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RESOURCE FILES

LNG Related Pollution

Compiled by Arthur MacKay Bocabec, NB, Canada September, 2012

RESOURCE FILES

WHAT ARE RESOURCEFILES?


Resource files are created from the contents of the working reference and publication files of Art MacKay and are made available for reference purposes. They contain documents, drawings, photographs and other resources accumulated over a 50 year period, including public domain materials as well as materials with copyrights held by Arthur MacKay and others. Since online resources come and go, they have been converted to PDFs to preserve their contents. They can be accessed directly where the links are still active. Copyright requirements are specified for each item if available. Art MacKay can be contacted at art@bayof fundy.ca to clarify availability for further publication. Entire files composed of physical documents, books, photos, cds, etc. are available and sold separately.

REFERENCES

FINAL REPORT
Identifying PoJ]utants in Species Regularly Consumed by Native Americans in the Passamaquoddy Bay Region

FY 1997 Environmental Justice Project

RESULTS OF THE TOXlCS MONITORING PROGRAM


March 9, 2001

Environmental Department of the Passamaquoddy Tribe at Pleasant Point PO Box 343 Perry, Maine 04667

Community Partner: Cobscook Bay Resource Center 4 Favor Street Eastport, Maine 04631

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Crealed by the Cobs cook Bay Resource Cenler from data provided by the Maine Department of Marine Resources and the Maine Office of GIS.

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ACKNOWLEDGEMENTS
We are grateful to the US Environmental Protection Agency for funding this project under the Environmental Justice program. For assistance in sample collection we would like to thank Fred Moore of the Passamaquoddy Tribe and Dennis Preston. The University of Maine Water Resources Institute and the State of Maine Health and Environmental Testing Laboratory analyzed the samples and provided assistance in initial project design. In particular we would like to thank Therese Anderson from WRI and John Nims and Michael Corbin from HETL for their generous willingness to go beyond the initial project workplan. Thanks to Barry Mower and Chuck Penney at the Maine Department of Environmental Protection for their cooperation in providing us with data and information about Maine's toxics and dioxin testing programs. We would especially like to thank John Sowles of the Maine Department of Marine Resources for his assistance in preparing this report. His comments and suggestions were invaluable.

ABSTRACT
In 1997 the Pleasant Point Passamaquoddy Tribe, in cooperation with its community partner, the Cobscook Bay Clam Restoration Project (which became the Cobscook Bay Resource Center in 1998), undertook this project to identify potential pollutants in marine species often consumed by tribal members. The Toxics Monitoring Program was designed to identify the levels of dioxin and thirteen priority pollutant metals in five marine species. The information gathered was intended to be used as baseline data describing the pollutant levels of certain species in the Passamaquoddy Bay region. Tissue samples were taken from species collected in Passamaquoddy Bay and in Cobscook Bay. A total of eight composite tissue samples were collected from the following species: lobster, soft-shell clam, cod, and sea scallop. Samples were analyzed for dioxin at the University of Maine at Orono Water Resources Institute lab and were analyzed for heavy metals at the State of Maine Health and Environmental Testing lab. Results obtained from analysis for heavy metals and dioxins were compared with other state, regional, and national studies including the EPA National Study of Chemical Residues in Fish, the State of Maine Surface Water Ambient Toxic Monitoring program, and the Gulf of Maine Council Gulf Watch Program. The comparisons to other studies are not meant to be used as a determinant of risk to public health. For health risk assessments to be made, the data must be independently reviewed by a professional risk assessor. It is recommended that the data reported here be independently reviewed by a human health risk assessor and that further, regular testing of these species be performed to determine trends or changes.

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JNTRODUCTION
In 1997 the Pleasant Point Passamaquoddy Tribe, in cooperation with its community partner, the Cobscook Bay Clam Restoration Project (which became the Cobscook Bay Resource Center in 1998), undertook this project to identify potential pollutants in marine species often consumed by tribal members. The Toxics Monitoring Program was designed to identify the levels of dioxin and thirteen priority pollutant metals in five marine species. The information gathered was intended to be used as baseline data describing the health of certain species inthe Passamaquoddy Bay region. The traditional fishing grounds of the Passamaquoddy Tribe include the St. Croix Estuary, Passamaquoddy Bay, and Cobscook Bay. Today, these areas support the tribe's cultural way of life as well as serving as a source of food. Each area is subject to varied point and nonpoint sources of pollution. In particular, the estuary is influenced by industrial outflow from several municipal wastewater treatment plants and a paper mill. The effects oftbese sources of pollution on estuarine and marine biota are largely unknown. Tribal members remain potentially at risk from a number of health threatening pollutants. There is a statewide warning against the consumption of lobster tomalley due to high dioxin content and other contaminants such as cadmium. Lobster and finfish in Passamaquoddy Bay are tested irregularly and infrequently for dioxin content. Other marine organisms such as clams are not tested in this area for dioxin and heavy metals. Studies performed nationally have documented concentrations of select toxins in fish and shellfish but most work has focused on freshwater, and not marine, species. In the National Study of Chemical Residues in Fish, undertaken by the U.S. Environmental Protection Agency, freshwater fish from thirteen sites in Maine were analyzed for dioxin (U.S. EPA, 1992 a and b). The mean concentrations for six dioxin congeners are summarized in picograms per gram in the table below. 2,3,7,8 TCDD 13.39 pg/g 1,2,3,7,8 PeCDD 1.50 pg/g 1,2,3,4,7,8 HxCDD 0.49pg/g 1,2,3,6,7,8 HxCDD 7.52 pg/g 1,2,3,7,8,9 HxCDD 0.67 pg/g 1,2,3,4,6,7,8 HpCDD 3.09 pg/g

In the same study, seven freshwater sites in Maine were analyzed for Mercury. The mean concentration for mercury in these sites was 0.30 ug/g. Nationally, 92.2 % of the 374 sites surveyed were found to have detectable levels of mercury in finfish. The mean concentration of mercury in freshwater fish nationally was 0.26 ppm.

In the National Contaminant Biomonitoring Program, freshwater fish were analyzed for their levels ofcadmiurn (U.S. EPA, 1995). In 1984, cadmium was found in a mean concentration level of 0.03 ppm in freshwater fish surveyed.

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Studies done outside the United States have documented the levels of mercury in marine fish and shellfish (U.S. EPA, 1995). Concentrations ofinorgaruc mercury were found to be between 0-5.6 ppm. However, most sites were found to have less than .5 ppm inorgaruc mercury for most species. The Maine Surface Water Ambient Toxic Monitoring Program is documenting the levels of toxics in freshwater fish and some marine species. In 1995, monitoring was accomplished for levels oftoxics in lobsters in eight sites along the Maine coast (Sowles, 1997). The table below sununarizes the results of this study in approximate average concentrations in micrograms per gram. Lobster Meat (dry weight) Arsenic Cadmium Chromium Copper Lead Mercury Selenium Zinc 19 ug/g 0.15 ug/g 0.41 ug/g 60.75 ug/g 0.84 ug/g .83 ug/g 2.65 ug/g 127.5 ug/g Lobster Tomalley (dry weight) 16.75 ug/g 7.69 ug/g 0.23 ug/g 253.75 ug/g 1.06 ug/g

.33 ug/g
2.63 ug/g 54.25 ug/g

The results of this project are meant to provide the Tribe, the Resource Center, and other interested parties with infonnation about the levels of heavy metals and dioxin in marine species in the Passamaquoddy Bay region. The data will be used to detennine future monitoring needs as well as providing the Tribe with information it needs to advise tribal members about the potential health effects of consuming fish and shellfish. METHODS Tissue samples were taken from species collected in Passamaquoddy Bay and in Cobscook Bay. A total of eight composite tissue samples were collected from the following species: lobster, soft-shell clam, cod, and sea scallop. The irutial proposal for this project called for flounder samples to be taken as well, however, samples of this species were not obtained. Lobster: Two composite samples were colJected in Passamaquoddy Bay between Gleason Point, Perry and the Robbinston Public Boat Landing by wire lobster trap. Each sample consisted offive individual animals. One sample was collected on 9/18/98 and the arumals ranged in size from 1 pound to 2 pounds 8 ounces. The second composite was collected on 10/5/98 and each individual ranged in size from 3 pounds to 3 % pounds. AJllobsters were sent to the lab in the shell.

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Soft-Shell Clam: Two composite samples were collected of this species. On 9/18/98, one sample was collected at Gleason Cove, Perry in Passamaquoddy Bay by hand harvest. This composite consisted of20 animals ranging in size from 70 rom to 87 rom. The second sample was collected on 9/18/98 below the ceremonial grounds at Pleasant Point in Cobscook Bay by hand harvest. This sample consisted of 18 animals ranging in size from 68 rom to 84 rom. All clams were sent to the lab in the shell. Cod: One composite sample of cod was collected on 8/28/98 in the deep hole off Pleasant Point in Passamaquoddy Bay. The sample consisted of five animals collected using a hand line. The animals ranged in sized from 1.10 pounds to 3 pounds. All cod composites consisted of whole fish. Sea Scallop: A total of three composite samples were collected for scallops. On 11/29/98, a sample was collected by a diver in Mill Cove, Robbinston which is in Passamaquoddy Bay. This sample consisted of 20 muscle only scallop meats and weighed a total of 1.5 pounds. On 11/30/98 two composites were collected by a dragger in Whiting Bay within Cobscook Bay. One sample consisted of 20 muscle only scallop meats weighing 2 pounds and the other consisted of 18 meats and weighed 2.05 pounds.
All samples were wrapped immediately after collection in aluminum foil and placed on ice. After being transported back to the project coordinator's residence they were placed in a freezer and kept frozen until transport to the University of Maine Water Research Institute lab. There shellfish samples were shucked and the soft tissue ground and homogenized. For cod, the whole body sample was used for the composite. The muscle tissue and the tomalley were separated for lobster and analyzed separately. A portion of each sample was analyzed for dioxins and furans at WRl while another portion was sent to the Maine Health and Environmental Testing lab in Augusta to be analyzed for heavy metals. Analysis for the following metals was performed: arsenic, beryllium, cadmium, chromium, copper, lead, mercury, nickel, antimony, selenium, silver, thallium, and zinc. Dioxins and furans were analyzed using EPA 1613, the method for tetra- through octachlorinated dioxins and furans by isotope dilution HRGC/HRMS. Samples were analyzed for metals using EPA 200-7.

RESULTS

Heavy Metals The following tables display the results of the heavy metals analysis for each composite sample. All results are expressed as parts per million and are in dry weight basis. The following codes apply in the sample identification numbers: PAS - Passamaquoddy Bay COB - Cobscook Bay

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SCA - Scallop LOB - Lobster TOM - Lobster Tomalley CLA-Clam COD-Cod In .the results table "ND" stands for Not Detected Down to the Reporting Limit and 'T' stands for Approximately.
Sample As Be

Cd

PAS-SCA-Ol COB-SCA-02 COB-SCA-03 PAS-LOB-Ol PAS-LOB-02 PAS-TOM-01 PAS-TOM-02 PAS-CLA-Ol COB-CLA-02 I PAS-COD-Ol
Sample Pb

4.6 5.2 5.3 31 72 15 37 8.1 2.9 11


Hg

NDO.05 ND 0.05 ND 0.05 ND 0.05 ND 0.05 ND 0.05 ND 0.05 0.05 ND 0.05 ND 0.05

0.26 0.29 0.30 0.18 J 0.1 I 7.2 44.4 004 0.21 NDO.l Ni

Cr 0.52 0.55 I 0.46 0.79 1.95 0.27 0.25 2.7 1.0 1.0
Sb

en
lA

0.97 1.1 100 125 225 500 13 3.8 3.1


Se

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PAS-SCA-Ol COB-SCA-02 COB-SCA-03 PAS-LOB-Ot PAS-LOB-02 PAS-TOM-Ot PAS-TOM-02 PAS-CLA-Ol COB-CLA-02 PAS-COD-01
Sample

NDOA NDOA
ND 0.4

NDOA
004

NDOA NDOA
1.2 0.57

0.16 0.21 0.37 0.57 1.01 0.19 0.37 0.33


0.11

NDOA NDOA NDOA


5.2 0.71 0.43 0.40 11 2.9

NDOA
Ae:

0.31

NDOA
Tl ND 0.5 ND 0.5 ND 0.5 ND 0.5 ND 0.5 ND 0.5 ND 0.5 ND 0.5 ND 0.5 ND 0.5 -6-

NDO.5 NDO.5 NDO.5 NDO.5 NDO.5 NDO.5 NDO.5 NDO.5 NDO.5 NDO.5 Zn 53 55 51 140 I 180 65 81

1.24 0.89 1.30 5.7 5.2 3.6

4A
2.4 0.93 2.8

PAS-SCA-01 COB-SCA-02 COB-SCA-03 PAS-LOB-01 PAS-LOB-02 PAS-TOM-Ol PAS-TOM-02 PAS-CLA-01 COB-CLA-02 PAS-COD-O!

