Addendum to: dioxin and heavy-metal contamination of shellfish and sediments in St. Louis Bay, Mississippi and adjacent marine waters.ABSTRACT We published an article (Elston et al. 2005) in Volume 24 of the Journal of Shellfish shellfish, popular name for certain edible mollusks (see Mollusca), e.g., oysters, clams, and scallops, and for certain edible crustaceans, e.g., crabs, lobsters, and shrimps. All are aquatic invertebrates with shells; they are not fish. Research demonstrating substantial contamination of St. Louis Bay, Mississippi with dioxins and heavy metals heavy metals, n.pl metallic compounds, such as aluminum, arsenic, cadmium, lead, mercury, and nickel. Exposure to these metals has been linked to immune, kidney, and neurotic disorders. , including chromium chromium (krō`mēəm) [Gr.,=color], metallic chemical element; symbol Cr; at. no. 24; at. wt. 51.996; m.p. about 1,857°C;; b.p. 2,672°C;; sp. gr. about 7.2 at 20°C;; valence +2, +3, +6. , nickel and arsenic that occurred in close proximity to a large titanium dioxide plant that has operated near the Bay since the early 1980s. We conducted an exhaustive evaluation of potential sources of contamination and concluded that the plant was the most likely source of contaminants. We were aided in this analysis by a variety of data including a preplant baseline study (Lytle & Lytle 1982) and a study of dioxin dioxin Aromatic compound, any of a group of contaminants produced in making herbicides (e.g., Agent Orange), disinfectants, and other agents. Their basic chemical structure consists of two benzene rings connected by a pair of oxygen atoms; when substituents on the rings are contamination in oysters harvested from Southern Mississippi conducted in 1997 (Fiedler et al. 1997). In this addendum addendum n. an addition to a completed written document. Most commonly this is a proposed change or explanation (such as a list of goods to be included) in a contract, or some point that has been subject of negotiation after the contract was originally proposed by we publish new information that further implicates the plant as the source of dioxin contamination, corrects minor underestimates from our original report in some of the WHO-TEQ (World Health Organization Toxic Equivalencies) for dioxins in St. Louis Bay and Mississippi Sound Mississippi Sound, arm of the Gulf of Mexico, c.100 mi (160 km) long and from 7 to 15 mi (11–24 km) wide, extending from Lake Borgne in Louisiana on the west to Mobile Bay in Alabama on the east. shellfish and also corrects the estimated magnitude of increase of dioxins in Southern Mississippi since 1997. These corrections do not change the conclusions of our original study. In fact, the increases in WHO-TEQs for shellfish and the new data obtained since publication of that article provide additional and substantial support for our conclusion that the plant is the primary source of dioxin contamination. In addition, these new data call into question the reliability and utility of data reported by the plant to the United States Environmental Protection Agency "EPA" redirects here. For other uses see EPA (disambiguation) and Environmental Protection Agency. The Environmental Protection Agency (EPA or sometimes USEPA Toxic Release Inventory for use in assessing the public health risk of releases from the plant. This new information demonstrates 2,3,7,8 TCDD TCDD tetrachlorodibenzodioxin. , the most toxic dioxin congener congener /con·ge·ner/ (kon´je-ner) something closely related to another thing, as a member of the same genus, a muscle having the same function as another, or a chemical compound closely related to another in composition and exerting and one recognized as a carcinogen carcinogen: see cancer. carcinogen Agent that can cause cancer. Exposure to one or more carcinogens, including certain chemicals, radiation, and certain viruses, can initiate cancer under conditions not completely understood. by the International Agency for Research on Cancer The International Agency for Research on Cancer (IARC, or CIRC in its French acronym) is an intergovernmental agency forming part of the World Health Organisation of the United Nations. Its main offices are in Lyon, France. , is in fact present on the plant site, a fact previously unknown and unreported, although we reported this congener in the two sediment samples adjacent