Document NEaZ2y0JRnX2E4brZyoVgXXBD

Chlorinated Hydrocarbons in the Marine Environment A Report Prepared by the PANEL ON MONITORING PERSISTENT PESTICIDES IN THE MARINE ENVIRONMENT of the COMMITTEE ON OCEANOGRAPHY NATIONAL ACADEMY OF SCIENCES WASHINGTON, D.C. 1971 HONS 070576 9 Preface It is most difficult to predict things to come for our society and for our environment. For society, the rapidity of technological advances and concomitant changes in living patterns limit our description of the future to a fraction of a decade at best. For the environment, alteration of our surroundings on a global basis takes place much more slowly, involving changes that often are imperceptible in a free* tion of a decade. Our ability to manipulate the environment, climate, and various assemblages of living organisms is the hallmark of our advanced technology. The consequences are yet to be understood. A few scientists have foretold the environmental catastrophes of the past. In the case of DDT, introduced to agriculture during World War II, there were warnings of its impending deleterious impact upon the environment several years after its first use as a pesticide. In 1946, Clarence Cottam and Elmer Higgins of the Fish and Wildlife Service wrote: From the beaming of Its wartime use as an iniecticide the potency of ddt hat been the cause of both enthusiasm end grave conoem. Some have come to con* aider it e cure aU for insect pests; others are alarmed because of its potential harm. The experienced control worker realises that dot, Uke every other effective in secticide orrodeadcide, is really a twowdged sword; the more potent the poison, iii Qian1 HONS IV PREFACE the mort duniga it it capable of doing. Mott organic tnd minartl poitont an specific to t dtgrM; they do not ttiika the innumerable animal and plant apedet with equal effectiveneat; if theta poitont did. the advantage of control of unde* Arabia tpedea would be more than offaet by the detriment to dehrabie and ben* ficial forms, ddt it no exception to this rule. Certainly such an effective poison will destroy beneficial insects, flahet, and wildlife. Although many more investigations are needed in all theta fields, it seems that the most pressing requirement is a study to determine the effects of DOT as ap plied to agricultural crops on the wildlife and game dependent upon an agricul tural environment. About 80 percent of our game birds, as well as a very high percentage of our nongams and insectivorous birds, and mammals are largely dependent upon an agricultural environment. In such places application of ddt will probably be heavy and widespread; therefore it is not improbable that the greatest damage to wildlife will occur there. Because of the sensitivity of fishes and crabs to DDT, avoid aa far as posaibia direct application to streams, lakes and coastal bays. Whenever ddt is used, make careful before and afttr observations of mam mals, birds, and flshss, and other wildlife. In the spring of 1970, the Committee on Oceanography estab lished the Panel on Monitoring Penutent Pesticides in the Marine Environment to study the impact of DOT and other chlorinated hy drocarbons, including those of industrial origin, on the marine envi ronment and to suggest courses of action baaed upon its findings. The Panel convened at WUUamstown, Maemchusetts, In July 1970, as par ticipants in the Study of Critical Environmental Problems (scep), arranged by the Maasachuaetts Institute of Technology. Through our studies and discussions, we see dearly that the obser vations and predictions of Cottam and Higgins have been confirmed by subsequent events. Yet man's knowledge of the fate and behavior of the chlorinated hydrocarbons in the marine environment remains inadequate. Estuarine fish-eating birds are building up such high body burdens of DDT tnd its degradation products that they are suffering extensive failures in the reproductive process. The mechanisms whereby ddt and its residues move from the continents to the ma rine environment to the Hah are still not clearly understood. This report is not intended to represent an exhaustive survey of the literature. It hat been prepared to alert the community of marine scientists to one of the more serious problems arising from the dis persal of man's materials to his surroundings. Emphasis has been placed upon DDT and its degradation products because they have been the most studied to date. Through this report, the Panel has attempted to point out lacunae in man's knowledge and to suggest