NDO.1 NDO.1 NDO.1 3.3 5.2 4.8 IDA 0.51 0.21 NDO.1

74
28 45

Dioxins The foJlowing tables display the dioxin analysis results for each composite sample. The codes described above still apply. The results are expressed as parts per trillion (ppt).

Sample ill
Compound 2378-tcdf 12378-pecdf 23478-pecdf 123478-hxcdf 123678-hxcdf 234678-hxcdf 123789-hxcdf 1234678-hpcdf 1234789-hpcdf ocdf 2378-tcdd 12378-pecdd 123478-hxcdd 123678-hxcdd 123789-hxcdd 1234678-hpcdd ocdd Total TEQ
(ND=O)
,

PAS-COD-Ol
DL(ng!K2) 0.11 0.25 0.25 0.25 0.25 0.25 0.25 0.5 0.5 0.5 0.10 0.25 0.25 0.25 0.25 0.5 0.5

PAS-LOB-Ol 0.59 <DL 0.48 <DL <DL <DL <DL <DL <DL 0.47 <DL <DL <DL <DL <DL 0.61 1.24 0.31 0.85 0.27 49.0

PAS-LOB-02 0.71 <DL 0.63 <DL <DL <DL <DL <DL <DL 0.33 <DL <DL <DL <DL <DL . 0.55 2.66 0.39 0.94 0.25 51.3

1.41 <DL 1.03 <DL <DL <DL <DL 0.48 <DL 3.25 0.14 0.19 <DL <DL <DL 1.33 5.67 1.00 1.20

Total TEQ (N])=DL) %Lipids Sample Weight


(g)

3.50 52.1

Sample ill
Compound 2378-tcdf 12378-pecdf 23478-pecdf 123478-hxcdf 123678-hxcdf 234678-hxcdf 123789-hxcdf 1234678-hpcdf 1234789-hpcdf DL(nl!!K1!) 0.11 0.25 0.25 0.25 0.25 0.25 0.25 0.5

PAS-CLA-Ol 0.95 <DL 0.51 <DL <DL <DL <DL <DL <DL -7-

COB-CLA-02 1.33 <DL 0.42 <DL <DL <DL <DL <DL <DL

PAS-SCA-Ol <DL <DL <DL <DL <DL <DL <DL <DL <DL

0.5

,.--.

oedf 2378-tcdd 12378-peedd 123478-hxedd 123678-hxedd 123789-hxedd 1234678-hpedd oedd Total TEQ
(ND==O)

0.5 0.10 0.25 0.25 0.25 0.25 0.5 0.5

0.35

0.43

0.63

<DL <DL <DL <DL <DL <DL


1.33 0.35 0.90 0.64 50.8

<DL <DL <DL <DL <DL <DL


1.85 0.34 0.90 0.70 50.0

<DL <DL <DL <DL <DL <DL


1.06 0.00 0.69 0.50 50.7

Tota) TEQ (ND=DL)

%Lioids
Sample Weight
(g)

=:=J
\

Sample ill

COB-SCA-02
DL(n~)

COB-SCA-03

COIDoound
2378-tcdf 12378-pecdf 23478-peedf 123478-hxedf 123678-hxedf 234678-hxcdf 123789-hxcdf 1234678-hocdf 1234789-hocdf ocdf 2378-tcdd 12378-pecdd 123478-hxcdd 123678-hxcdd 123789-hxcdd 1234678-hocdd ocdd Total TEQ
(ND=O)

0.11 0.25 0.25 0.25 0.25 0.25 0.25 0.5 0.5 0.5 0.10 0.25 0.25 0.25 0.25 0.5 0.5

<DL <DL <DL <DL <DL <DL <DL <DL <DL


0.51

<DL <DL <DL <DL <DL <DL <DL <DL <DL


0.37

<DL <DL <DL <DL <DL <DL


0.95 0.00 0.69 0.32 50.2

<DL <DL <DL <DL <DL <DL


0.66 0.00 0.69 0.34 49.8

Total TEQ (ND=DL)

%Lioids
Sample Weight
(g)

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T oma JI ey Resu JtS Sample ill


Compound 2378-tcdf 12378-pecdf 23478-pecdf 123478-hxcdf 123678-hxcdf 234678-hxcdf 123789-hxcdf 1234678-hpcdf 1234789-hpcdf ocdf 2378-tcdd 12378-pecdd 123478-hxcdd 123678-hxcdd 123789-hxcdd 1234678-hpcdd ocdd Total TEQ (ND=O) Total TEQ (ND=DL) %Lipids Sample Wei2bt (2) DUnVl\.2) 0.55 1.25 1.25 1.25 1.25 1.25 1.25 2.50 2.50 2.50 0.50 1.25 1.25 1.25 1.25 2.50 2.50

PAS-TOM-01 10.6 1.65 4.33 1.06 2.33 1.41

PAS-TOM-02 15.6 1.33 7.85 0.95 3.57 2.26

<DL <DL <DL


1.35 1.08 2.79 1.16 6.09 1.35 8.33 12.6 8.60 8.75 14.2 10.1

<DL <DL <DL


2.21 1.52 3.66 1.21 7.95 1.88 9.41 14.3 12.6 12.8 20.8 10.0

Dioxin Totals PAS-COD-Ol PAS-LOB-01 0.26 0.15 2.17 0.95 1.66 1.95 1.87 2.51 PAS-LOB-02 0.36 0.20 1.85 1.47 1.53 2.37 2.19 3.62 PAS-CLA-Ol 0.42 0.31 2.42 2.06 1.79 2.14 1.65 3.05 COB-CLA-02 0.21 0.18 2.31 .1.85 2.01 2.34 1.15 2.66

TeDF TeDD peeDF peeDD RxCDF RxCDD HpCDF HpCDD

0.42 0.53 3.22 2.61 2.08 1.88 2.49 3.85

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PAS-SCA-01

COB-SCA-02 0.09 0.14 1.75 1.86 2.06 2.97 1.21 2.01

COB-SCA-03 0.17 0.21 1.51 2.36 2.31 3.36 0.95 1.66

PAS-TOM-O 1 I PAS-TOM-02 63.2 18.2 35.9 19.6 23.5 42.8 2.31 14.8 58.3 21.6 43.8 31.2 31.4 51.7 1.65 16.2

TCDF I TCDD PeCDF PeCDD HxCDF HxCDD HpCDF HpCnn

0.13 0.21 1.61 1.47 1.85 1.33 0.76 1.15

DISCUSSION
In the following discussion an attempt is made to compare the results of this study with results from other state and regional dioxin and heavy metal testing programs. Unfortunately we have not been able to identify studies which used the exact species that we did in the case of all contaminants. We acknowledge that comparing results from a scallop to a mussel for example is not strictly appropriate. However, we have made some of these comparisons in order to fonn an initial general context. This study has established a baseline for dioxin and heavy metals in clams, cod, lobster and scallops for the Passamaquoddy region and in future studies better comparisons will be able to be made.

Dioxin
There are 75 different isomers of dioxin, the most toxic of which is the cWorinated 2,3,7,8TCDD isomer. Only seven of the 75 cogeners are thought to have dioxin-like toxicity. There are 135 individual furan compounds. Of these, only 10 are thought to have dioxin-like toxicity. (Horsley and Witten, Inc., 1998) "Dioxins/furans are highly persistent in the environment, have a strong affinity for fine grained sediments and accumulate in biological tissue. These contaminants accumulate in fish in proportion to the body lipid content and the age of the animal. PCDDs are particularly resistant to biological breakdown, concentrate in fatty tissues and are not readily excreted. Consequently, repeated exposures can rapidly increase body burdens." (Horsley and Witten, Inc., 1998) There are no uses for dioxin, it is a waste product created from industrial processes. Dioxin is a probable human carcinogen. (Dioxin Reassessments) In Maine, the only continual testing program for dioxin is carried out by the Dioxin Monitoring Program (DMP). This program is responsible for yearly sampling below at least 12 known or likely sources of dioxin releases to the environment. There has been a health advisory in Maine on the consumption oflobster tomalley because of dioxin contamination since 1994. (Mower, 1996)

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Conclusions When comparing the results from lobster meat and tomalley samples in the Passamaquoddy study with the Maine Dioxin Momtoring Program (DMP), the levels of dioxin appear to be very similar. The following charts (Figure A and B) display levels of dioxin compounds in lobster meat and tomalley samples collected under the Maine program and under the Passamaquoddy study. Each label has a two digit code for the year the sample was collected and a three letter code representing the site where it was collected. The following site codes apply: BBH BRK COR KRP SCB SCR PAS Brave Boat Harbor, Kittery (DMP) Brooklyn (DMP) Corea (DMP) Kennebec River Estuary (DMP) Saco Bay (DMP) S1. Croix Estuary (DMP) Passamaquoddy Bay (Passamaquoddy study)

Figure A: Levels oftbe dioxin compound TCDF in lobster meat expressed as parts per trillion.

0.8 0.7 0.6 .

0.5 0.4

93SCB

94BBH

94KRP

94SCB

98PAS

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Figure B: Levels of the dioxin compound TCDD in lobster tomalley expressed as parts per triJlion.

93KRP 935GB 94BBH 94KRP 945GB 95BRK 95KRP 96COR 96KRP 965CR 98PAS

The scarcity of data on the levels of dioxin in cod, scallops, or clams makes it difficult to say with certainty if the levels observed in the Passamaquoddy study are cause for concern. Further testing on these organisms as well as lobster should be undertaken in the future. Trace Elements The results of this study describe levels of heavy metals found in cod, scallops, clams, or lobsters in the Passamaquoddy Bay region. The data have been compared with several state, regional, and national studies of chemical contaminants in fish and shellfish in order to compare the levels of contaminants found in this region to other areas and studies. These studies include the Environmental Protection Agency (EPA) National Study of Chemical Residues in Fish, the Maine Department of Environmental Protection Surface Water Ambient Toxic Monitoring Program (SWAT), the Gulf of Maine Council Gulf Watch Program, and NOAA National Status and Trends Program. The following discussion will detail the results of these comparisons for each species tested.
It is beyond the scope oftrus project to identify sources of the following pollutants in the Passamaquoddy Bay region. Points of origin of metals in the natural environment are widely varied and may include historical or contemporary industrial outputs, naturally occurring background levels, atmospheric deposition or other sources.

Arsenic Arsenic is a human carcinogen that is wjdespread in the environment. Seafood normally contains arsenic in the order of milligrams per kilogram however, most of it is in an organic fonn that is far less toxic than inorganic arsenic. The highest concentrations of arsenic are found in bottom feeding fish and crustaceans. Lobsters, specifically, are known to store arsenic. (Adams, 1993a; GulfofMaine Land Based Pollution Sources) The Passamaquoddy study reports whole arsenic levels, not broken down into organic/inorganic munbers.

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The NOAA National Status and Trends Program Benthic Surveillance Project samples species of bottom dwelling marine finfish and analyzes the levels of certain heavy metals in their tissues. There are nine sites in Maine where sampling occurs for this program. Species of fish collected include longhorn sculpin and winter flounder. Data collected from these sites from 1984-1992 reports a minimum average value of2.35 ug/g and a maximum average value of 14.92 ug/g for arsenic. (Hannon eta1.; 1998) The Passamaquoddy study found whole fish concentrations in cod of 11 ug As/g (Table 1) which is about average. To make a proper comparison, however, cod should be compared to other cod. Our data may be the first such analysis on cod. Table 1: Comparisons of trace element levels in marine finfish from the Passamaquoddy study and the National Status and Trends program. AH data are expressed in ug/g dry weight. Passamaquoddy NS&TMIN NS&TMEAN NS&TMAX

MEAN
Silver Arsenic Cadmium Chromium Copper Mercury Nickel Lead Selenium Zinc
ND

11
ND 1 3.1 0.31 ND ND 2.8 45

0.13 2.35 0.31 0.16 2.5 0.05 0.09 0.21 3.53 78.1

0.69 8.16 1.78 0.5 20.0 0.25 0.42 1.6 5.7 126.9

1.59 14.92 4.51 0.87 68.98 0.42 1.75 8.22 9.93 192

NOAA National Status and Trends Program Mussel Watch project samples mollusks and analyzes the levels of heavy metals in their tissues. Arsenic was measured throughout the United States from 1986-1993. The mean As concentration found during this program in mollusk tissue was 9.3 ug/g. (O'Connor and Beliaefl) In the Passamaquoddy study, As concentrations in clams averaged 5.5 uglg and in scallops 5.0 uglg, well below the mean concentration found by the Mussel Watch program. The 1995 Maine SWAT program report shows an average total As concentration in lobster meat along the coast of 19 uglg. The average arsenic concentration in lobster meat in the Passamaquoddy study was 51.5 ug/g, exceeding the SWAT average by a large amount. The SWAT program average concentration of As for lobster tomalley was 16.75 ug/g. (Sowles, 1997) Lobster tomalley in the Passamaquoddy study had an average As concentration of 26 ug/g, again exceeding the SWAT program findings. (Figure 1)

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Figure 1: Comparison of average concentrations of Arsenic in lobster meat and tomalley in the Passamaquoddy study and the S\VAT program. All values are expressed in ug/g.