to the plant outfall out·fall n. The place where a sewer, drain, or stream discharges. outfall Noun Brit, Austral & NZ the mouth of a river, drain, or pipe: in our original report. KEY WORDS: dioxin, furan furan: see furfural. , trace metals, chromium, nickel, St. Louis Bay, oysters INTRODUCTION As described in our original report (Elston et al. 2005), St. Louis Bay, Mississippi is a 3,860-ha elliptical-shaped, shallow embayment with a relatively narrow entry to the western end of Mississippi Sound. Based on our July 2004 study, we concluded that dioxins and heavy metals, including chromium, nickel and arsenic, found in the Bay were the result of operations by a titanium dioxide plant located on the northern shoreline of St. Louis Bay and the release of these contaminants from the plant into the environment including into St. Louis Bay. We based these conclusions on a comparison of 2004 contaminant contaminant /con·tam·i·nant/ (kon-tam´in-int) something that causes contamination. contaminant something that causes contamination. values with values from earlier studies including preplant operation periods, along with an evaluation of other possible sources of contaminants, as well as by comparison with data reported to the United States Environmental Protection Agency (USEPA USEPA United States Environmental Protection Agency ) Toxic Release Inventory. Data for this inventory is provided by the plant to the USEPA but the data may be estimated and made without any actual analytic measurement. Subsequent to the publication of our original article, we have obtained new data not previously available on dioxin analysis from samples taken on the actual plant site. We have also reviewed our original data and determined that we underestimated certain of the toxic equivalencies (TEQs) of St. Louis Bay and adjacent Mississippi Sound oysters by a factor of about 12%. We also determined that in an effort to compare our 2004 data to a previous evaluation of oysters from southern Mississippi (Fiedler et al. 1997), which used an obsolete system of estimating toxic equivalencies (I-TEQ), we overestimated the probable increase in dioxin contamination of southern Mississippi oysters since 1997. In this study we present the new data further implicating im·pli·cate tr.v. im·pli·cat·ed, im·pli·cat·ing, im·pli·cates 1. To involve or connect intimately or incriminatingly: evidence that implicates others in the plot. 2. the plant as the source of contamination and correct minor errors in our original report. We strongly emphasize that these errors do not change the conclusions of our original report, even without the new data, which adds substantially to the strength of our conclusion that the plant is the source of dioxin contaminants. MATERIALS AND METHODS Field Collection of Samples Samples were collected by Aqua-Tech Laboratories of Bryan, Texas Bryan is a city in Brazos County, Texas, United States. As of the 2000 census, the city had a total population of 65,660. It is the county seat of Brazos CountyGR6 for dioxin and other analyses between May 19 and 21, 2005 from the titanium dioxide plant site on the northern shore of St. Louis Bay or were delivered to Aqua-Tech Laboratories by agents for the plant. These samples were then submitted to Columbia Analytical Services (CAS) of Houston, Texas “Houston” redirects here. For other uses, see Houston (disambiguation). Houston (pronounced /'hjuːstən/) is the largest city in the state of Texas and the . Dioxins were analyzed by EPA EPA eicosapentaenoic acid. EPA abbr. eicosapentaenoic acid EPA, n.pr See acid, eicosapentaenoic. EPA, n. Method 8290, as referenced in the original report, by CAS. The field samples collected on the plant site were solid material from bags containing "ore matter", from "dust piles", "dust" and "scale scraped from line 2 fume fume Occupational medicine A solid suspension resulting from condensation of the products of combustion. See Inhalant Vox populi verbTo be in the midst of a mental mini-meltdown. stack-near top." RESULTS Dioxins and Furan Values From Shellfish Dioxin and furan concentrations expressed as toxic equivalencies for shellfish collected in and near St. Louis Bay are shown in Table 1. Toxic equivalencies (TEQs) are expressed as WHO-TEQs (Vanden Berg et al. 1998) and I-TEQs (USEPA 1989), for comparison with a previous evaluation of oysters