remedial actions. We have extended and amplified on the predictions HONS 07057a MSFACS V of Cottam and Higgins, made over 25 yean ago, hoping that a similar report will not be noceaary 25 yean hence. The one-month Study of Critical Environmental Problems, which covered tnvel expenses of the Panel members, was supported by a group of thirteen federal agencies and four private foundations. Many members of the Study contributed substantially to the Panel's report. Appendix A, on the proposed base-Une sampling program, and Appen dix B, on identification of globally distributed wastes in the marine environment, were prepared as working papers in cooperation with other scientists participating in SCEP and are included here with the permission of the Study. There working papers, along with others prepared for SCEP, will be published in the forthcoming MIT Press publication Man's Impact on Tintstrial and Oceanic Ecosystems, edited by William H. Matthews, Frederick E. Smith, and Edward D. Goldberg. The preparation of this report was carried out as one of s series of studies under the auspices of the Ocean Affairs Board. The Board was formed in December 1970 to enlarge upon the activities and responsi bilities of the former NAS Committee on Oceanography (formed in 1957). The Board operates under the joint sponsorship of the Office of Naval Research, the Atomic Energy Commisrion, the Department of the Interior, the National Science Foundation, the National Oce anic and Atmospheric Administration, and the Coast Guard. PANEL ON MONITORING PERSISTENT PESTICIDES IN THE MARINE ENVIRONMENT Edward D. Goldberg, Chairman Philip Butler Paul Meier David Menzel Gerald Paulik Robert Risebrough Lucille F. Stickel MOKS 070579 Contents CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT Summary and Recommendation!, 1 U.S. and World Production of Chlorinated Hydrocarbons, 2 Transport of DDT Residues and PCI's to the Marine Environment, 4 Distribution of Chlorinated Hydrocarbons in the Marine Environment, 6 The Ecological Impact, 8 Plankton,8;Crustaceans,9;MoUuiks,9;Fish, 10;Birds, II Biochemical Effects, 13 Recommendation: A National Effort to Curtail Long-Term Effects of Chlorinated Hydrocarbons on Community Structure, 14 Recommendation: A Chlorinated Hydrocarbon Base-line Program for the Marine Environment, 15 Recommendation: Removal of Obstacles to Public Access to Chemical Production Data, 17 VI HONS 070580 APPENDIX A: PROPOSED BASE-LINE SAMPLING PROGRAM Wind Systems, 23 Ocean Current Systems, 26 Organisms, 26 Rivers, 31 Glacial, Rain, and Sediment Samples, 34 Summary, 35 APPENDIX B: IDENTIFICATION OF GLOBALLY DISTRIBUTED WASTES IN THE MARINE ENVIRONMENT VII MGNS 070581 EDWARD D. GOLDBERG PHILIP BUTLER PAUL MEIER DAVID MENZBL ROBBRT W. RISBBROUGH LUCILLE F. STICKEL Chlorinated Hydrocarbons in the Marine Environment SUMMARY AND RECOMMENDATIONS The oceans are an ultimate accumulation site for the persistent chlori nated hydrocarbons. As much as 25 percent of the ddt compounds produced to date may have been transferred to the sea. The amount of DDT compounds in the marine biota is estimated to be less than 0.1 percent of total production, yet this amount has produced a de monstrable impact upon the marine environment. Populations of fish-eating birds have experienced reproductive failure and decline. With continued accumulations of persistent chlorinated hydrocarbons in the marine ecosystem, additional species will be threatened. Continued release of these pollutants to the envi ronment can only accelerate the accumulation of unacceptable levels of persistent chlorinated hydrocarbons in the tissues of marine food fish. Certain risks in the utilization of chlorinated hydrocarbons are especially hard to quantify, but they require serious consideration. The rate et which such subtttnoes degrade to harmless products in the marine system is unknown; the half-lives of some of the more per sistent materials are certainly of the order of years, and perhaps even 1 HONS 070502 2 CHLORINATED HYDROCARBONS IN THK MARINI ENVIRONMENT of decades or centuries. If most of the remaining 75 percent of the persistent chlorinated hydrocarbons is now in reservoirs that will in time transfer their contents to the sea, we may expect an increased level of these substances in marine organisms, despite future improve ments of manufacturing practices. In fact, if these compounds de grade with half-lives of decades or longer, there will be no opportu nity to redress the consequences. The more the problems