60

50
40

30

Passamaquoddy

o SWAT

Lobster Meat

Lobster Tomalley

Beryllium Berylliwn is a naturally occurring chemical component of certain kinds of rocks. It is generally released into the environment through the incineration of fossil fuels and primarily has negative effects on the lungs. (Public Health Statement, 1988)
BerylJiwn was not detected in any of the samples analyzed during the Passamaquoddy study.

Cadmium Cadmiwn is a carcinogen which bioacclliDulates in fish and shellfish. In theUS, the average person eats food with about 30 micrograms of cadmium in it each day. It accumuJates in the body and the concentration increases with age. (Adams, 1993b and GulfofMaine Land Based Pollution Sources)
Cadmiwn was not detected in the whole body cod sample in this study. (Table 1) NOAA Mussel Watch data from 1990 records a geometric mean value for cadmium in mollusks sampled from Gulf of Maine locations of 1.1 uglg and a high value for these same locations of 1.52 ug/g. The high value is detennined by adding one standard deviation to the geometric mean. Levels of cadmium in mussels from 23 Maine reference stations had an average value of 1.75 uglg and a high value of3.14 ug/g. The high value for the Maine reference stations is the arithmetic mean plus three times the standard deviation. The Gulfwatch program was established by the Gulf of Maine Council on the Marine Envirorunent to use the blue mussel as an indicator of organic and inorganic contamination in the envirorunent. 1995' Gulfwatch data reports a geometric mean value of 1.6 uglg of cadmium in mussels. (Chase et aI, 1996) Cadmium concentrations in clams in the Passamaquoddy study averaged .31 uglg while levels in scallops averaged .28 ug/g. These results appear to be low. (Figure 2)

14 -

Figure 2: Comparison of average concentrations of Cadmium in shellfish. All values are expressed in ug/g dry weight.

1.8 1.6 1.4 1.2


1

0.8

0.6
0.4

0.2

o
Pass. Clams Pass. Scallops Mussel Watch
ME Ref. Stations

Gulfwatch

In the Maine SWAT program, average concentrations of cadmium in lobster meat were found to be 0.15 uglg. The average Cd concentration in the Passamaquoddy study was similar at 0.14 uglg. The SWAT program also showed an average Cd concentration of7.69 uglg in lobster tomalley. (Sowles, 1997) Lobster tomalley in the Passamaquoddy study exhibited a mean Cd concentration of25.8 uglg, which is higher than the SWAT findings.

Chromium Chromium is an essential trace element in humans and virtually all foods contain chromium at levels up to 0.5 ppm. Sources ofCr in food include meats, mollusks, and crustaceans, however, finfish are a poor source of dietary Cr. Surveys of contaminants in fish and shellfish (conducted by FDA and NMFS) have found mean levels ofCr ranging from 0.1 ppm to 0.9 ppm wet weight. (Adams, 1993c)
The NOAA National Status and Trends Benthic Surveillance program found a minimum average chromium concentration of 0.16 uglg and a maximum average concentration of 0.87 uglg in fish at nine Maine sites. (Hannon et aI, 1998) The chromium concentration for cod in the Passamaquoddy study is 1.0 uglg. (Table 1) The Mussel Watch program found a geometric mean value of Cr in mussels of 1.39 uglg and a high value of2.78 uglg. The reference mean reported value for Cr at Maine reference stations was 1.53 uglg while the reported high value was 3.51 uglg. The Gulfwatch program found an average concentration of 1.9 uglg Cr in mussels in the Gulf of Maine. (Chase et aI, 1996) In comparison, the Passamaquoddy study found an average Cr concentration of 1.85 uglg in clams. The average level of Cr in scallops in this study was 0.51 uglg. (Table 2)

- 15 -

Table 2: Comparisons of trace element levels in marine shellfish between the Passamaquoddy study, NOAA Mussel Watch, Gulfwatch, and Maine Reference Stations. All values are averages expressed in uglg dry weight. Gulfwatch Passamaquoddy Mussel Passamaquoddy Watch Clams Scallops 0.09 0.36 0.22 ND Silver 1.6 0.31 0.28 1.1 Cadmium 1.9 1.85 1.39 0.51 Chromium 7.9 10.3 8.4 1.2 Copper 0.39 0.13 0.22 0.25 Mercury 1.3 1.18 6.95 ND Nickel 3.2 2.97 0.89 ND Lead 97 51 53 92 Zinc

The average concentration of Cr reported under the 1995 SWAT program for lobster meat was 0.41 ug/g. The mean concentration of chromium (1.37 ug/g) in lobster meat found in the Passamaquoddy study was higher. The levels of Cr in lobster tomalley tested under the SWAT program was shown to be 0.23 uglg on average. (Sowles, 1997) The average value ofCr in tomalley in the Passamaquoddy study were similar at 0.26 uglg.
Copper Copper is a naturally occurring essential element commonly found in many foods. Copper accumulates in the liver and may disrupt that organ's metabolism. (Public Health Statement, 1990)

The NOAA NS&T Benthic Surveillance program found a minimum average concentration of 2.5 uglg of copper and a high value of 68.98 uglg in sculpin and flounder. The average eu concentration from these nine sites is 20.0 uglg. (Hannon et aI, 1998) In contrast, the concentration of copper in whole body cod in the Passamaquoddy study is 3.1 uglg. (Table 1) The Gulfwatch program found a geometric mean concentration of copper in mussels of7.9 uglg. The mean value ofCu in mussels found in the NOAA NS&T Mussel Watch program was 10.3 uglg with a high value of 11.6 uglg. The average concentration found at Maine reference stations for copper in mussels was 6.9 uglg and the high value found at these sites was 10.7 uglg. (Chase et aI, 1996) Cu concentrations in the Passamaquoddy study average 8.4 uglg in clams and 1.2 uglg in scallops. (Table 2) The Maine SWAT program found an average level of copper in lobster meat of 60.75 ug/g. The results of the Passamaquoddy study for copper in lobster meat showed a mean concentration of 112.5 ug/g. These results appear to be elevated in comparison with the rest of the state. Lobster tomalley tested under the SWAT program had an average concentration of 253.75 uglg. (Sowles, 1997) The average Cu level in tomalley in the Passamaquoddy study was higher at 362.5 ug/g. (Figure 3)

- 16 -

Figure 3: Comparison of average concentrations of Copper found in lobster during the Passamaquoddy study and the SWAT program. All values are reported in ug/g dry weight.

400 350 300 250 200 150 100 50


O~-

Passamaquoddy QSWAT

Meat

Tomalley

Lead Lead is an element with no nutritive value. Lead bioaccumuIates in fish and shellfish. The average daily dietary intake is 5-10 micrograms per person. Surveys of contaminants in shellfish have found mean lead levels ranging from 0.1 ppm- 0.8 ppm. Lead is particularly toxic to children and is a probable carcinogen. (Adams, 1993d)

No lead was detected in cod, scallops, or lobster during this study. The average lead concentration reported for the Maine reference stations is 2.6 uglg with a high value of6.0 uglg. The NOAA Mussel Watch program geometric mean value forPb is 2.97 ug/g and the high value is 6.75 uglg. Gulfwatch data for lead in mussels reports a mean level of 3.2 . uglg. In comparison, the Passamaquoddy results for Pb in clams average 0.89 uglg. (Figure 4)

- 17 -

Figure 4: Com parison of average concentrations of Lead in shellfish. All values are reported in uglg dry weight.

3.5
3

2.5
2 1.5
1

0.5

Pass. Clams Mussel Watch

ME Ref. Stations

Gulfwatch

Mercury Practically all mercury in fish tissue is in the fonn of methylmercury which is toxic to humans and animals. Mercury has been found in both fish and shellfish. It accumulates efficiently in the aquatic food web and predators have the highest concentrations. Fish consumption dominates the pathway for human and wildlife exposure to methylmercury. (Horsley and Witten, Inc., 1998; Young)

"Preliminary comparison of concentrations of mercury in mussels from Maine with the rest of the US indicate high concentrations and confirms similar data that Maine waters in general have abnormally high concentrations of mercury for North America. These levels appear to be associated with historical or recent industrial activity." (Horsley and Witten, Inc., 1998) The NOAA NS&T Benthic Surveillance program minimum average value for mercury in marine finfish in Maine is 0.05 ug/g with a maximum value of 0.42 ug/g. The average concentration for these sites between 1984 and 19..92 for Hg is 0.25 ug/g. (Harmon et aI, 1998) Similarly, the level of mercury found in cod in the Passamaquoddy study is 0.31 ug/g. (Table 1) The Mussel Watch geometric mean value for mercury is 0.13 ug/g with a high value of 0.31 uglg. The Gulfwatch program found an average level ofHg in mussels of 0.39 uglg. The mean concentration of mercury at the Maine reference stations is 0.12 uglg and the high value is 0.48 uglg. (Chase et aJ, 1996) In comparison, average mercury levels found in the Passamaquoddy study were 0.25 uglg for scallops and 0.22 uglg for clams. (Table 2) (Figure 5) - 18 -

Figure 5: Com parison of average and high concentrations of Mercury in shellfish. All values are reported in ug/g dry weight.

0.45 u - - - - - - - - - -

0.5

o0.4 .35
0.3

rn ~
I..l--------'

Mean

.High

0.25 0.2 0.15 0.1 0.05


O~~

tn E tn CO co_ a.. 0

en

tncoa.. ~

tn 0

.c.

tn

en

The SWAT program found average concentrations of mercury in lobster meat to be 0.83 uglg dry weight. The levels of mercury in lobster meat in the Passamaquoddy study averaged 0.79 uglg. Tomalley tested under the SWAT program exhibited an average mercury level of 0.33 ug/g. (Sowles, 1997) Results of the Passamaquoddy study for tomalley were similar, with a mean concentration of 0.28 ug/g.

Nickel Nickel is widely distributed in foods such as cereals, nuts, and cocoa. Surveys of contaminants in shellfish conducted by FDA and NMFS have found mean nickel levels ranging from 0.2 ppm2.2 ppm. (Adams, 1993e)
Nickel was not detected in the whole body cod sample or in the scallop samples under the Passamaquoddy study. Gulfwatch reports a geometric mean value of 1.3 uglg of nickel in mussels. The mean reference value for 23 Maine sites for Ni in mussels is 1.8 uglg and the high value is 2.9 uglg. The NOAA Mussel Watch program found a mean Ni level of 1.18 ug/g and a high value of 1.72 ug/g. The Passamaquoddy study reports a higher average Ni concentration of6.95 uglg in clams. (Figure 6)

- 19 -

Figure 6: Average concentrations of Nickel in shelJfish. All values are reported in uglg dry weight.

7
6

5
4

2
1

o
Pass. Clam Mussel Watch
ME Ref. Stations

Gulfwatch

The Passamaquoddy study found average Ni levels in lobster meat of2.96 uglg and in tomalley of 0.42 uglg. Nickel was not tested for under the SWAT program.

Antimony Antimony is a metalloid element that is a common urban air pollutant. Long tenn exposure to Sb may affect the blood and liver. (Young, 1992)
Antimony was not detected in any of the samples taken during the Passamaquoddy study.

Selenium Selenium is an essential nutrient that is toxic at high concentrations. Humans are exposed to Se in food and intakes range between 0.071 - 0.152 milligrams per person per day on average. Selenium amounts in fish are usually between 0.1 and 0.7 ppm. Seafood may contain the highest levels of Se of any food source. (Public Health Statement, 1989)
The NS&T Benthic Surveillance program minimum average level of Se is 3.53 uglg and the high value is 9.93 ug/g. The average level of Se in finfish between 1984 and 1992 is 5.7 ug/g. (Harmon et aI, 1998) The concentration ofSe in cod in the Passamaquoddy study is 2.8 ug/g. (Table 1) The NOAA NS&T Mussel Watch program monitored molluscan tissues around the United States for the presence of selenium between 1986 and 1993. The average concentration of Se in mollusc tissue during this time period is 2.5 ug/g. (O'Connor and Beliaeff) The Passamaquoddy study average concentration of Se in clams is 1. 7 uglg and in scallops is 1.14 ug/g.