from southern Mississippi (Fiedler et al. 1997). The only data revisions we present are contained in Table 1 from our original report (Elston et al. 2005) and are shown in the revised Table 1 in this addendum. The sample site locations are given in the original report. In summary, the revised data in Table 1 indicates: There was no change in percent lipid of shellfish from the 15 shellfish sample tracts. All values for WHO-TEQ (ND = 1/2), except for shellfish tracts 2 and 3, were increased by about 12% from the originally reported values because of a decimal place decimal place n. The position of a digit to the right of a decimal point, usually identified by successive ascending ordinal numbers with the digit immediately to the right of the decimal point being first: error in one toxic equivalency equivalency the combining power of an electrolyte. See also equivalent. factor (TEF TEF Tracheoesophageal fistula, see there ). There is no change in these values for shellfish tracts 2 and 3. The average WHO-TEQs are thus correspondingly increased. All values for I-TEQ (ND = 1/2) and I-TEQ (ND = 1/2 [corrected for lipid]), except those for shellfish tracts 2 and 3 and the average values, were correct in the original report and consistent with those of Table 1 in this report. However, the I-TEQ values and I-TEQ lipid adjusted values for shellfish tracts 2 and 3 are revised downward to 0.411 and 0.332 pg/g and 74.679 and 94.866 pg/g, respectively, from the original report. The average I-TEQ values for all transects, shown at the bottom of these columns, are also correspondingly reduced slightly. Dioxins and Furan Values on the Titanium Dioxide Plant Site Various dioxin and furan congeners were found in samples taken at the plant site. We report here only the finding of congener 2,3,7,8 TCDD from seven of the on-site samples. The concentrations of this congener ranged from 0.153 ng/kg to 21.1 ng/kg in solid samples, expressed on a dry weight basis. DISCUSSION Significance of Corrected Toxic Equivalents of Dioxins in Shellfish The increase in actual calculated toxic equivalency factors using the World Health Organization system (WHO-TEQ) simply strengthens our conclusion that the shellfish are contaminated contaminated, v 1. made radioactive by the addition of small quantities of radioactive material. 2. made contaminated by adding infective or radiographic materials. 3. an infective surface or object. with dioxins and furans, that the most likely source is the titanium dioxide plant located on the north shore of St. Louis Bay and that such contamination may contribute to a public health risk. The reduction in the two calculated I-TEQ values for shellfish tracts 2 and 3, changes our estimate of the increase in dioxins in Mississippi shellfish since 1997. These I-TEQ values were only calculated so that our data could be compared with the 1997 United States Food and Drug Administration United States Food and Drug Administration (FDA), n.pr a unit of the Public Health Service created to protect the health of the nation against impure and unsafe foods, drugs, and cosmetics. data published by Fiedler et al. (1997). From our original calculations we estimated that total dioxins in shellfish had increased by a factor of between 1.7 and about 8.0 times since 1997, during an interval when dioxins were decreasing in foodstuffs foodstuffs npl → comestibles mpl foodstuffs npl → denrées fpl alimentaires foodstuffs food npl → nationwide because of reduced industrial emissions of these contaminants. Our revised I-TEQ estimates show that the actual estimated range of increase should be 1.7-3.1 times. This estimated increase is fortunately not as large as originally calculated but still represents an unexpected increase that runs counter to the national trend, suggesting a nearby source of contamination. This increase of between 1.7 and 3.1 times should still be a cause for concern. Discovery of 2,3,7,8-TCDD on the Titanium Dioxide Plant Site We examined the United States Environmental Protection Agency Toxic Release Inventory (TRI TRI Toxics Release Inventory (US EPA) TRI Touch Research Institute TRI Taux de Rentabilité Interne (French: internal rate of return) TRI Taux de Rentabilité Interne TRI Tile Roofing Institute ) Program's TRI Explorer (www.epa.gov/enviro/html/tris/) (USEPA 2003) data in our original study to assess the