are studied, the more unexpected effects are identified. In view of the findings of the past decade, our predic tion of the potential hazards of chlorinated hydrocarbons in the marine environment may be vastly underestimated. The Panel makes the following recommendations, which will be developed and expanded in the remainder of the report: A massive national effort should be made immediately to effect i drastic reduction of the escape of persistent toxicants into the envi ronment, with the ultimate aim of achieving virtual cessation in the shortest possible time. Programs should be designed both to determine the rates of entry of each pollutant into the marine environment and to make base-line determinations of the distribution of the pollutants among the com ponents of that environment* These should be followed by a program of monitoring long-term trends in order to record progress and to document possible disaster. The laws relating to the registration of chemical substances and the release of production figures by government should be examined and perhaps revised in light of evidence of environmental deteriora tion caused by some of these substances. U.S. AND WORLD PRODUCTION OF CHLORINATED HYDROCARBONS The U.S. production figures for DDT, for the aldrin-toxaphene* group, and for polychlorinated biphenyls (PCB's) are presented in Table l. The United States utilizes 70-80 percent of its production of the aldrin-toxaphene group and about 30 percent of the DDT manufactured. The remaining materials sre exported (Stickel, 1966). It is difficult to collect world production data for these materials because the information available is inadequate. Although some "Includes aldrin, chlordans, dMdrln, endiin, hsptscUor, and toxiphsnt. MGNS 070583 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT 3 TABLE 1 VI.S. Production of Chlorinated Hydrocarbons. In Units of 10* |/yr Ycsr 1968 1967 1966 1965 1964 1963 1962 1961 1960 1959 1958 1957 1956 1955 1954 1953 1952 1951 1950 1949 1948 1947 1946 1945 1944 Total DDT* 63.4 47.0 64.2 64.0 56.2 81.3 75.9 77.9 74.6 71.2 66.0 56.6 62.6 59.0 44.2 38.4 45.4 48.2 35.5 17.2 9.2 22.5 20.7 (5.1 4.4 1,220.0 Aldrin-Toxaphene Group* 52.7 54.6 59.3 54.0 47.9 48.2 48.3 47.2 41.2 39.5 44.7 34.3 39.4 3S.0 20.5 _ - - 670.0 rc* 5 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ - 5 *Chsmtaal Economics Sscvico, Department of liutnoas snd Industrial Economies, Stanford Rimsieb Institute (1951). 'Eitlmat# based upon eonsumor tafonmttoa. yurly figures may be found for a given country, comprehensive data for the major producers have not yet been compiled, hampering mass* balance calculations for dispersion of these materials around the earth and making an understanding of their behavior in nature difficult. An urgent need for such data is clear. Even more pressing is the need for the production figures for the polychlorinated biphenyls, which have been in use since the early 1930's. An inspection of the production and utilization figures that were available to us (Food and Agriculture Organiza* n, 1969) suggests MOMS 070584 4 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT that the total world production of DOT and the aldrin-toxaphene group is probably no more than one and one half times that of the United States. Thus, as a first approximation, the integrated world production (i.e., the total amount since production began) of ddt is 2.0 X101J g, and the production of the aldrin-toxaphene group is 1.0 X 10ia g. The production rate used in calculations, both for ddt and for the aldrin-toxaphene group, is I011 g/yr. TRANSPORT OF DDT RESIDUES AND PCB'S TO THE MARINE ENVIRONMENT The principal routes for transport of DDT residues* from places of application on land to the ocean are rivers, sewage outfalls, and the atmosphere. Total annual surface runoff of water from all continents has been estimated st 3.7 X I01* cc. The maximum concentration of DDT resi> dues in water reported in a survey of rivers of the western United States was about 100 parts per trillion (Manigold and Schultze, 1969; Bailey and Hannum, 1967). If all rivers of the world contained this maximum, 3.7 X10* g of DDT residues (approximately 3 percent of the annual production of the world) would be transported annually to the sea. This figure is probably inflated, perhaps by a factor of 10. A more conservative figure may be reached by observing that DDT residues transported by the Mississippi River into the Gulf of Mexico have been estimated at 10T g annually (Risebrough