- 20 -

The SWAT program reported average Se concentrations of2.65 ug/g for lobster meat and 2.63 ug/g for tomalley. (Sowles, 1997) The Passamaquoddy study results for Se exceed these amounts with levels averaging 5.45 ug/g for lobster meat and 4.0 ug/g for tomalley.
Silver Silver is a relatively rare metal that occurs naturally. It has no known physiologic function. (Faust, 1992)

Silver was not detected in cod or scallops under the Passamaquoddy study. The average concentration of silver in clam samples collected under the Passamaquoddy study (0.36 ug/g) was higher than the average concentration of Ag in mussels samples (0.09 uglg) collected in Maine and Eastern Canada under the Gulf Watch program. This result is also higher than the average concentrations of Ag found in the Mussel Watch program (0.22 ug/g) and the Maine reference sites (0.12 uglg). However, the Passamaquoddy average for Ag in clams is lower than the high values reported for these two studies (0.51 uglg and 0.4 uglg respectively). (Chase et al, 1996) The SWAT program average concentration of silver in lobster tomalley (3.32 uglg) was lower than the average concentration of Ag detected in tomalley during the Passamaquoddy study which was 7.6 ug/g. Silver was not detected in lobster meat during the SWAT study (Sowles, 1997), however an average concentration of 4.25 ug/g was found in lobster meat in the Passamaquoddy study.
Thallium Thallium metal and its compounds are highly toxic. The primary targets for T1 exposure are the nervous and reproductive systems. (Borges, 1994)

Thallium was not detected in any samples during the Passamaquoddy study.
Zinc

Zinc is an essential human element. Zinc is released into the environment through many human activities and can cause gastrointestinal problems. (Opresko, 1992) Zinc was not detected in scallop samples in the Passamaquoddy study. The Benthic Surveillance program found a minimum average level of78.1 uglg and a maximum average value of 192 ug/g of zinc in sculpin and flounder. (Harmon et aI, 1998) The concentration of Zn in cod in the Passamaquoddy study is 45 uglg well below the minimum concentration found in the NOAA study. (Table 1) The Passamaquoddy study found an average concentration of Zn in clams of 51 uglg and in scallops of 53 ug/g. These results are lower than the average concentrations found in the Gulfwatch program (97 uglg), the Mussel Watch program (92 ug/g) and the Maine reference stations (89 ug/g). (Chase et aI, 1996) (Figure 7) - 21 -

Figure 7: Average concentrations of Zinc in sbellfish. All values are reported in uglg dry weigbt.

100 90 80
70 60 50

40 30

20
10

o
Pass. Clam Pass. Scallop Mussel Watch ME Ref. Gulfwatch Stations

Zinc was found in lobster meat during the SWAT program at an average concentration of 127.5 ug/g. The average level ofZn in lobster meat found during the Passamaquoddy study was 160 ug/g. Tomalley analyzed in the SWAT program had an average level of54.25 ug/g. In the Passamaquoddy study Zn in tomalley averaged 73 uglg. (Sowles, 1997) Both lobster meat and tomalley levels in the Passamaquoddy study were lUgher that the SWAT program.

Conclusions Results of the trace element analysis indicates levels of thirteen heavy metals present in the marine environment in the Passamaquoddy region. Three elements: beryllium, antimony, and thallium, were not found at all. None of the pollutants were found to be high in Passamaquoddy scallops in comparison to the studies discussed in this report. Only nickel and silver levels appear to be high in clams in comparison to the same studies. However, as noted earlier, comparisons are made against blue mussels and not directly against clams which are known to be in more contact with sediment. Passamaquoddy cod samples were compared to the NOAA Benthic Surveillance program. These comparisons indicate that only the level of chromium is elevated, but again comparisons are to species other than cod. In comparing levels of trace elements in lobster meat and tomalley from the Passamaquoddy region with the Maine SWAT program, the Passamaquoddy values are higher in many cases. (Table 3) Specific contaminants which are higher include arsenic, cadmium, chromium, copper, selenium, silver, and zinc.

- 22-

Table 3: Comparisons of average trace element levels in lobster meat and tomaUey between the Passamaq uoddy study and the Maine SWAT program. All values are expressed in uglg dry weight. Lobster Meat Passamaquoddy 51.5 0.14 1.37 112.5 0.79 5.45 4.25 160 SWAT 19 0.15 0.41 60.75 0.83 2.65
127.5

Tomalley Passamaquoddy 26 25.8 0.26 362.5 0.28 4.0 7.6 73 SWAT 16.75 7.69 0.23 253.75 0.33 2.63 3.32 54.25

Arsenic Cadmium Chromium Copper Mercury Selenium Silver Zinc

RECOMMENDATIONS This report describes the levels of 13 heavy metals and dioxin in the tissues of four species of marine organisms. The data have been compared with the results of other studies that have looked at levels of these pollutants in the marine environment. The purpose ofthis report is to document levels of contaminants found in lobster, cod, clams, and scallops in the Passamaquoddy Bay region during this study. The report is not intended to address human health concerns relating to consumption of marine species. It is recommended that this data be reviewed independently by a human health risk assessor and that further, regular testing of these marine species be pertonned in order to establish baseline and monitor for changing levels. It would be infonnative to continually review the literature to find data on the species reviewed in this project. Finally, as funds permit, individual replicates or replicate composites would permit a better assessment of confidence around the means.

- 23-

REFERENCES
Adams, Michael A; Bolger, Michael; Carrington, Clark D.; Coker, Curtis E; Cramer, Gregory M.; DiNori, Michael 1.; and Dolan, Scott. 1993a. Guidance Documentfor Arsenic in Shellfish [Online]. US Food and Drug Administration. Available: http://vrn.cfsanJda.gov/-frfiguidas.html [2000, June 27]. Adams, Michael A; Bolger, Michael; Carrington, Clark D.; Coker, Curtis E; Cramer, Gregory M.; DiNori, Michael 1.; and Dolan, Scott. 1993b. Guidance Document/or Cadmium in Shellfish [Online]. US Food and Drug Administration. Available: http://vrn.cfsan.fda.gov/-frf/guidcd.html [2000, June 27]. Adams, Michael A; Bolger, Michael; Carrington, Clark D.; Coker, Curtis E; Cramer, Gregory M.; DiNori, Michael 1.; and Dolan, Scott. 1993c. Guidance Document/or Chromium in Shellfish [Online]. US Food and Drug Administration. Available: http://vm.cfsan.fda.gov/-frf/guidcr.html [2000, June 27]. Adams, Michael A; Bolger, Michael; Carrington, Clark D.; Coker, Curtis E.; Cramer, Gregory M.; DiNori, Michael 1.; and Dolan, Scott. 1993d. Guidance Documentfor Lead in Shellfish [Online]. US Food and Drug Administration. Available: http://vrn.cfsan.fda.gov/-frfi'guidpb.html [2000, June 27]. Adams, Michael A; Bolger, Michael; Carrington, Clark D.; Coker, Curtis E; Cramer, Gregory M.; DiNori, Michael 1.; and Dolan, Scott. 1993e. Guidance Documentfor Nickel in Shellfish [Online]. US Food and Drug Administration. Available: http://vrn.cfsan.fda.gov/-frfi'guidni.html [2000, June 27]. Beryllium. 1988. In Public Health Statement [Online]. Agency for Toxic Substances and Disease Registry. Available: http://www.atsdr.cdc.govrroxProfiles/phs8807.html [2000, June 27]. Borges, Tim and Daugherty, Mary Lou. 1994. Toxicity Summary for Thallium [Online]. Risk Assessment Information System. Available: http://risk.lsd.oml.gov/tox/profiles/thallium_CV1.shmtJ [2000, June 27]. Chase, Margo; Coomb, Karen; Crawford, Robert; Harding, Gareth; Hennigar, Peter; Jones, Stephen; Pederson, Judith; Robinson, William; Sowles, John; and Taylor, Darrell. 1996. Evaluation of Gulfwatch 1995: Fifth Year of the Gulf of Maine Environmental Monitoring Plan. Gulf of Maine Council on the Marine Environment. Copper. 1990. In Public Health Statement [Online]. Agency for Toxic Substances and Disease Registry. Available: http://www.atsdr.cdc.govrroxProfiles/phs9008.html [2000, June 27]. Dioxin documents. In Dioxin Reassessment [Online]. US Environmental Protection Agency. Available: http://www.epa.gov/ncealpdfs/dioxin/dioxreass.htm [2000, June 27]. - 24 -

Faust, Rosmarie A. 1992. Toxicity Summary for Silver [Online]. Risk Assessment Information System. Available: http://risk.lsd.ornl.gov/toxiprofiles/silver_CV1.shtml [2000, June 27]. Gottholm, B. William and Turgeon, Donna D. 1992. Toxic Contaminants in the GulfofMaine. National Oceanic and Atmospheric Administration, Rockville, Md. Gulfwatch. In GulfofMaine Environmental Monitoring Program [Online] Gulf of Maine Council on the Marine Environment. Available: http://www.gulfofmaine.org/library/gulfwatch/ [2000, June 27]. Harmon, Michelle R.; Gottholm, B. William; and Robertson, Andrew. 1998. A Swnmary of Chemical Contaminant Levels at Benthic Surveillance Project Sites (1984-1992). National Status and Trends Program. NOAA Technical Memorandum NOS ORCA 124. ' Horsley and Witten, Inc. 1998. Impacts ofContaminants on the Resources ofthe GulfofMaine. [Online]. Commission for Environmental Cooperation. Available: http://www.cec.org/statepage/Contam.htm [2000, June 27] Mierzykowski, Steven E. and Carr, Kenneth C. 1998. Environmental Contaminants in Fish and Mussels from Meddybemps Lake, the Dennys River, and East Machias River: Eastern Surplus Superfund Site, Meddybemps, Maine. U.S. Fish and Wildlife Service, New England Field Office, Special Project Report: FY98-MEFO-I-EC. Mower, Barry. 1996. Dioxin Monitoring Program. DEPLW98-14. Maine Department of Environmental Protection. Mussel Watch data. In NOAA's National Status and Trends Program [Online]. Available: http://spa. nos.noaa. gov/projects/nsandt/nsandt. html [2000, June 27]. O'Connor, Thomas P. and Beliaeff, Benoit. Recent Trends in Coastal Environmental Quality: Results from the Mussel Watch Project. National Status and Trends Program. NOAA. Opresko, Dennis M. 1992. Toxicity Summary for Zinc and Zinc Compounds [Online]. Risk Assessment Infonnation System. Available: http://risk.lsd.ornl.gov/toxlprofiles/zn.shtml [2000, June 27]. Selenium. 1989. In Public Health Statement [Online]. Agency for Toxic Substances and Disease Registry. Available: http://www.atsdr.cdc.govrroxProfiles/phs8921.html [2000, June 27]. Sowles, John; Mower, Barry; Davies, Susan; and Tsomides, Leon. 1997.1995 Surface Water Ambient Toxic Monitoring Program, Technical Report. DEPLW97-1. Maine Department of Environmental Protection. Total Arsenic (As). In GulfofMaine Land Based Pollution Sources [Online]. Available: http://sposerver.nos.noaa.gov/projects/gomaine/as.html [2000, June 27]. - 25 -

Total Cadmiwn (Cd). In GulfofMaine Land Based Pollution Sources [Online]. Available: http://sposerveLnos.noaa.gov/projects/gomaine/cd.html [2000, June 27].

u.s. Environmental Protection Agency. 1992a. National Study a/Chemical Residues in Fish
Volume 1. EPA 823-R-92-008a. Office of Science and Technology, Washington DC.

u.s. Environmental Protection Agency. 1992b. National Study ofChemical Residues in Fish
Volume 11. EPA 823-R-92-008b. Office of Science and Technology, Washington DC.

u.s. Environmental Protection Agency. 1995. Guidance for Assessing Chemical ContaminanJ
Data/or use in Fish Advisories Volume 1. EPA 823-R-95-007. Office of Water, Washington DC.
Young, Robert. Toxicity Summary/or Mercury [Online]. Risk Assessment Infonnation System. Available: http://risk.lsd.omJ.gov/tox/profiles/mercUTy_CV 1.shmtl [2000, June 27]. Young, Robert A. 1992. Toxicity Summary for Antimony [Online]. Risk Assessment Infonnation System. Available: http://risk.lsd.oml.gov/tox/profiles/antimony.shmtl [2000, June 27].

