Island Sound data, care is required when samples contain large amounts of sand.

On the other hand, mollusks are superior to sed-

A

O) O~

o

2 0 '

15 �84

10

�9 x : z 3 e- o

t ~ o o

I - - ,.- 0 : 0 ,i-

Fig. 9. Copper concentrations (means and standard devia- tions) in mussels collected at three Long Island Sound sites on four occasions between November 1986 and December 1987. In all cases three composite samples were analyzed.

iment for monitoring annual temporal trends. The central problem with sediment is that the age of a surface sample is usually unknown. Even if only 1 cm layers are sampled and sedimentation rates ex- ceeded 1 cm yr -I, biological mixing of sediments would prevent annual samples of the upper 1 cm from being independent records of contamination. In contrast, contaminant levels in mollusks can change fairly rapidly in response to the surround- ings. Roesijadi et al. (1984), for example, moved mussels from a contaminated area to a clean area and vice versa and found that tissue levels of trace elements reflected the environmental levels in two months. In similar transplanting studies with oys- ters, Pittinger et al. (1985) found that organisms' polycylic aromatic hydrocarbon concentrations were adjusted to steady-state levels in matters of days. Pruell et al. (1987) exposed mussels to a sus- pension of contaminated sediment and found levels of polychlorinated biphenyls and polyaromatic hy- drocarbons to increase to a steady-state level in about 20 d.

The NS&T program is attempting to monitor trends in contamination through the annual col- lection and analysis of mollusks. Given that mol- lusks adjust to changes in contamination on time scales of a few months or less, it is fair to expect chemical concentrations in succeeding years to be independent of one another. Surface sediments, on the other hand, are mixtures of material de- posited over several years. Samples collected in succeeding years should, to a large extent, be es-

Contaminat ion Distr ibut ions, Trends, Effects 287

TABLE 3. Results of sediment toxicity tests based on survival of the amphipod Ampelisca abdita. Each sediment sample was tested five times and each test employed 20 individuals. Results are listed as the mean number of deaths during the ten-day exposures in flowing seawater. No significant (p < 0.05) differ- ences were found among the sites. (Scott, SAIC Narragansett, Rhode Island, unpublished data.)

Mean N u m b e r S i t e / C O D E o f Dea ths SD

Central Long Island Sound (Control site) 0.6 0.5

Housatonic River 3.2 2.6 Sheffield Island 2.4 1.8 Huntington Harbor 1.6 1.1 Hempstead Harbor 1.8 1.3 Mamaroneck 2.6 1.7 Throgs Neck 2.2 0.8 Hudson Raritan, Lower Bay 1.8 2.0 Hudson Raritan, Upper Bay 1.6 1.1

sentially the same material, and chemical concen- trations will not be independent.

BIOLOGICAL RESPONSE TO CONTAMINATION

In addition to monitoring spatial and temporal trends in chemical contamination, NS&T studies in Long Island Sound have focused on the bioef- fects of contaminants.

Routine histopathological analysis of livers have been made on 30 winter flounder collected at each of the two Benthic Surveillance sites in each year between 1984 and 1986 (NMFS 1988). One liver neoplasm was found in fish from the western site; none were found in fish collected at the eastern site. Gronlund et al. (1991) have summarized re- sults from 1987 collections of winter flounder at four stations in the sound: western Long Island Sound north of Lloyd Neck, New York (the west- ern Benthic Surveillance site); the mouth of Nor- walk River, Connect icut ; Morris Cove, Con- necticut (south of New Haven); and Niantic Bay, Connecticut. Morris Cove is a contaminated em- bayment within New Haven Harbor where winter flounder with liver tumors had previously been found (Murchelano and Wolke 1985). DNA ex- tracted from livers offish in Morris Cove was found to be combined with chemicals that were probably metabolites of PAHs. Similar adducts have been identified in hepatic DNA isolated from fish col- lected in parts of Elliott Bay (Seattle, Washington) and Boston Harbor (Stein et al. 1989).

NS&T studies are also exploring the possibility that winter flounder in Long Island Sound are suf- fering reproductive damage. Since 1987, egg fer- tilization and development have been examined for winter flounder collected at six sites: Shoreham and Hempstead Harbor, New York, and Madison, New Haven, Milford and Norwalk, Connecticut

288 D.D. Turgeon and T. P. O'Connor

(NMFS 1989). In 1987 and 1988, the condition of eggs, embryos, and larvae from 200 female winter flounder were compared with those from two sites in the Boston Harbor area. Among the Long Island Sound sites, the New Haven (Morris Cove) floun- der embryos had the most abnormalities and the lowest percent of viable hatch. Johnson et al. (I 988) have found that English sole in parts of Puget Sound have lost all or part of the ability to generate eggs. This type of reproductive damage, which is not evident through examination of eggs and their de- velopment, is now being quantified for winter flounder in Long Island Sound.

Tests, in 1989, of sediment toxicity based on survival of the amphipod Ampelisca abdita have not revealed toxic conditions at any of the NS&T sites on Long Island Sound or at the more contaminated sites in the Hudson-Raritan Estuary (Table 3). Tests had previously found toxic conditions in Long Is- land Sound at Black Rock Harbor, a part of Bridge- port Harbor that is extremely contaminated (Rog- erson et al. 1985).

Sunda and Huntsman (personal communication) analyzed water samples from 100 coastal sites (40 in Long Island Sound) in the northeastern United States for total dissolved copper and zinc concen- trations, and for free-ion copper activities that cor- respond to the potential for copper toxicity to ma- rine organisms. Total copper concentrations in excess of 30 nM were among the highest and were found in samples from the East River, Stamford Harbor, Norwalk Harbor, Bridgeport Harbor, New Haven Harbor, and the Connecticut and Housa- tonic river estuaries. Free cupric ion activities were in a potentially toxic range in surface water samples from Stamford Harbor, Bridgeport Harbor, New Haven Harbor, and central Long Island Sound. This observation is being pursued with direct mea- surements of toxicity, but toxicity, if it is found, would appear to be in isolated locations.

All of these observations: discrete instances of high Cu concentrations in water, the lack of re- sponse in sediment bioassays, the single instance of a liver tumor at the western Benthic Surveillance site, and the genetic and reproductive damage found in Morris Cove but not elsewhere, imply .that effects of contamination can be found in Long Is- land Sound but that they occur in isolated areas.

ACKNOWLEDGMENTS

This paper has benefited from reviewer comments. We are especially grateful to D. A. Wolfe for thoughtful and clarifying suggestions.

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