et a/., 1968b). The total river transport of DDT residues from the continental United States might be ten times that of the Mississippi, approaching I0C g. Domestic U.S. use of dot between 1961 and 1968 has ranged between 5 and 8 X 10>0 g/yr, thousands of times more than can be carried in the rivers; therefore, probably only about 0.1 percent (10* g) of the annual production of DDT reaches the oceans by surface runoff. The contribution of industrial effluent to hazardous pollution of the sea or of rivers that enter the sea cannot be quantitatively incor porated into the balance sheet for the oceans, but it cannot be disre garded. In Great Britain the source of chlorinated hydrocarbon residues found in the Firth of Clyde was traced (Holden, 1970), re- *DDT residue! is a term defining dot, DDE, end DOD. odd end DDE are me> taboUtsa of ddt, and ddd m also a pesticide in its own right. MGNS 070565 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT 5 suiting in the discovery that approximately 1 ton of PCB per year was dumped in the ocean with the sewage sludge from Glasgow sewage treatment plants. A comparable amount was dumped into the North Sea from the wastes of Manchester and into the Thames estuary from the wastes of London. Individual factories could not be identified as the source because many use the same sewers. In the United States, PCB's in aquatic organisms were similarly traced, disclosing a factory leakage on the Escambia River in Florida (Duke et a!., 1970). dot residues enter the atmosphere by several routes, including aerial drift during application by rapid vaporization from water sur faces (Acree et at., 1963) and by vaporization from plants and soils (Nash and Beall, 1970). Once in the atmosphere, DDT residues may travel great distances, entering the sea in precipitation or in dry fall out. There are few data for estimating these rates of transfer. Sam pling of DDT residues in precipitation has been most extensive in Great Britain, where total accumulation was measured at seven sta tions between August 1966 and July 1967. The mean concentration in those rainwater samples was 80 parts per trillion (Tarrant and Tatton, 1968), about twice that reported for meltwaters of recent Antarctic snow (Peterle, 1969). The DDT residues in south Florida precipitation averaged 1,000 parts per trillion in 18 samples taken at four sites between June 1968 and May 1969 (Yates et o/M 1970). Total annual precipitation of water over the oceans has been esti mated at 3.0 X 10M cc (Sverdrup era/., 1942). If this precipitation had an average concentration of DDT residues of 80 parts per trillion, a total of 2.4 X1010 g of DDT resdues would be transported annually to the oceans, about one quarter of the estimated total annual pro duction of DDT. It is at least plausible that the atmosphere is the major route for transfer of DDT residues into the oceans. Other chlorinated hydrocarbons with similar physical and chemical characteristics can be expected to have similar dispersal mechanisms. Dieldrin, which readily volatilizes into the atmosphere (Lichtenstein et a/., 1968), has bean found in airborne particulates over the ocean (Risebrough et a!., 1968b) and in rainwater (Tarrant and Tatton, 1968). Polychlorinated biphenyls have alto been detected in rainwater (Tarrant and Tatton, 1968). PCB has not yet been measured in river waters, but there is evidence that It occurs in the biota of the Atlantic in quantities of the same magnitude as residues of the DDT group. The relative importance of river transport, aerial fallout, sewage out falls, and dust discharge of PCB into the sea remains to be determined. MGNS 070586 6 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT DISTRIBUTION OF CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT Few data are available to document the concentration of chlorinated hydrocarbons (including PC8's) in the open ocean environment. How ever, a few observations indicate that DDT and its residues are prob ably distributed throughout the marine biosphere. Cray whales con tain up to 0.4 ppm DDT residues in their blubber, and sperm whales, up to .6 ppm (Wolman and Wilson, 1970). Gray whales feed largely on benthic organisms in the Chukchi and Bering seas, and sperm whales feed on larger pelagic organisms. Sea birds (petrels and shearwaters), which feed on planktonic organisms far from land, have concentrations of DDT residues as high as 10 ppm (Risebrough, unpublished data). Migratory Osh (tuna) cany up to 2 ppm of these same compounds