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VallejoCPR Graphic

Home Risks & Dangers Emissions Facts The Bechtel-Shell plants will bring a number of sources of pollution into Vallejo: The power plant The LNG ships The diesel-fueled dredgers, tugs and Coast Guard security vessels Helicopters The Power Plant According to Shell, the 900-megawatt power plant alone will release over 1,692 tons per year (that's 4.9 tons per day!) of smog-producing, asthma-aggravating greenhouse gasses and cancer-causing toxic pollutants into Vallejo's air. The following represent some of the emissions from the proposed power plant: 201.9 tons of Nitrogen Oxides (403,800 pounds) 876.3 tons of Carbon Monoxide (1,752,600 pounds) 41.7 tons of Volatile Organic Compounds such as Benzene (a known human carcinogen), Hydrocarbons (many known to cause cancer), and Reactive/Precursor Compounds (83,400 pounds) 129.6 tons of PM-10 (very detrimental to health, as these particulates readily lodge in the lungs and cause toxic effects; 259,200 pounds) 18.3 tons of Sulfur Dioxide (a criteria pollutant that causes acid rain; 36,600 pounds). These levels of contamination consider only the proposed power plant, and do not consider the transport ships, LNG offloading, regasification facility, dredging, pipelines, trucking, and/or accidents at the facility. Marine Vessel Emissions LNG tanker emissions and the emissions of other so-called "secondary sources" are a major health concern. These marine vessels are not subject to Bay Area or EPA emissions regulations, though they may be subject to CEQA review. So far, Bechtel-Shell have avoided any public discussion of the significant emissions from secondary sources, other than to say that they should not be regulated because they are not attached to the land, according to Shell's David Thomson. Unfortunately, unlike attempts to mitigate power plant emissions with 160-foot stacks, there is no way to redirect emissions from the vessels away from our town or our neighbors downwind. LNG Tanker Emissions The LNG tankers are powered by huge steam turbines, which are fueled by LNG, diesel and bunker fuel.

Shells David Thomson, a former LNG ship captain, stated that these tankers will burn 100 tons per day of fuel, three times per week during their 24-hour turnaround and offloading time at the south end of Mare Island. Diesel and bunker fuel make up 20 percent of that amount -- 3,120 tons. The total fuel burned from the LNG tankers alone would be: 100 tons per day, three days per week 156 days per year 15,600 tons per year Emissions from Dredgers, Tugs and Coast Guard Security Vessels Extensive and constant use of diesel-powered vessels will contribute significantly to the toxic emissions. Along with the LNG Tankers, these vessels contribute so-called "secondary emissions", which are not subject to EPA regulations, and use diesel, one of the dirtiest and most harmful of the commercial fossil fuels. Dredgers will contribute significantly to toxic emissions. Dredging to maintain the turning basin and offloading terminal for the LNG ships will be virtually constant because the Napa River produces a high amount of silt. In addition, massive dredging will be required to deepen ten miles of the Pinole Shoal. Multiple tugboats and Coast Guard security vessels will operate alongside the LNG tankers three days a week. UPDATE! Bechtel-Shell Admit Marine Vessel Emissions Will Exceed Power Plant Emissions! On November 13, 2002, David Stein from the Bay Area Air Quality Management District addressed the City's Health and Safety Subcommittee. Mr. Stein revealed that he had been given emissions data by Bechtel-Shell for one tanker and one tugboat, and that those emissions alone would exceed the power plant emissions! Curiously, this is an underestimate of the actual emissions for the marine vessels because Bechtel-Shell left out the multiple tugboats, the coast guard escort vessels, and the constant use of diesel-fueled dredgers. Diesel Risks and Lack of Regulation of Marine Vessel Emissions There are no standards for foreign-flag vessels entering U.S. ports -- all LNG ships are foreign flag. The United States Environmental Protection Agency (EPA) is considering extending certain regulations to foreign-built vessels, but is receiving heavy opposition from the shipping industry. The EPA recognizes that marine vessel emissions are a major concern and is currently proposing regulations that would require all future marine vessels built in the U.S. to comply with emissions standards. Diesel particulate matter is a huge modern health problem, accounting for 70 percent of the total toxic risk to Californians from air pollution," according to the Bay Area Air Quality Management District. Diesel has recently been added to Californias Proposition 65 hazardous substance list, and garnered attention after the release of studies in early 2002 confirming that diesels toxic particulates cause lung cancer and other respiratory diseases. More on diesel pollution Emissions Mitigation

One of Bechtel-Shell's recent ad campaigns was designed to lessen concerns about emissions from their proposed project. They offer the solution of emissions offsets that will allegedly Clear the Air in Vallejo." The problem with this ad campaign is that it omits a critical fact that most Vallejo and Solano County residents would need to know -- that the impact of emissions trading on air pollution will be regional, not local. While the air may become cleaner elsewhere, it will become dirtier in Vallejo. To begin operating their power plant in Vallejo, Bechtel-Shell would be required to trade "emissions credits" with other polluting businesses. These businesses could be located anywhere in the huge 600square mile, nine-county Bay Area Air Quality Management District. This would include counties as far away as Santa Clara and San Mateo. Unfortunately, because there are no "point sources" of pollution in our area that can be scaled back enough to compensate for the massive increase in pollutants from the power plant alone, Bechtel-Shell will have to go elsewhere to look for a business that will stop polluting so they can start polluting here. Bechtel-Shell would pay these businesses to pollute less to compensate for increasing Vallejo's air pollution. No Mitigation of the Massive Marine Vessel Emissions Even more egregious is Bechtel-Shell's concealment of the fact that they would not be required to mitigate the massive amounts of pollution from the marine vessels. This is because of the regulatory structure - as long as the power plant emissions falls below a certain level, they local regulators will not consider emissions from the marine vessels - despite the fact that they will exceed the power plant's. So while emissions will be lowered in that other community, the Bay Area will suffer a net increase in emissions - because only the power plant emissions would be mitigated - the ships and boats will cause our overall Bay Area pollution to increase. And here, in Vallejo and Solano County, we will suffer from a major local increase in pollution. Related Links: Emissions Banking Information Detailed discussion of Vallejo's Air Quality and impact of the project emissions Environmental Scientist Gayle Edmisten Watkin

2002 maggdog communications Photos courtesy of Michael Halberstadt, Joyce Scharf and Friends of VallejoCPR Page Last Updated Jan 8, 2003 Email: info@VallejoCPR.org

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W Lin, N Zhang, A Gu - Energy, 2010 - Elsevier ... To reduce the air pollution brought about by waste emission from fuel cars, China is positively accelerating the research on LNG vehicles. ... Some new standards have been proposed while some previous standards have been revised to include LNG related topics. ... Cited by 25 Related articles Get at CISTI All 4 versions Cite

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The Assessment of Combustion Related Hazards Associated with the Spillage of LNG
JA Eyre, MJ Pikaar, JL Rosenfeld - International Conference on Liquefied , 1900 - trid.trb.org ... and Share. Title: THE ASSESSMENT OF COMBUSTION RELATED HAZARDS ASSOCIATED WITH THE SPILLAGE OF LNG. Accession Number: 00650113. Source Agency: Maritime Technical Information Facility. Abstract: In ... Cited by 2 Related articles Cite More

Thermodynamic-analysis-based design and operation for boil-off gas flare minimization at LNG receiving terminals
C Liu, J Zhang, Q Xu, JL Gossage - Industrial & Engineering , 2010 - ACS Publications ... Related Content. Optimization of the Operation of Boil-Off Gas Compressors at a Liquified Natural Gas Gasification Plant Industrial & Engineering Chemistry Research: ... Liquefied natural gas (LNG) is the most economical way of transporting NG over long distances. ... Cited by 4 Related articles All 5 versions Cite

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Marine transportation of LNG (liquified natural gas) and related products


RG Wooler - 1975 - osti.gov ... Title, Marine transportation of LNG and related products. ... LIGHTNING; NUCLEAR POWER; OIL SPILLS; REVIEWS; SAFETY ENGINEERING; STEAM GENERATION; STEAM GENERATORS; TRANSPORTATION SYSTEMS; WATER POLLUTION; BOILERS; DOCUMENT ... Cited by 1 Related articles All 4 versions Cite More

LNG: truck fuel of the future?


T Blakemore - TRANSPORT ENGINEER, 1997 - trid.trb.org ... It is inherently cleaner than any other fossil fuel, because it produces less carbon-related pollution when burned. Its high energy density means that its vehicles do not have the short range of other vehicles using alternative fuels. The LNG fuel tank is much lighter than the CNG ... BL Direct Cite More

Analysis possibilities of cost reduction related to boil-off fuel gas being carried on LNG gas carriers
M Giernalczyk - Journal of KONES Selected full texts, 2007 - baztech.icm.edu.pl ... However, the mentioned way causes losses of cargo and air pollution. ... Moreover, author presents further design development of LNG carriers ... Possibilities of cost reduction related to boil-off fuel gas, the Moss RS standard setup for gas reliquefaction system, example of dual fuel ... Cite More
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M Tampier, M Pattenden, P Probe - 2006 - pollutionprobe.org ... gas combined cycle plants. Such pricing becomes even more attractive when one factors in externalities, such as the environmental and health costs related to pollution from the use of fossil fuels. In addition, as green power ... Related articles All 5 versions Cite More

Risks Related to the Maritime Transportation of Oil and Gas (mainly Crude oil, LPG, and LNG)-A Conceptual Study and Empirical Outlook on the Baltic Sea and UK
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Technical Evaluation of LNG Engines for Heavy Duty Vehicles.


K NARUSAWA, T SATO, S HORI - Comprehensive , 2000 - sciencelinks.jp ... 2) Pollution reduction and efficiency improvement of LNG engine (direct fuel injection system, and pre-mixed fuel injection system ... of bench test and examination based on simulation model, we were able to confirm probability of practical application of LNG engine ... Related Articles ... All 2 versions Cite More

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Marine Chemistry 90 (2004) 91 105 www.elsevier.com/locate/marchem

Speciation and bioavailability of mercury in well-mixed estuarine sediments


Elsie M. Sunderland a,b,*,1, Frank A.P.C. Gobas a, Andrew Heyes c, Brian A. Branfireun d, Angelika K. Bayer d, Raymond E. Cranston e, Michael B. Parsons e
School of Resource and Environmental Management, Simon Fraser University, Burnaby, British Columbia, Canada V5A 1S6 b Office of Science Policy (8104S), Office of Research and Development, United States Environmental Protection Agency, 1200 Pennsylvania Ave. N.W., Washington, DC 20007, USA c Chesapeake Biological Laboratory, University of Maryland Center for Environmental Science, University System of Maryland, P.O. Box 38, Solomons, MD 20688-0038, USA d Department of Geography, University of Toronto at Mississauga, 3359 Mississauga Road North, Mississauga, Ontario, Canada L5L 1C6 e Natural Resources Canada, Geological Survey of Canada (Atlantic), Bedford Institute of Oceanography, P.O. Box 1006, Dartmouth, Nova Scotia, Canada B2Y 4A2 Received 12 June 2003; received in revised form 19 November 2003; accepted 16 February 2004 Available online 7 June 2004
a

Abstract Despite regulations controlling anthropogenic mercury sources in North America, high levels of mercury in coastal fish and shellfish are an ongoing problem in Maritime Canada and the Northeastern United States. This study presents sediment core data from a macrotidal estuary located at the mouth of the Bay of Fundy showing stratigraphic profiles of total and methylmercury concentrations and potential methylation rates measured using stable mercury isotopes. The results show that in contrast to the expected methylmercury profile typically observed in unmixed sediments, methylmercury production occurs throughout the estimated 15-cm-thick active surface layer of these well-mixed sediments. The resulting large reservoir of methylmercury in these sediments helps to explain why mercury concentrations in organisms in this system remain high despite emissions reductions. Current management policies should take into account the expected delay in the response time of wellmixed estuarine systems to declines in mercury loading, considering the greater reservoir of historic mercury available in these sediments that can potentially be converted to methylmercury and biomagnify in coastal food chains. D 2004 Elsevier B.V. All rights reserved.
Keywords: Methylmercury; Estuaries; Enrichment factor; Sediment burial; Bay of Fundy