potential release of dioxins and furans from the plant. The data appearing in this inventory is submitted by the industrial plant on a voluntary basis. No report of 2,3,7,8-TCDD release from the titanium dioxide plant was ever found in our examination of the EPA-TRI database. However, as we reported previously, the only two locations in which congener 2,3,7,8-TCDD were found in the sediments of St. Louis Bay in our study were from sediment sites 2 and 3, the two sediment stations located closest to the plant outfall site. This new data thus adds support to our conclusion that the dioxins, including 2,3,7,8-TCDD found in sediments adjacent to the plant outfall, originated from the plant site. In addition, the detection of 2,3,7,8-TCDD from scale scraped from the top of the line 2 fume stack (now dismantled) demonstrates with certainty that 2,3,7,8-TCDD was released into the atmosphere from this fume stack and constitutes a source of the compound deposited in St. Louis Bay. Conclusions of Original Report and this Report The data corrections in this report do not change the conclusions of the original report (Elston et al. 2005). In fact, Table 1 shows that the WHO-TEQ values for shellfish in St. Louis Bay and adjacent waters of Mississippi Sound are, on average, about 1% greater than previously reported. Thus, if any modification of conclusions is indicated from this change, it is that there is more concern about dioxin contamination in shellfish than previously reported. The reduction in the two values for shellfish sample tract numbers 2 and 3 expressed as I-TEQs and lipid adjusted I-TEQs change the range of estimated increase of dioxins in Mississippi shellfish since 1997. As indicated in the original report, an increase in such concentrations is surprising at a time when national trends are for decreasing concentrations of dioxins in food stuffs (e.g., USEPA 1991, Smith et al. 1995, Pearson et al. 1995, Pinsky & Lorber 1998, Winters et al. 1998). However, we acknowledge that the calculated upper estimate of increase is by a factor of about 3.1 rather than by a factor of about 8. Therefore, the corrected estimate is that dioxins in shellfish from southern Mississippi appear to have increased by a factor of from 1.7-3.1 between 1997 and 2004. Perhaps the most significant new information is the documentation of the presence of 2,3,7,8-TCDD on the titanium dioxide plant site. This compound, which is assigned the reference WHO-TEF of 1.0, is recognized as the most toxic dioxin and as a carcinogen by the World Health Organization's International Agency for Research on Cancer (WHO 1997). The new information that now confirms the previously and apparently unknown or unreported presence of 2,3,7,8-TCDD on the site supports our belief that the concentrations of this congener found in marine sediments marine sediment Any deposit of insoluble material, primarily rock and soil particles, transported from land areas to the ocean by wind, ice, and rivers, as well as the remains of marine organisms, products of submarine volcanic activity, and chemical precipitates from near the plant outfall, and at a further site in Mississippi Sound, originated from the plant site. The lack of reporting of this congener on the EPA-TRI site, given the demonstration of 2,3,7,8-TCDD on the site, further calls into question the reliability and utility of the EPA-TRI data as a means of assessing public health risk. As we noted in the original report, because of the specific source of metals, particularly chromium and nickel, the increase of these in sediments and particularly in shellfish, the association of dioxin with the plant outfall and the lack of other reporting of large sources of these contaminants in the watershed, we conclude that the most likely source of these elevated contaminants in St. Louis Bay and the adjacent waters of Mississippi Sound is the titanium dioxide plant on the northern shore of St. Louis Bay. In addition, with respect to dioxin contamination of St. Louis Bay and adjacent Mississippi Sound, this conclusion is strengthened by the new data presented in this addendum showing the presence of 2,3,7,8-TCDD on the plant site. ACKNOWLEDGMENTS Funding for the new data presented in this study was provided to Chemical Consulting Services of College Station, Texas College Station is a city in Brazos County, Texas, situated in Central Texas. It is located in the heart of the Brazos Valley. The city is located within the most populated region of Texas, near to three of the 10 largest cities in the United States - Houston, Dallas, and San by contract from Baron &Budd, P.C., Dallas, Texas “Dallas” redirects here. For other uses, see Dallas (disambiguation). The City of Dallas (pronounced [ˈdæl.