in their gonads, and other marine mammals carry up to 800 ppm in their fat (Butler, 1969). In the latter two cases, it is not known whether these concentrations resulted from localized contact in coastal waters or were accumulated during the life of the organisms in the open ocean. In the coastal environment, DDT and its residues range from undetectable levels to 5.4 ppm in oysters (Butler, 1969). Concentra tions within these limits are highly variable locally and vary consider ably even within the same estuary. In spite of the paucity of useful data, some assumptions can be made for the marine environment, excluding estuaries, by assigning likely values for DDT residues to the biota of the open ocean and ex tending the calculations to a global basis. Such computations are valu able in that they identify potential sinks and provide order-of-magnitude estimates of most probable distributions. The following assumptions are made: 1. The standing crop of plankton (plant and animal) is 3 X 10,s g (Menzel, unpublished data). 2. The standing crop of fish is 6 X 1014 g, equal to 10 times the present annual fish harvest (Rhyther, 1969). 3. The concentration of DDT residues in plankton averages 0.01 ppm. 4. The concentration of Dr T residues in fish avenges 1.0 ppm. 5. A homogeneous distribution of DDT in the mixed layer (the upper 100 m of seawater, which are homogenized by the action of winds) has resulted from atmospheric transport from the continents. MGNS 0 70567 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT 7 By assigning the values in assumptions (3) and (4) to the calculated standing crop of organisms, (1) and (2), it is estimated that the total plankton now contain 3.0 X 107 g and fish 6 X 10" g of s>dt residues, both insignificant fractions of the total annual input of these residues to the environment (1011 g). We propose these estimates as upper limits to the size of the pool. With a saturation level of DDT* in water of 1 ppb (Bowman et of., 1960) and the volume of the mixed layer (upper 100 m of the ocean) as 0.025 X1014 ml, the surface waters of the ocean are capable of ac commodating a load of 7.5 X IQ13 got DDT, or approximately 3$ times the total production to date. There is no indication, however, thst DDT introduced into the marine environment is uniformly dis tributed in the mixed layer. Enrichment is likely to occur in the sea's surface film, which contains fatty acids and alcohols. If this is the case, predictions indicate (a) that DDT may be stripped from this film by bacteria and phytoplankton, thus entering the food chain; (b) that it adsorbs to airborne particles that sink through the water column (in this case the compound is probably ingested by grazing organisms that do not discriminate between living and inert particles); or (c) that it codistills with water or la injected back Into the atmosphere as aero sols and is redistributed, leading to neither a net increase or decrease in concentration at the surface. Lacking any data for concentrations in the waters of the open sea, it is impossible to estimate directly how much is present that is not incorporated into living organisms. However, estimates of fallout in rain suggest that one quarter of the world's production of DDT may have entered the ocean, lta aerial distribution it probably uneven, de pendent upon weather patterns and proximity to major sources of input. If only 0.01 percent (10* g) can be accounted for in pelagic marine organisms, 0.50 X 1012 g (one quarter of total production) should be present in solution and in the bottom sediments. In order to balance input with accountable fractions, the surface mixed layer volume (0.02S X10M ml) should contain concentrations of approximately 5 X 10~ta g/ml, given a residence time of 5 years and an annual input of 0.25 X10`l g of DDT per year. "Saturation lavaU of odd and DDE have not yet been measured. HONS 070586 8 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT THE ECOLOGICAL IMPACT The acute and chronic toxicity or chlorinated hydrocarbons has been identified by observing the effects of chlorinated hydrocarbons under controlled laboratory conditions. The exposure of test populations of marine fauna to serial dilutions of these pollutants in flowing seawater has shown that they affect growth, reproduction, and mortality at concentrations currently existing in the coastal environments. These laboratory effects and their field counterparts are summarized in the following sections. Plankton The addition of chlorinated