* Corresponding author. Office of Science Policy (8104R), Office of Research and Development, United States Environmental Protection Agency, 1200 Pennsylvania Ave. N.W., Washington, DC 20007, USA. Tel.: +1-202-564-6754; fax: +1-202-565-2925. E-mail address: sunderland.elsie@epa.gov (E.M. Sunderland). 1 This research was conducted while Dr. Sunderland was a graduate student at Simon Fraser University and reflects the authors personal views. This study is not intended to portray policies or views of the U.S. EPA. 0304-4203/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.marchem.2004.02.021

1. Introduction Mercury emissions from anthropogenic sources in Maritime Canada and the Northeastern United States have declined by more than 50% from peak levels in the 1970s as a result of pollution control measures (Sunderland and Chmura, 2000). However, there is no

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evidence of similar declines in the concentrations of mercury in marine birds, fish and shellfish from the Bay of Fundy region of Canada, which is a catchment for atmospheric mercury contamination from industrialized regions of Central Canada and the United States (Chase et al., 2001; Evers et al., 1998; NESCAUM et al., 1998). Methylmercury (MeHg) levels in fish and invertebrates surpass Environment Canadas tissue residue guideline of 0.033 ppm (0.16 nmol g 1) for the protection of all aquatic life (CCME, 2000; Chase et al., 2001), and at the highest trophic levels, total mercury concentrations exceed the Health Canada guideline of 0.5 ppm (2.5 nmol g 1) for safe consumption by humans (Gaskin et al., 1973, 1979; NESCAUM et al., 1998). A better understanding of the relationship between concentrations in organisms and emissions reductions is needed to develop effective strategies for reducing potential human health impacts of mercury in the Bay of Fundy. The conversion of inorganic mercury to methylmercury is a critical process affecting the relationship between mercury inputs and concentrations in biota. The majority of mercury released as a byproduct of human activities and present in the environment is inorganic mercury, but only the most toxicorganic form, MeHg, bioaccumulates in organisms (Bloom, 1992). There is considerable evidence that production of MeHg is principally a biologically mediated reaction carried out by sulfate-reducing bacteria in marine sediments (Benoit et al., 1999; King et al., 1999). Because these microbes are anaerobes, benthic sediments in coastal systems often provide the most suitable environment for MeHg production (Choi and Bartha, 1994). Coastal sediments also act as a reservoir for past and present mercury inputs due to the affinity of inorganic mercury species for particulates and organic matter (Gagnon et al., 1996; Mason and Lawrence, 1999). Two of the main factors determining the exposure of coastal organisms to mercury are therefore: (i) the amount of inorganic mercury in the sediments that is converted to MeHg; and (ii) the geochemical conditions that affect the activity of methylating bacteria and the availability of inorganic mercury for methylation. To gain insight into the temporal response of mercury concentrations to changes in mercury inputs, it is important to understand both of these factors.

The Bay of Fundy has the worlds largest tides, reaching up to 16 m at the mouth of the bay (Gregory et al., 1993). Tseng et al. (2001) observed that mixing of sediments in the fluid mud profile of a turbid macrotidal estuary in France creates a distinct geochemical environment that facilitates the activity of microbial populations converting inorganic mercury to MeHg. Based on these data, we hypothesized that physical mixing in the Bay of Fundy will change the geochemical characteristics of the surface sediments and increase the depth of the active sediment layer where methylation takes place. The active sediment layer is operationally defined in this study as sediments that can potentially exchange mercury with the water column and buried sediments through resuspension, diffusion and burial. Thus, the thickness of the active layer is a function of the depth of biological mixing and the depth of physical mixing/continual reworking (Boudreau, 2000). The relatively thick active sediment layer in the Bay of Fundy may effectively increase the amount of total and methylmercury in the sediment compartment that is available to organisms, as compared to other more static estuarine systems. In this paper, the effects of sediment mixing are explored by investigating ambient profiles of total mercury and MeHg and potential MeHg production rates measured in sediment cores from contrasting sites at the mouth of a freshwater tributary and in well-mixed regions of a coastal embayment located at the mouth of the Bay of Fundy. Evidence is presented that demonstrates the effects of mixing on the depth and geochemistry of the active sediment layer in this system. The implications for mercury uptake at the base of the food chain and the temporal response of this system to reductions in anthropogenic mercury emissions are discussed.

2. Methods 2.1. Study site Sediment cores were collected in Passamaquoddy Bay and the St. Croix River Estuary between May and August 2001 (Fig. 1). Passamaquoddy Bay is a semienclosed macrotidal estuary located at the mouth of the Bay of Fundy. The mean tidal range in Passamaquoddy Bay is 6 8 m, making it a turbid, tidally

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Fig. 1. Map of the study area showing sampling locations for gravity cores, push cores and isotope cores.

dominated system (Gregory et al., 1993). The St. Croix River is the main freshwater inflow to Passamaquoddy Bay and runs along the border between Canada and the United States. Related investigations (Sunderland, 2003) show that total mercury concentrations in surface sediments in Passamaquoddy Bay and the St. Croix River Estuary range between 50 and 750 pmol g 1 dry weight, with the highest concentrations found at the head of the St. Croix River Estuary. 2.2. Field sampling 2.2.1. Push cores Eight 15-cm-long surface sediment push cores were obtained from a large volume, modified Van Veen grab sampler at selected locations in May and August 2001 using acid-washed PVC/Plexiglas core

tubes (Fig. 1). Duplicate cores were collected at sites SC-1, PB-3 and PB-7 and analyzed for total mercury and MeHg. Push cores collected at sites PB-7 and PB8 were only analyzed for total mercury. All cores were extruded at 2-cm intervals in the laboratory on shore, and all samples were frozen until analysis. Sulfide concentrations in the wet sediments of push core subsamples were analyzed using an ion-specific electrode after addition of sulfide antioxidant buffer according to the method outlined by Wildish et al. (1999). Redox potential (Eh) was measured at the sediment surface of gravity core and push core sampling locations using an Orion platinum redox electrode and a calomel reference electrode. 2.2.2. Gravity cores Multiple gravity cores (n = 20) were collected to characterize the geochemical profile of sediments in

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Passamaquoddy Bay and the St. Croix River Estuary using a 1.5-m-long gravity corer (Fig. 1). Gravity cores were sectioned into 5-cm vertical intervals to a depth of 20 cm, after which they were divided into 10cm increments. Sediments were placed in polyethylene sample containers and cooled at temperatures < 4 jC to minimize chemical transformations following extrusion. Vertical gradients of dissolved ammonium and sulfate were measured in sediment porewaters within 24 h of sampling to estimate present-day sediment accumulation rates following the method developed by Cranston (1991, 1997). This method estimates sediment burial rates within a factor of 2 of radiometric dating (Cranston, 1991) and is particularly useful in erosion and transport regions of the estuarine basin where sediments cannot be dated using traditional methods. All cores were freeze-dried and archived for further analysis. In addition to total mercury, gravity cores were analyzed for a spectrum of metals including Fe, Li, Mn and Pb. Subsamples for metal analysis were prepared by digesting 1.0 g of freeze-dried sediment in 5.0 ml of concentrated nitric acid for approximately 24 h at 60 jC. Flame atomic absorption analyses were carried out using a Varian 220FS spectrometer for Fe, Li and Mn. Electrothermal atomic absorption analysis of Pb was carried out using a Varian 220FS spectrometer fitted with a Varian GTA110 graphite furnace. Relative precision and accuracy limits, estimated from replicate analyses of CANMET-certified reference materials (STSDs 1 4) and an internal GSC standard (EMG-017), were determined to be F 3% for Fe, Li and Mn and F 5% for Pb. Total and organic carbon was determined in 0.5 g of freeze-dried sediment using a Leco WR-112 carbon analyzer. Inorganic carbon was removed using 1 M hydrochloric acid prior to organic carbon measurements. Precision and accuracy were estimated to be F 0.03 wt.% based on replicate analyses of calibration standards. 2.2.3. Sediment porewaters Sediment porewater samples were separated from selected push cores (n = 2) and surface sediment samples (n = 23) collected at the push core and gravity core sampling locations. Porewaters were extracted under a nitrogen atmosphere by transferring the bulk sample into 50-ml acid-washed polycarbonate centrifuge tubes. Tubes were purged with N2 prior to

transfer, centrifuged at 3000 rpm for 30 min, followed by vacuum filtration with disposable 0.2-Am cellulose nitrate filter units. All filters were rinsed with 1% HCl and distilled deionized (18 V Millipore filtration system) water immediately prior to use. Porewater samples for total mercury analysis were preserved in 0.5% ultrapure HCl, while MeHg samples were immediately frozen until analysis. 2.2.4. Isotope cores At two stations (SC-1 and PB-3), duplicate intact sediment cores were spiked at 1-cm intervals with inorganic mercury isotope [91.95% 199Hg(II) from Oak Ridge Batch #168490] that was pre-equilibrated with seawater. Cores were incubated at ambient seawater temperature for 4 h, extruded and frozen until analysis for conversion of 199Hg(II) into methylated mercury. The purpose of this work was to determine a methylation potential for these sediments rather than using the isotope as a tracer because the added 199 Hg(II) may be more available for methylation than the in situ Hg(II). 2.2.5. Polychaetes Polychaete worms (Nephtys sp.) were collected from benthic sediments at the same sampling locations as push cores, gravity cores and isotope cores. Samples were obtained by immediately sieving the wet sediments collected using a modified Van Veen grab sampler on board the sampling vessel. Polychaetes were identified in the laboratory, flushed with deionized water for 24 h and frozen until analysis for mercury. Biological samples were analyzed for total mercury using the same methodology as sediment samples. 2.3. Mercury analyses Samples for total and MeHg analyses were placed in 125-ml acid-washed polypropylene specimen jars and were immediately cooled to < 4 jC. Upon returning to the laboratory, all samples were frozen until analysis. Wet sediment samples were analyzed for total mercury by digestion in 5:2 concentrated nitric sulfuric acid solution and oxidation with bromine monochloride (BrCl) under Class 100 clean room conditions. Aqueous samples were digested with BrCl for at least 12 h before analyses.

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Immediately prior to analysis, the excess bromine in all samples was neutralized with an equivalent volume of 10% hydroxylamine hydrochloride. All samples were then reduced with stannous chloride, purged with nitrogen gas and trapped on gold packed columns. Quantification was by dual-stage gold amalgamation and cold-vapor atomic fluorescence spectroscopy (CVAFS). This procedure was based on EPA Method 1631, Gill and Fitzgerald (1987) and Bloom (1989). Methylmercury was determined by steam distillation, aqueous phase ethylation using sodium tetraethylborate, purging onto Tenaxk packed columns, gas chromatography separation and CVAFS detection following a technique by Bloom and Fitzgerald (1988) and Horvat et al. (1993), modified by Branfireun et al. (1999). The same methods were used for samples spiked with 199 Hg(II) isotope except that detection was made using an HP4500 Inductively Coupled Plasma-Mass Spectrometer (ICP-MS) (Gill and Fitzgerald, 1987; Hintelmann and Evans, 1997). The method detection limit (MDL) for total mercury in sediment solids was 0.95 pmol g 1 (n = 19), determined as three times the standard deviation of the mean of the sample blanks. For aqueous samples, the MDL based on a 150-ml sample volume was 0.20 pM (n = 18). Precision, measured as the relative percent difference (RPD) between digest duplicates (sediment solids) and analytical duplicates (aqueous phase), were 9.6% (n = 24 pairs) and 5.7% (n = 2 pairs), respectively. Calibration curves of at least r2 = 0.99 were achieved daily or samples were rerun. Accuracy was measured both by spike recoveries and using the MESS-3 marine sediment certified reference material (454 F 45 pmol g 1) from the National Research Council of Canada. Recoveries averaged 103 F 10% (n = 12) and 459 F 80 pmol g 1 for all MESS-3 samples (n = 9). Samples from runs with poor recoveries ( < 80%) were reanalyzed. For MeHg, the MDL was 0.032 pM (n = 6) in the aqueous phase and 0.035 pmol g 1 (n = 16) for sediment solids. For ICP-MS, the detection limit was 0.075 pmol g 1 and sample reproducibility was 10% for ambient MeHg and 23% 199 for the CH3 Hg isotope concentration. Isotope detection was further constrained to 0.5% of the ambient concentration. The RPD for distillation duplicates was 18.1% (n = 21), while the average recovery of spikes between 0.5 and 2.5 pmol g 1 of wet sediment was

106 F 26% (n = 12). Some of this variability can be attributed to uncertainty as to the true concentration of the sediment sample being spiked, as reflected in the RPD of distillation duplicates. A wet to dry weight conversion was determined for each sample analyzed by oven-drying subsamples of wet sediments for at least 24 h at 60 jC. 2.4. Statistical analysis Nonparametric bivariate correlation matrices (Spearman rank correlation coefficients, rs) were developed for gravity core and push core data to investigate covariation between total mercury (HgT), MeHg, %MeHg and potential methylation rates. For gravity core data, Hg-T profiles were analyzed as a function of other metals with known anthropogenic origins such as Pb and other geochemical data including porewater sulfate and ammonium concentrations.

