ho lo 1Bq1ar1h it9Vf1I ators N! 1sigo1offl oibijf? . iefu Isnenino3 tIerI2 Isfnemnoiivn3 nema2e22A bLob iiii Wql U.S.,. DEPARTMENT 0~.:CONIIVI~RcE . .,::,, : ~:;::: 5$ National Oceanicand -Atmospheric Administrationj,,y ~ .Z, ,;.. (9 UAJL011WduIJ of the Alaskan Final Reports of Principal Investigators Volume 5. Biological Studies Outer Continental Shelf Environmental Assessment Program Boulder, Colorado 80303 March 1979 t I U.S. DEPARTMENT OF COMMERCE Juanita M. Kreps, Secretary OTARJ National Oceanic and Atmospheric Admirustration Richard A, Frankl Administrator The facts, conclusions and issues appearing in these reports are based on interim results of an Alaskan environmental studies program managed by the Outer Continental Shelf Environmental Assessment Program (OCSEAP) of the National Oceanic and Atmospheric Administration (NOAA), U.S. Department of Commerce, and primarily funded by the Bureau of Land Management (BLM), U.S. Department of Interior, through interagency agreement. DISCLAIMER Mention of a commercial company or product does not constitute an endorsement by National Oceanic and Atmospheric Administration. Use for publicity or advertising purposes of information from this publication concerning proprietary products or the tests of such products is not authorized. ii CONTENTS Flu # INVESTIGATOR(S) AGENCY TITLE PAGE 75 Donald C. Malins Northwest and Assessment of 1 Alaska Fisheries Available Literature o Center, Seattle on Effects of Oil Pollution on Biota in Arctic and Subarctic Waters 340 C. J. Lensink U.S. Fish& Migration of Birds 245 J. C. Bartonek Wildlife Service, in Alaska Marine Anchorage Habitats 441 P. G. Mickelson Institute of Avian Community 289 Arctic Biology, Ecology at Two Fairbanks Sites on ?3spenberg Peninsula in Kotzebue Sound, Alaska 458 Gerald F. Shields Institute of Avian Community 608 Leonard J. Peyton Arctic Biology, Ecology of the Fairbanks Akulik-Inglutalik River Delta, Norton Bay, Alaska iii ADMINISTRATIVE DOCUMENT: OCSEAP FINAL REPORT Contract #: R7120818 Research Unit: 75 Reporting Period: July 1, 1975-September 30, 1976 Number of Pages: ASSESSMENT OF AVAILABLE LITERATURE ON EFFECTS OF OIL POLLUTION ON BIOTA IN ARCTIC AND SUBARCTIC WATERS Donald C. Malins, Editor Environmental Conservation Division National Marine Fisheries Service, NOAA Northwest and Alaska Fisheries Center 2725 Montlake Boulevard East Seattle, Washington 98112 November 1976 PETROLEUM IN MARINE ENVIROWNTS AND ORGANISMS INDIGENOUS TO THE ARCTIC AND SUBARCTIC Donald C. Malins Editor Environmental Conservation Division National Marine Fisheries Service Northwest and Alaska Fisheries Center 2725 Montlake Boulevard East Seattle, Washington. 98112 This is the third and final section of a three section final report. Sections I and II were published as follows: Malins, D.C., Editor (1977). Effects of Petroleum on Arctic and Subarctic Marine Environments and Organisms, Academic Press, NY. September 1976 2 INTRODUCTION The material included in this volume comprises Section 111 of the Literature Review commitment under OCSEAP Research Unit 75. The objectives were: review of the available literature as described in Task Element Cl: (a) on toxicity of crude oils and crude oil components (including heavy metals), and (b) on the composition and toxicity of formation waters, various drilling muds, and their components: Compare these toxicities on the basis of species, life stage, temperature exposure, water source, oil source, geographic source of organism, and presence of heavy metals. The subjects included in this section encompass the potential sources and levels of trace metals in the marine environment and their potential biological effects in relation to petroleum drilling and transport operations in arctic and subarctic environments. Four metals-- cadmium, lead, chromium, and nickel--were chosen for detailed study in relation to their biological effects on organisms. The rationale for this choice was based on the metal compositions of petroleums, the respective metal toxicities, and other considerations. (See Chapter by Clark and Brown). Section III represents the efforts of eight specialists on the staff of the Environmental Conservation Division of the Northwest and Alaska Fisheries Center. The extent of coverage and the emphasis and interpretation of findings are uniquely the authors. In submitting this document, appreciation is again extended to the individuals acknowledged in Section 1. Donald C. Malins Principal Investigator 3 SECTION III POTENTIAL IMPACT OF TRACE METALS FROM PETROLEUM DRILLING AND TRANSPORT OPERATIONS ON ARCTIC AND SUBARCTIC MARINE ENVIRONMENTS: SOURCES, LEVELS AND BIOLOGICAL EFFECTS LEVELS & SOURCES OF CRITICAL TRACE METALS IN THE MARINE ENVIRONMENT Robert C. Clark, Jr. ACUTE TOXICITY OF HEAVY METALS Donovan R. Craddock. PATHOLOGY OF ARCTIC AND SUBARCTIC MARINE SPECIES AND EXPOSURE TO TRACE METALS ASSOCIATED WITH PETROLEUM Harold O. Hodgins & Joyce W. Hawkes . METABOLISM OF TRACE METALS: BIOACCUMULATION & BIOTRANSFORMATION IN MARINE ORGANISMS Usha Varanasi &Donald C!. Malins . BEHAVIORAL & PHYSIOLOGICAL EFFECTS INDUCED BY SUBLETHAL LEVELS OF HEAVY METALS William R. Reichert. GE!4ERAL EFFECTS OF METALS ON THE ECOSYSTEM HerbertR. Sanborn. 