hydrocarbons to laboratory cultures of molluscan larvae and the phytoplankton on which they feed causes, with increasing concentrations, decreased growth rates, developmen tal failures, and increased mortality (Ukeles, 1962; Davis, 1961). By extrapolation, toxaphene levels observed, in one estuary of the south eastern United States in 1967, for example, were high enough to have caused the death of a majority of the phytoplankton suitable as food for molluscan larvae (Butler, 1969). In the open ocean, phytoplankton are at the base of the food chain and may act as primary concentrators of chlorinated hydrocarbons from the water. Laboratory evidence is available demonstrating inhibi tion of photosynthesis in single-celled marine plants by DDT, dieldrin, and endrin (Wurster, 1968; Menzei etal., 1970). It is doubtful, how ever, that these results are ecologically meaningful. The concentra tions necessary to induce significant inhibition far exceed expected concentrations in the open ocean and exceed by ten times the solu bility of DDT (I ppb) in water. One species tested was insensitive to concentrations of all three pesticides up to 1 ppm. Therefore, toxic ity may vary interspecifically, and, if not universally toxic, a chlori nated hydrocarbon might exert some control on species succession in the nearshore environment. If chlorinated hydrocarbons are concentrated in surface oil films, it is not improbable that concentrations there may reach levels suffi cient to cause acute toxicity to plants. Considering that this layer may extend 1 mm in depth, its effect would be to reduce total production within the euphotic zone (100-m depth) by about 10**. It must be borne in mind, however, that plants and bacteria may provide an effective means of extracting these hydrocarbons from the surface film. Partition coefficients have not been experimentally determined MGNS 070569 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT 9 from marine species but have been established as approximately 1,000 in the case of dieldrin for a freshwater alga (Reinert, 1967). These or ganisms are available as food to grating and surface-skimming feeders. The important fact here is not the effect of chlorinated hydrocarbons on primary production, but rather that plants may be the vehicle for transferring these compounds from the water to higher trophic levels. Experimental evidence from the calanoid copepod Pseudodiaptomus comatus has shown that the development of adults from nauplii is completely blocked when hatched from egg-bearing females main tained in seawater containing 10 parts per trillion DDT (Menzel, Anderson, and Randtke, unpublished data). Significant mortality was observed at 5 parts per trillion. These concentrations of DDT are lower than expected in rainwater falling on the sea surface (80 parts per trillion). These observations cannot be applied to the open oceans, because, as noted earlier, no measurements of DDT concen trations are available from these waters. Crustaceans Bioasaay tests show that laboratory populations of commercial species of shrimp and crabs as well as zooplankton are killed by exposure to chlorinated hydrocarbons, such as DDT and PCB, in the parts per bil lion range (Butler, 1964; Duke et at., 1970). Continuous exposure of shrimp to DDT concentrations of 0.2 ppb caused 100 percent mor tality in 18 days, and a concentration of 0.12 ppb caused 100 percent mortality within 28 days (Nimmo et al., 1970). Concentrations of this magnitude have been detected in Texas river waters flowing into commercially important shrimp nursery areas (Manifold and Schulze, 1969). Certainly in such contaminated areas there are significant in creases in mortalities of juvenile crustaceans. In California the declin ing production of Dungenesa crabs may be associated with observed DDT residues in the developing larvae. Polychlorinated biphenyls (Aroclor 12S4) at a concentration of S.O ppb caused 72 percent mor tality in 20 days to test populations of pink shrimp (Penaeus duorarum)\ these shrimp had accumulated 33 ppm of the PCB in their tis sues (Duke etal., 1970). Mollusks The chlorinated pesticides and PCB's characteristically interfere with the growth of oysters. One ppb of the PCB Aroclor 1254, for HONS 070590 10 CHLORINATSD H YD ROCARSONS IN THE MARINE ENVIRONMENT example, causes a 20 percent decrease in shell growth (Duke et ai., 1970). Many pesticides interfere with oyster growth at levels as low at 0.1 ppb (Butler, 1966b), in the ambient water. Moltusks generally