3. Results 3.1. Speciation in the active sediment layer Fig. 2 shows mercury speciation in sediment cores from contrasting physical regions. The St. Croix River station (SC-1) is located at the head of the St. Croix River Estuary where the sediment accumulation rate was estimated to be between 1 and 2 mm year 1 based on the gradients in dissolved ammonium found in the gravity cores using the method developed by Cranston (1991, 1997). In contrast, stations PB-3 and PB-4 are located on opposite sides of the main basin of Passamaquoddy Bay (Fig. 1), near the center of two tidally dominated circulation gyres (Greenberg et al., 1997) that are expected to result in significant mixing of these sediments. 3.1.1. Total mercury (Hg-T) At station SC-1 (Fig. 2a), there is a pronounced subsurface peak in total mercury (Hg-T) that may be the result of historic mercury discharges from a chloralkali facility that operated along the river in the 1970s. Concentrations of Hg-T in the sediments decrease from the head of the river estuary into the center of Passamaquoddy Bay. The uniform Hg-T

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Fig. 2. Speciation of mercury measured in push cores from contrasting depositional (SC-1) and well-mixed sediments (PB-3 and PB-4). Data include ambient total mercury (Hg-T), methylmercury (MeHg) and the fraction of total mercury in the sediments present as MeHg (%MeHg). Mercury isotope experiments were used to estimate the potential methylation rates at the head of the St. Croix River Estuary (SC-1) and the center of Passamaquoddy Bay (PB-3).

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profiles at stations PB-3 and PB-4 on both sides of Passamaquoddy Bay (Fig. 2b and c) provide further evidence that these sediments are also well mixed. 3.1.2. Methylmercury (MeHg) The effects of differing physical dynamics on MeHg production are illustrated by the contrasting MeHg profiles (Fig. 2) at the head of the river estuary (SC-1) relative to the well-mixed areas in the center of Passamaquoddy Bay (PB-3 and PB-4). The fraction of total mercury present as methylmercury (%MeHg) in these sediments is strongly correlated with potential methylation rates measured in cores spiked with mercury isotopes (rs = 0.88, p < 0.01), supporting the premise that %MeHg is a reasonable approximation of the relative rates of Hg methylation in these sediments. This relationship has also been seen in other estuarine sediments (Benoit et al., 2003). At station SC-1, MeHg production is taking place in a narrowly constrained subsurface zone. There is a subsurface peak between 2 and 4 cm in ambient MeHg concentrations, %MeHg and potential methylation rates measured in isotope cores. Ambient MeHg concentrations decline rapidly in the oxic surface layer and beyond depths of several centimeters, while methylation rates indicated by both the %MeHg and the isotope core data are low to nondetectable, respectively, in these depth intervals. For example, the %MeHg ranges between 0.54% and 0.76% in the 2 4 cm subsurface peak in MeHg production at station SC-1, compared to 0.28% in the surface layer, and between 0.11% and 0.34% at depths greater than 6 cm. This profile is typical of those observed in other studies of relatively unmixed lake and estuarine sediments, which show that the %MeHg in estuarine sediments is generally less than 0.5%, particularly in the oxic surface sediments and at depth, and that MeHg production occurs in a relatively narrow subsurface zone within the sediments (e.g., Benoit et al., 1998a; Bloom et al., 1999; Gagnon et al., 1996). In the mixed sediments at stations PB-3 and PB-4, the ambient MeHg profiles and %MeHg suggest that MeHg conversion is taking place at all depths in the surface sediment layer. Methylmercury concentrations and %MeHg are both relatively uniform at all depths (Fig. 2b and c) and potential methylation rates measured at station PB-3 are detectable throughout the entire profile studied. At station PB-4, the %MeHg

ranges between 0.62% and 0.92%, which is in the same range as the 2 4 cm subsurface peak in %MeHg at site SC-1 that corresponds to maximum methylation rates. Additionally, the mean %MeHg in integrated surface samples (0 10 cm depth) from multiple locations throughout Passamaquoddy Bay (n = 45) was 0.88%, again, characteristic of sediments where MeHg is being actively produced in situ in the sediment column. These data support the premise that in the well-mixed sediments of Passamaquoddy Bay, MeHg production is taking place both at the sediment water interface and throughout the 15-cm-thick active surface layer. 3.2. Porewater solids partitioning Porewater samples in this study represent operationally defined dissolved concentrations of total mercury and methylmercury since colloidal matter binds mercury in the < 0.2-Am size fraction (Guentzel et al., 1996). Porewater concentrations of Hg-T ranged between 50 and 150 pM (Table 1) and are significantly elevated above the levels expected on the basis of solid-phase concentrations, as they are in the same range as sites heavily impacted by historical pollution, such as Lavaca Bay, TX (Bloom et al., 1999). Accordingly, the range in partition coefficients (log Kd) for Hg-T between 3.12 and 3.76 (l kg 1) in Passamaquoddy Bay is lower than those observed in other systems (Bloom et al., 1999; Leermakers et al., 1995; Turner et al., 2001). Elevated levels of Hg-T in porewaters of Passamaquoddy Bay sediments are consistent with the effects of mixing in this system, which is causing substantial recycling of Hg in the surface sediments and an increased fraction of colloidally bound Hg-T in the porewaters.
Table 1 Porewater Hg-T and MeHg data from surface sediment grab samples at stations SC-1 and PB-1 through PB-5 Station SC-1 PB-1 PB-2 PB-3 PB-4 PB-5
a b

Hg-T (pM) 135 150a 55 80a 50 80b

MeHg (pM) 2.3 4.7a N/A 2.7a 3.4b 7.2a

Means of triplicate samples. Means of duplicate samples.

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+ Porewater NH4 concentrations >0.5 mM indicate anoxic sediments that are below the active sediment layer due to lack of oxidation of ammonium produced by decomposition of organic matter (Buckley, 1991; Buckley and Cranston, 1988) and allow an upper boundary to be placed on the depth of the active sediment layer. These sediments may be considered truly buried and effectively removed from further interaction with the sediment water interface. Data from other cores collected throughout Passamaquoddy Bay further confirm that the depth of the active sediment layer based on porewater ammonium data is generally between 15 and 30 cm (Table 2). This relatively large volume of sediments in the active sediment layer results in a large pool of historic HgT that can potentially be converted to MeHg. Data on porewater sulfate levels in gravity cores from Passamaquoddy Bay indicate that sulfate reduction is taking place at all depths within these sediments, including at the sediment surface (Fig. 3, Table 2). Anoxic reduction of sulfate based on a geochemical threshold established in the literature is indicated by porewater sulfate concentrations < 24 mM (Buckley, 1991; Buckley and Cranston, 1988). In all Passamaquoddy Bay sediments, porewater sulfate levels are very close to this level, supporting the idea that these sediments are in the oxic-transitory range that is most conducive for the activity of SRB. Although porewater sulfate data (Fig. 3) indicate anaerobic reduction of sulfate, which typically corresponds to a redox potential of approximately 200 mV (Wildish et al., 1999), redox potentials (Eh) measured in surface sediments varied between 213 and 512 mV (Sunderland, 2003). The large variability in redox measurements and length of time (>5 min) needed in the field for the redox probe to achieve equilibrium may both signify the presence of Eh microniches in the surface layer (Wildish et al., 1999); however, these data should be interpreted with caution as variability may also reflect measurement errors associated with these types of Eh measurements. Sulfide concentrations measured in the surface sediments using an ion-specific electrode were also highly variable, ranging between 10 and 4000 AM in replicate samples taken at a single sampling station (Table 3). The large variability in sulfide concentrations and the presence of Eh microniches show rapid transitions in the sediment geochemistry in the surface

Porewater MeHg concentrations are also elevated relative to systems with similar Hg-T concentrations in sediments such as the Patuxent River, MD (Benoit et al., 1998a), but partition coefficients (log Kd) ranging between 2.20 and 3.00 (l kg 1) are in the same range as values found in other studies (Benoit et al., 1998a; Bloom et al., 1999). These results suggest that MeHg concentrations are enriched in both the solid and dissolved phases and support the hypothesized increase in MeHg production in well-mixed sediments. 3.3. Geochemical characteristics of the sediment column
+ Fig. 3 shows porewater ammonium (NH4 ) and sulfate levels measured in gravity cores collected in + Passamaquoddy Bay. Porewater NH4 concentrations that are consistently >0.5 mM occur below a depth of 30 cm at station PB-3 (Fig. 3) and below 15 cm at station PB-4 (Table 2).

Fig. 3. Porewater sulfate and ammonium concentrations measured in gravity cores from Passamaquoddy Bay and the St. Croix River Estuary. Sulfate concentrations < 24 mM indicate the anoxic reduction of sulfate and ammonium concentrations >0.5 mM indicate the presence of fully reduced buried sediments.

E.M. Sunderland et al. / Marine Chemistry 90 (2004) 91105 Table 2 Geochemical characteristics of gravity cores from Passamaquoddy Bay Station ID SC-1 SC-2 PB-1 PB-2 PB-3 PB-4 PB-5 PB-6 PB-7 PB-8 PB-9 PB-10 PB-11 PB-12 PB-13 PB-14 PB-15 PB-16 PB-17c PB 18 Length (cm) 105 55 50 130 100 130 130 130 140 130 127 105 130 130 130 130 130 130 130 75 Organic carbon (%) 1.11 4.21 0.41 1.05 0.24 1.37 0.92 1.74 1.01 1.77 1.05 1.65 0.76 1.48 1.11 2.17 0.81 1.57 1.00 1.36 0.28 1.15 0.94 1.39 1.15 1.34 1.46 1.60 1.15 1.63 1.03 1.68 0.79 1.69 0.87 1.04 1.08 1.65 0.44 1.43 NH+ > 0.5 mM depth 4 interval(s) (cm)a 50 105 NI NI 5 10; 15 130 30 100 15 130 NI 5 130 100 140 15 130 60 127 40 105 40 130 60 130 60 130 NI 70 100 50 130 30 130 NI SO2 < 24 mM depth 4 interval(s) (cm) 50 105 5 10 0 5; 10 15 50 60; 80 130 0 5; 50 60; 70 80; 90 100 0 5; 10 50 0 10; 50 60; 120 130 0 5; 40 50; 120 130 15 20; 60 80 0 5; 40 50; 120 130 0 5; 10 15; 90 100; 110 127 60 70 NI NI NI NI NI NI NI NI

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Range in SO2 4 mMb 20 26 22 27 22 24 19 29 22 26 23 28 23 26 23 26 23 26 23 26 20 26 23 28 24 27 24 27 24 27 24 27 24 27 24 27 24 27 24 27

NI = no indication of reduction. There is an evidence of reduction in all cores except PB-14 and PB-18, and even in these cores, the sulfate levels are very close to the geochemical cutoff characterizing reducing conditions. a Concentrations of NH+ > 0.5 mM measured in porewaters indicates lack of oxidation of ammonium produced by decomposition of organic 4 matter. In a number of cores, the presence of consistently >0.5 mM NH + at depth suggests anoxic buried sediments. 4 b Minimum to maximum SO2 concentrations measured in porewaters throughout each core are reported. Note that the range in SO2 4 4 concentrations are all very close to the geochemical cutoff (24 mM) indicating anoxic reduction of sulfate. This supports the supposition that most of these sediments are in the oxic transitory range where there is a large gradient in redox potential, ideal for the activity of sulfate-reducing bacteria. c Top 30 cm of core PB-17 missing.

layer that provide conditions most favorable to methylating microbes and are indicative of the effects of organic-rich mottles or pockets in the surface sediments.
Table 3 Variability in sulfide concentrations measured in surface sediment grab samples from Passamaquoddy Bay Sulfide concentrations (uM) Station PB-1 PB-2 PB-3 PB-4 PB-5 PB-6 PB-8 PB-9 PB-10 Mean 213 659 554 667 1471 363 167 393 92 N 9 7 12 6 9 6 3 4 3 Min 23 190 32 480 10 33 42 30 36 Max 1500 1300 1100 800 4000 1000 370 1200 150