əs] or [ˈdæl. . LITERATURE CITED Elston, R. A., E. W. Cake, Jr., K. Humphrey, W. C. Isphording & J. E. (Jack) Rensel. 2005. Dioxin and heavy-metal contamination of shellfish and sediments in St. Louis Bay, Mississippi and adjacent marine waters. J. Shellfish Res. 24:227-241. Fiedler, H., K. R. Cooper, S. Bergek & C. Rappe. 1997. Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) in food samples collected in southern Mississippi, USA. Chemosphere chemosphere: see atmosphere. 34:1411-1419. Lytle, T. F. & S. J. Lytle. 1982. Heavy metals in oysters and clams of St. Louis Bay, Mississippi. Bull. Environ. Contam. Toxicol. 29:50-57. Pearson, R. F., D. L. Swackhamer & S. J. Eisenreich. 1995. Concentrations, inventories and accumulations of polychlorinated dibenzo-p-dioxins and dibenzofurans in the sediments of the Great Lakes Great Lakes, group of five freshwater lakes, central North America, creating a natural border between the United States and Canada and forming the largest body of freshwater in the world, with a combined surface area of c.95,000 sq mi (246,050 sq km). . Organohalogen Compounds 24:267-271. Pinsky, P. & M.N. Lorber. 1998. A model to evaluate past exposure to 2,3,7,8-TCDD. J. Expo. Anal. Environ. Epidemiol. 8(2): 187-206. Smith, R. M., P. W. O'Keefe, D. Hilker, S. Conner & E. Posner. 1995. Direct and indirect contributions of atmospheric PCDDs and PCDFs to Hudson River Hudson River River, New York, U.S. Originating in the Adirondack Mountains and flowing for about 315 mi (507 km) to New York City, it was named for Henry Hudson, who explored it in 1609. Dutch settlement of the Hudson valley began in 1629. national estuarine research reserve The National Estuarine Research Reserve program of the United States government under the auspices of the National Marine Protected Areas Initiative. The program establishes federal-state partnerships under the Coastal Zone Management Act to create a system of estuarine research sediment cores. Organohalogen Compounds 24:141-145. USEPA. 1989. Interim procedures for estimating risks associated with exposures to mixtures of chlorinated chlorinated /chlo·ri·nat·ed/ (klor´i-nat?ed) treated or charged with chlorine. chlorinated charged with chlorine. chlorinated acids some, e.g. dibenzo-p-dioxins and dibenzofurans (CDDs and CDFs) and 1989 update. Washington, D.C.: Risk Assessment Forum. EPA/625/3-891016). See also http://www.epa.gov/ wtc/dioxin/dioxin fact sheet.html for discussion of USEPA discussion of toxic equivalency factors. USEPA. 1991. Chlorinated dioxins and furans in the general United States United States, officially United States of America, republic (2005 est. pop. 295,734,000), 3,539,227 sq mi (9,166,598 sq km), North America. The United States is the world's third largest country in population and the fourth largest country in area. population: NHATS FY87 results. Report EPA-560/5-91-003. Office of Toxic Substances, United States Environmental Protection Agency, Washington, DC. USEPA. 1997. Polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) by high-resolution gas chromatography/ high resolution mass spectrometry mass spectrometry or mass spectroscopy Analytic technique by which chemical substances are identified by sorting gaseous ions by mass using electric and magnetic fields. (HRGC/HRMS). SW846, Method 8290. United States Environmental Protection Agency. Washington, DC. http://www.epa.gov/epaoswer/hazwaste/test/pdfs/8290.pdf USEPA. 2003. Toxic Release Inventory (http://www.epa.gov/tri). United States Environmental Protection Agency. Washington, DC. Vanden Berg, M., L. Birnbaum, A. T. C. Bosveld, B. Brunstrom, P. Cook, M. Feeley, J. P. Giesy, A. Hanberg, R. Hasegawa, S. W. Kennedy, T. Kubiak, J. C. Larsen, F. X. R. van Leeuwen, A. K. D. Liem, C. Nolt, R.E. Peterson, L. Poellinger, S. Safe, D. Schrenk, D. Tillitt, M. Tysklind, M. Younes, F. Waern & T. Zacharewski. 