concentrate these chemicals and thus serve as indicators of pollution levels in marine waters. Coastal monitoring samples have demon* strated that the magnitude of chlorinated hydrocarbon residues in mollutks are directly correlated with the application rates of these agricultural chemicals in adjacent river basins (Butler, 1967). Fish Marine fish are almost universally contaminated with chlorinated hy drocarbon residues. There is an expected concentration of such resi dues in lipid tissues such as the ovary. In the speckled sea trout on the south Texas coast, DDT residues in the ripe eggs are about 8 ppm. This level may be compared with the residue of 5 ppm in freshwater trout that causes 100 percent failure in the development of sac fry or young fish. The evidence is presumptive for similar reproductive fail ure in the sea trout. Sea-trout inventories in the Laguna Madre in Texas have shown a progressive decline from 30 fish per acre in 1964 to 0.2 fish per acre in 1969 (Table 2). It is significant that few juve nile fish have been observed there in recent years, although in less contaminated estuaries 100 miles away there Is a normal distribution of sea-trout year classes (Butler, 1969). Declines in the productivity of fish in California coastal waters have not yet been correlated with residues of chlorinated hydro- TABLE 2 Capture of Ssi Trout in Laguna Madre* You Number of See Trout Captured per Acre 1964 196$ 1966 1967 1968 1969 30 23 12 2.7 0.2 From Butler tt4. (1971). *No data mM for 19*7, m bunloanea daatioyad Ml the (Uhiiu gui. Tha docUna bi the Haber? tea baea oaty la tbe jevaaHa trout, wMcb eUndnetM tha poaaMIty of ovw-rWMny. The ODT laaitfeee la the soma of the adult trout reach a maximun of t ppm prior to pamdas. HONS 070591 CHLORINATED HYDROCARBONS IN THS MARINI ENVIRONMENT 11 carbons. However, the sale of some California mackerel has been prohibited because DDT residues exceed permissible human tolerance levels, even in the processed product. A kill of Mississippi River fish in 1963-1964 was traced to chemi cals entering the river system front an insecticide-manufacturing plant (Mount and Putnidd, 1966). Exceedingly high endrin concentrations were found in nearby sewers and in a riverside dump. Laboratory experiments have also established the concentration of several chlorinated hydrocarbons, including DDE, that damage repro ductive success of birds, fish, and marine invertebrates. Only prelimi nary work on the effects of PCB on marine organisms has been re ported. Concentrations of one or more chlorinated hydrocarbons in species from the marine environment exceed those found to have deleterious effects in the laboratory and have been correlated with population decreases or reproductive failures of a number of marine species. Signs of incipient damage that can be expected to develop further with continuing accumulation have also been reported. Birds Chlorinated hydrocarbon residues have seriously affected both adult birds and their reproduction. Deaths of bald eagles (Mulhern et a/., 1970), common loon (Butler, 1966a), and peregrine falcons (Jefferies and Prestt, 1966) have been correlated with lethal amounts of chlori nated hydrocarbons in body tissues. Widespread mortality of many coastal birds in the Netherlands and population decline of the sand wich tern were traced to dieldrin contamination of the Dutch Wadden Sea and the coastal North Sea resulting from factory effluent. Sea eagle reproduction has failed, and outright mortality has occurred in the Baltic Sea In association with very high levels of DDT compounds and PCI in the tissues (Jensen et a/.. 1969). Studies of museum series of eggs indicate that eggshell thinning has occurred since the mid-i 940's in a wide range of species of fish-eating birds and birds of prey. Where shell thinning has occurred, the popu lations have usually declined (Ratcliffs, 1967; Hickey and Anderson, 1968). Eggshell thinning and consequent population decline have been linked to chlorinated hydrocarbon residues found in eggs and in the body tissues of birds. In experimental studies, DOE in the diet of mallard ducks resulted in thin eggshells and reduced hatching success; p,p'-ODT produced HONS 070592 12 CHLORINATED HYDROCARBONS IN THB MARINE ENVIRONMENT the same effects, but to lesser degree (Heath tt at., 1 969). Both DDE alone and a combination of p,p'-DDT and dieldrin in the diet of American kestrels resulted in thin eggshells; the test of DOT plus diel drin was carried out long enough to show reduced