Visual inspection of sediment cores from Passamaquoddy Bay in the field revealed the presence of black, organic-rich mottles interspersed with the dominant light brown oxic clay muds. There was also detectible H2S odour in the presence of these mottles, indicating anoxia. Based on these data, we hypothesize that the anoxic organic-rich pockets in Passamaquoddy Bay sediments effectively increase the volume of sediments suitable for formation of MeHg by SRB by increasing the transition zone between oxic and anoxic sediments. The resulting geochemical environment would be comparable to that observed by Tseng et al. (2001) in a turbid macrotidal estuary in France where methylation of mercury was measured in analogous anoxic pockets occurring within a fluid mud profile. These organic carbon pockets facilitate MeHg production throughout the relatively deep active sediment

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Table 4 Concentrations of metals measured in gravity cores Station PB-7 Sediment depth (cm) 02 24 46 68 8 10 10 + 02 24 46 68 8 10 10 + 0 5 10 15 20 30 40 50 60 70 80 0 5 10 15 20 30 40 50 60 70 80 90 100 Hg (pmol g 1) 204 219 219 219 214 219 214 219 224 209 214 209 284 219 244 214 125 70 55 90 184 65 65 229 249 319 379 274 189 80 80 50 40 45 40 40 1 Fe (nmol g 1) 48.0 45.3 44.8 37.8 39.2 41.0 47.6 49.2 50.3 50.9 49.8 41.0 44.2 41.9 46.9 52.1 54.1 50.1 53.7 54.6 54.4 56.0 63.6 44.9 41.9 40.8 44.4 43.9 41.5 38.3 39.2 35.6 35.8 34.4 36.2 34.9 N/S Li (Amol g 1) 5.48 4.90 5.48 5.48 5.33 5.48 6.20 6.34 6.34 6.20 6.48 6.05 4.76 3.89 5.62 6.20 4.47 6.05 6.20 6.20 6.48 6.63 6.92 5.91 5.91 5.76 6.05 6.05 6.48 6.48 5.76 5.91 7.06 6.05 5.76 5.91 0.359 p < 0.05 Mn (Amol g 1) 6.46 6.37 6.70 5.35 5.44 5.72 6.63 7.15 6.75 7.41 7.12 5.88 5.37 5.61 6.13 6.81 6.55 6.92 7.15 7.48 6.83 7.44 8.17 7.04 6.84 6.73 7.19 6.61 7.06 6.72 6.12 5.66 5.39 5.37 5.97 5.66 N/S Pb (nmol g 1) 67.6 67.6 72.4 67.6 72.4 72.4 77.2 67.6 62.7 67.6 62.7 57.9 38.6 43.4 48.3 29.0 38.6 24.1 24.1 24.1 24.1 29.0 24.1 91.7 91.7 115.8 91.7 106.2 62.7 43.4 33.8 29.0 33.8 29.0 33.8 33.8 0.758 p < 0.001

PB 8

SC 1

PB-3

Correlation with Hg (rs)

Pearson correlation coefficients (r) for metals as a function of Hg are shown below concentration data for each core. N/S = correlation is not significant.

layer in Passamaquoddy Bay, thereby accounting for the observed enrichment in MeHg in the sediment porewaters and the high %MeHg in the solid-phase sediments. 3.4. Anthropogenic mercury in Passamaquoddy Bay Anthropogenic sediment enrichment factors (ASEFs) were calculated from Hg-T concentrations

measured in sediment cores at stations SC-1 and PB3. Mixing of these sediments means it is not possible to obtain detailed information on historical Hg-T loading from these cores and that traditional dating methods using 210Pb and 137Cs could not be applied (Smith, 2001). However, ASEFs calculated from the difference between mercury concentrations in the sediments that accumulated prior to human influence and those at the surface provide a simple method for

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estimating the overall enrichment in this system resulting from anthropogenic pollution. Present-day burial rates of approximately 1 2 mm year 1 measured in this study suggest that sediments below 40-cm depth in gravity cores should represent Hg-T concentrations in the sediments prior to significant human sources of mercury, while allowing a wide margin for integration of the sediment column due to mixing. Diagenetic remobilization of mercury in sediment cores can cause peaks in mercury concentrations in the surface sediments that are not indicative of anthropogenic pollution (Benoit et al., 1998b; Walton-Day et al., 1990). However, the lack of significant correlations between Hg-T concentrations and redox-sensitive metals such as Fe and Mn (Table 4) suggests that redistribution of mercury through diffusion and co-precipitation is not a significant factor in gravity cores from Passamaquoddy Bay. To

isolate the natural and anthropogenic components of metal enrichment, iron (Fe) and lithium (Li) can both be used as normalizing factors to correct for the mineralogical and granulometric variability in the sediments (Loring, 1991). However, there were no significant correlations between Hg-T and Fe or Li in these sediments; thus, it can be assumed that the observed Hg-T profiles are not caused by changes in grain size and/or mineralogy. The range of background concentrations (i.e., those that are naturally occurring) of Hg-T in Passamaquoddy Bay cores was estimated from 95% confidence limits around Hg-T concentrations below 40 cm in the gravity cores. Anthropogenic sediment enrichment factors shown in Fig. 4 include the surface of gravity cores and push cores collected at stations SC-1 and PB-3. For surface sediments obtained from push cores at the same sampling stations (0 15 cm), Hg-T concentrations

Fig. 4. Anthropogenic sediment enrichment factors (ASEFs) for Hg-T at the head of the St. Croix River and the center of Passamaquoddy Bay. ASEFs are used to estimate modern/background Hg-T levels in Passamaquoddy Bay sediments. The lower graphs in the figure depict gravity core Hg-T data, while ASEF profiles shown for the surface sediments are from push cores taken from the same sampling stations.

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measured in the upper horizon of the sediments were divided by the upper 95% confidence limit value for background mercury levels to produce the plots of ASEFs shown in Fig. 4. The results presented in Fig. 4 show that ASEFs in Passamaquoddy Bay range between 3 and 6 and up to 26.3 at the head of the St. Croix River where localized historical discharges are likely the most important source of contamination. The enrichment factors for Passamaquoddy Bay are in the same range as other studies that show a global scale increase in atmospheric mercury deposition of two to four times the preindustrial levels (Swain et al., 1992; Engstrom et al., 1994), suggesting that the majority of Hg-T in these sediments is derived from atmospheric sources. The high degree of correlation between lead, which is known to exhibit a strong anthropogenic signal, and Hg-T concentrations (rs = 0.76, p < 0.001; Table 4) provides further evidence of anthropogenic enrichment in these cores. The results of this analysis indicate that the majority of the mercury in the active sediment layer of Passamaquoddy Bay is from historic inputs of mercury from anthropogenic sources.

4. Discussion This study presents evidence showing that mixing of the active sediment layer in Passamaquoddy Bay

results in geochemical changes in the sediment column that enhance the activity of methylating microbes. In marine sediments, net methylation rates are highest in the transition zone between oxic and anoxic conditions because these conditions are most conducive to the activity of SRB (Hintelmann et al., 2000; King et al., 2001). In addition, these microbes require organic matter as a substrate for microbial activity (Mason and Lawrence, 1999). Physical mixing in the Bay of Fundy may enhance the transfer of sulfate and carbon and introduces more bioavailable inorganic mercury into the deeper sediment, potentially stimulating the methylating activity of SRB. Regular disturbances through mixing also appear to create a unique geochemical environment more likely to exhibit microzonal redox gradients, compared to the classic down profile gradients of sediments in which less physically dynamic conditions may limit the activity of microbial populations that methylate mercury. Fig. 5 is a conceptual diagram that contrasts the features of mercury speciation and sediment geochemistry observed in well-mixed sediments in this study with the characteristic profile of mercury speciation typical of depositional sediments. As illustrated in Fig. 5, production of MeHg in sediments from unmixed depositional systems must be modeled as a two-compartment system, taking into account that MeHg production occurs in a narrow

Fig. 5. Conceptual model of mercury speciation in contrasting depositional and well-mixed sediments.

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zone in the redoxcline below the oxic surface layer of these sediments. In well-mixed systems, such as Passamaquoddy Bay, the sediment compartment is better described by System 2 (Fig. 5) where MeHg production occurs throughout a relatively deep active sediment layer and is facilitated by the presence of organic-rich anoxic pockets or mottles. Additionally, MeHg production occurs at the sediment water interface in the well-mixed sediments, potentially providing a vector for MeHg entry into the water column and resulting in the exposure of organisms feeding at the sediment surface. The dynamic physical mixing occurring in Passamaquoddy Bay results in the creation of an approximately 15-cm-thick active sediment layer. Burial provides the main removal mechanism for historic mercury that has accumulated over time. In Passamaquoddy Bay, the sediment burial rate estimated from this study is approximately 1 2 mm year 1. This means that the active sediment layer is comprised of a relatively large reservoir of Hg-T consisting of mainly historical pollution (Fig. 4) that has accumulated in the sediments over many decades. In contrast, in a depositional system, the active layer is typically much shallower (e.g., 3 5 cm) resulting in a much smaller reservoir of Hg-T that can be potentially converted to MeHg by methylating microbes. As an illustrative example, the reservoirs of MeHg in mixed and unmixed systems with comparable Hg-T concentrations were estimated using the Hg-T data from gravity cores SC-1 and PB-3 (Fig. 4) and push core data for %MeHg in the 14-cm surface horizon (Fig. 2). Using an average sediment density of 2.7 g cm 3 and an average concentration of solids in the sediments of 0.67 g cm 3 for both sites, the reservoir of MeHg on an areal (1 m2) basis are approximately 3.5 and 2.4 Amol in the mixed and unmixed sediments, respectively. According to these calculations, the reservoir of MeHg is almost 50% higher in the well-mixed sediments when compared to depositional sediments with similar Hg-T concentrations. The physical mechanism of mixing may also provide a vector for MeHg entry into the water column and food web through organisms feeding at the sediment water interface. In the well-mixed sediments, MeHg production occurs throughout the active sediment layer, including at the sedimentwater interface as illustrated in the push core profiles for

Passamaquoddy Bay (Fig. 2b and c). In contrast, the oxic sediment layer in unmixed, depositional systems can act as a geochemical barrier to diffusing MeHg through the precipitation of MeHg with Fe and Mn hydroxides (Gagnon et al., 1996). In depositional areas, this oxic layer can inhibit the entry of MeHg to the water column and limit exposure of all but burrowing benthic organisms. In the well-mixed sediments of Passamaquoddy Bay, the enhanced levels of Hg-T and MeHg in the porewaters of surface sediments are consistent with rapid cycling of mercury in this system at the sediment water interface that is facilitated by the physical dynamics of the area. Preliminary evidence for increased availability of mercury to organisms in wellmixed sediments is provided by the observed differences in the mean concentrations of total mercury measured in polychaetes collected from sediment grabs at the head of the St. Croix River Estuary (n = 3) compared to well-mixed sediments in Passamaquoddy Bay (n = 10). These data show that concentrations of mercury in polychaetes are significantly higher ( p < 0.01) in the well-mixed sites (55 F 14 pmol g 1 wet wt.) than at the head of the river estuary (38 F 5 pmol g 1), despite significantly lower spatially averaged concentrations of Hg-T in surface sediments from Passamaquoddy Bay ( f 150 pmol g 1) relative to the head of the river estuary ( f 550 pmol g 1) (Sunderland, 2003). The results of this study help to elucidate why concentrations of mercury in organisms from this coastal system are still high despite large emissions reductions. In Passamaquoddy Bay, there is a linear relationship between Hg-T and MeHg in the sediments (Sunderland, 2003), which means that increases or decreases in Hg-T emissions should eventually translate into corresponding changes in MeHg concentrations in sediments and ultimately organisms. However, the results of this study suggest that there is a large lag time between reduced mercury inputs and changes in ambient concentrations because historic mercury inputs are slowly being converted to MeHg over the 15-cm-thick active sediment layer and removal of mercury through sediment burial is relatively slow. This hypothesis is currently being further tested through the application of a mercury cycling model for the region.

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Acknowledgements This work was supported by a strategic grant from the Natural Sciences and Engineering Research Council of Canada (NSERC), the Gulf of Maine Council on the Marine Environment and the NSERC Postgraduate Scholarship Program (ES). We acknowledge the assistance of Janice Weightman from Simon Fraser University who collected and identified biological samples. We thank the staff at Huntsman Marine Science Centre, Fisheries and Oceans Canada and the Geological Survey of Canada for supplementary data and technical support during field data collection including Hugh Agaki, John Dalziel, Gareth Harding, Doug Loring, Bob Murphy, Peter Vass and Dave Wildish. We would also like to thank Phil Yeats and John Dalziel at the Bedford Institute of Oceanography and two anonymous reviewers for their helpful comments during preparation of this manuscript. This is Geological Survey of Canada Contribution No. 2003056. References
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