4 LEVELS AND SOURCES OF CRITICAL TRACE METALS IN THE MARINE ENVIRONMENT by Robert C. Clark, Jr. Environmental Conservation Division . I. INTRODUCTION. .O “ ● * “ A. Nature of certain elements in the environment . B. Bioconcentration of trace elements. C. Classification of trace elements. II. CRITICAL TRACE METALS IN PETROLEUM. A. Copper and mercury. “ . B. Chromium. 1. Levels. 2. Sources . c. Nickel. ● . ● . 1. Levels. ✎ . ✎ . 2. Sources . ✎ . ✎ . D. Cadmium . 0 s . ‘ . 1. Levels. 2. Sources . E. Lead. e . 1. Levels. 2. Sources . III. CRITICAL TRACE METALS IN THE AQUATIC ENVIRONMENT. IV. REFERENCES. v. TABLES. 5 a LEVELS AND SOURCES OF CRITICAL TRACE METALS IN THE MARINE ENVIRONMENT by Robert C. Clark, Jr. Environmental Conservation Division INTRODUCTION Over 80 elements have been identified and quantified in seawater and at least 60 of them have been found in some crude petroleums or in the associated production waters. Pollutants produced by industrial technology contain a broad spectrum of heavy metals and other inorganic materials. The rapid advances of technology have resulted in steady increases in the drilling for and the transportation of crude oiI. and in the development of an enormous petrochemical industry capable or producing thousands of by- product or waste substances. Petrochemical wastes include both organic and inorganic substances. The gamut of these industrial wastes eventually makes its way into the environment with the majority ending up in some compartment of the marine environment [1]. NATURE OF CERTAIN ELEMENTS IN THE ENVIRONMENT Some of the elements in petroleum are also found in seawater where they range in concentration from a few percent to parts per trillion (10-9) . The ecological aspects, or effects, of these elements may range from beneficial (essential) to detrimental (toxic). Any assessment of the biological effects of trace metals from petroleum on the marine environment must consider the I.evels of these elements in petroleum, drilling chemicals, and production (brine) waters; the levels naturally present in seawater; the chemical form of the metals; and the reactivity and toxicity of the chemical forms of the metals. 6 , J Table 1 summarizes the known information about the elements found in seawater and in petroleum and its production waters. Concentration units are given in micrograms per liter of solution (approximately parts per billion, 10-9 Or ppb)o Data on concentrations of the elements in sea- water and on the principal chemical form (species) were taken mainly from the National Academy of Sciences publication Marine Chemistry [2], the text, Introduction .to Marine Chemistry, by Riley and Chester [3], and the recent comprehensive review of minor elements in seawater by Brewer [108]. The principal chemical form of the element found in seawater can be an important factor in an element’s effect on the marine biota. The lethal concentration of some toxic elements varies with the valency states of the elements (chromium in the +3 or +6) 01 with their chemical forms (methyl mercury is more toxic than mercuric chloride). Table 1 [column titled “Principal and (% free)”] also contains an estimate of the percentage of the chemical form present in the undissociated state in seawater. Some of the compounds may be present in the solvated states; others may consist of ion-pairs which result from a purely electrostatic attraction between 0 oppositely charged ions, such as MgS04 (11% of magnesium occurs in sea- 0 water as this ion-pair), MgHC03+ (l%), MgC03 (0.3%) [4]. An element may be present in seawater only at low levels for one or both of two reasons. First, it may be very reactive in the marine environ- ment so that its removal by biological or sedimentary means is rapid. Secondly, the source materials may contain low levels of the element. Thus aluminum, a major constituent in igneous rocks, is a minor element in seawater because of its high reactivity. One estimate of the relative reactivity of elements can be obtained on the basis of their residence times in seawater. Elements with long residence times--the lower atomic number alkali metals and alkaline earths (excluding beryllium)--are characterized by the low reactivity of their ions. Those with short residence times (less than 1,000 years: Be, Al, Fe, La, Ce, Pr, Nd, Sm,