1998. Toxic Equivalency Factors (TEFs) for PCBs, PCDDs, PCDFs for Humans and Wildlife. Environmental Health Perspectives 106 (12). EHP EHP abbr. 1. effective horsepower 2. electric horsepower Online: http:// ehp.niehs.nih.gov/members/1998/106p775-792vandenberg/ vandenberg-full.html Winters, D.L., S. Anderson, M. Lorber, J. Ferrario & C. Byrne. 1998. Trends in dioxin and PCB PCB: see polychlorinated biphenyl. PCB in full polychlorinated biphenyl Any of a class of highly stable organic compounds prepared by the reaction of chlorine with biphenyl, a two-ring compound. concentrations in meat samples from several decades of the 20th century. Organohalogen Compounds 38:75-77. World Health Organization 1997. International Agency for Research on Cancer. Available at: http://www-cie.iarc.fr/htdocs/monographs/vo169/ dioxin.html RALPH ELSTON, (1) * EDWIN W. CAKE, JR., (2) KAREN HUMPHREY Karen Humphrey was mayor of Fresno, California between 1989 and 1993. She was Fresno's first and to date only female mayor. She lost re-election to businessman Jim Patterson. List of Fresno Mayors
(1) AquaTechnics Inc. PO Box 687 Carlsborg, Washington Carlsborg is a census-designated place (CDP) in Clallam County, Washington, United States. The population was 855 at the 2000 census. Geography Carlsborg is located at (48.084085, -123.170290)GR1. 98324; (2) Gulf Environmental Associates, 2510 Ridgewood Road, Ocean Springs, Mississippi Ocean Springs is a city in Jackson County, Mississippi (USA), about 2 miles east of Biloxi. It is part of the Pascagoula, Mississippi Metropolitan Statistical Area. The population was 17,225 at the 2000 census. The town has a reputation as an "arts community. 39564; (3) Department of Earth Sciences, University of South Alabama The University of South Alabama is a public, doctoral-level university in Mobile, Alabama, USA. It was created by the Alabama Legislature in 1963, and replaced existing extension programs operated in Mobile by the University of Alabama. , Mobile, Alabama 36688; (4) Chemical Consulting Services, 1300 Angelina Court, College Station, Texas 77840; (5) Rensel Associates Aquatic Sciences, 4209 234th Street N.E., Arlington, Washington Arlington is a city located in northern Snohomish County, Washington, USA, bordered by the city of Marysville to the south. As of the 2004 census, the city had a total population of 14,491. 98223 * Corresponding author. E-mail: ralph@aquatechnics.com
TABLE 1.
Dioxin toxicity equivalent concentrations for St. Louis Bay,
Mississippi shellfish samples. (1)
Shellfish
Sample WHO-TEQ
Trach Percent (ND-1/2)
Number Lipid [[pg/g].sub.2]
1 0.35% 0.639
2 0.55% 0.444
3 0.35% 0.376
4 0.70% 0.419
5 0.66% 0.451
6 0.53% 0.438
7A 0.54% 0.414
7B 0.71% 0.508
7C 0.60% 0.437
8 0.34% 0.389
9C 0.46% 0.389
9D 0.64% 0.391
15 0.58% 0.340
16 0.46% 0.381
17 1.07% 0.457
Average all samples: 0.431
Average oysters only
(all except #1): 0.417
I-TEQ
Shellfish (ND = 1/2)
Sample I-TEQ [corrected for
Trach (ND-1/2) lipid]
Number [[pg/g].sub.3] [[pg/g].sup.4]
1 0.579 165.544
2 0.411 74.679
3 0.332 94.866
4 0.379 54.147
5 0.413 62.505
6 0.400 75.474
7A 0.364 67.429
7B 0.451 63.568
7C 0.379 63.118
8 0.330 96.995
9C 0.364 79.124
9D 0.352 55.038
15 0.294 50.627
16 0.334 72.654
17 0.391 36.561
Average all samples: 0.385 74.155
Average oysters only
(all except #1): 0.371 67.628
(1) Toxicity equivalencies (WHO-TEQ and I-TEQ) calculated
using World Health Organization toxic equivalence factors
(WHO-TEF, Vanden Berg et al. 1997) and International toxic
equivalency factors (I-TEF, USEPA 1989), respectively. All
values expressed as pg dioxin equivalent per g of shellfish
tissue, wet weight. Congeners measured are shown in Table 2
of Elston et al. 2005.
(2) Values in this column are calculated using values for
non-detects at 1/2 the detection limit (ND = 1/2) (USEPA 1989).
(3) Values in this column are given to provide a basis for
comparison with Fiedler et al. (1997) who used I-TEF conversion
factors and used 1/2 the limit of quantification for no detect
congener values.
(4) Values in this column are adjusted for lipid, assuming that
all dioxins and furans are contained in lipids, and thus
represent the calculated concentration using such an assumption.
Thus the values in the far right column are comparable to the
values published by Fiedler et al. (1997), after adjustment
so that only the congeners measured in each study are
included in a comparison.
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