hatching success (Porter and Wiemeyer, 1969; Wiemeyer and Porter, 1970). Black duck egg samples at Atlantic coastal sites in the United States showed highest residues of chlorinated hydrocarbons in states where duck reproduction is poorest. Nationwide sampling of wing tissues showed highest residues in the same areas (Reichel and Addy, 1968; Heath, 1969). In three states from which bald eagle eggs were analyzed, residues of DDT and dieldrin were highest in the eggs from the state where reproduction is poorest and has declined to nearly zero (Krsntzef of., 1970). Samples of brown pelican eggs from 12 Atlantic and Gulf colonies showed greatest shell thinning in the Carolina colonies, where popula tions have declined precipitiously. On the basis of museum series, it has been determined that shell thinning has occurred in all areaa (Blus, 1970; Anderson and Hickey, 1970). In the marine ecosystems of southern California, where concentra tions of the DDT compounds in fish may exceed 10 parts per million (Risebrough f a/., 1971), a disastrous reproductive failure occurred in 1969 among brown pelicans on Anacapa Island as a result of egg shell collapse (Jehl, 1969; Keith at at., 1970; Risebrough et at., 1970). In this area, the brown pelicans and double-created cormorants are no longer able to reproduce. At moat, four brown pelicans hatched in southern California in 1969 among approximately 1,200 nesting at tempts (Risebrough, Sibley, and Kirven, unpublished data). In 1970, only one brown pelican hatched in 500 attempts (Great, unpublished data). No double-crested cormorants were fledged in southern Cali fornia in 1969, and only one brood was fledged in 1970 (Gress, Risebrough, Jehl, and Kiff, unpublished data). The cause in all cases was a failure of the eggs to hatch because of breakage during incuba tion. Concentrations of the DDT compound DDE in the lipid fractions of the eggs were correlated inversely with shell thickness in brown pelican eggs from Anacapa Island, the Islas de Coronados in Mexico, other localities in Bgja California, and four colonies in Florida (Risebrough, Gress, Anderson, and Schreiber, unpublished data). By comparing pelican eggs from California and Florida, where the relative amounts of DDE and PCB are very different, the time investi- M0NS 070593 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT 13 gators concluded that DDE is the major cause of shell thinning in the brown pelican eggs. Pelican eggs collected on Anacspa in 1962 showed a critical level of shell thinning, but less than the thinning observed in 1969 and 1970 (Anderson and Hickey, 1970). Young pelicans were still produced on Anacapa in 1963 and 1964 (Banka, 1966). From the observed relationships between DDE concentration and shell thinning it can be concluded that between 1962 and 1969, accumulations of chlorinated hydrocarbons in the southern California marine ecosystem psssed t level critical to the brown pelican. Shell thinning has also been detected in marine and coastal birds in northern California, including the common murre (Gress, unpublished data), the ashy petrel (Risebrough and Coulter, unpublished data), and the American egret (Pratt and Risebrough, unpublished data). Continued buildup of chlorinated hydrocarbons in this ecosystem and in other marine ecosystems around the world will cause reproductive failures in these and other marine species. BIOCHEMICAL EFFECTS Several physiological effects of chlorinated hydrocarbons could ac count for shell thinning and for the abnormal behavior observed in contaminated populations. In affecting nerves, chlorinated hydro* carbons, including DDE, are believed to block the ion-transport pro cess by inhibiting one or more ATPases in the nerve membrane (Matsumura and Patil, 1969; Koch, 1969) that causes the required energy to be made available. Transport of ionic calcium across membranes such as those in the shell gland of birds is also an energy-requiring process dependent upon membrane ATPase (Comdino ttal., 1968). Inhibition of these enzymes by DDE could account for the concentration-effect curves obtained for shell thickness and DDE concentration in eggs of the brown pelican, double-crested cormorant (Anderson et a/., 1969), snd herring gull (Hickey and Andenon, 1968). DDE has also been found to Inhibit the enzyme carbonic anhydrase (Peakall, 1970; Risebrough et al.t 1970; Bitman et a/., 1970), essential for the depo sition of calcium carbonate in the eggshell and for the maintenance of pH gradients across membranes such as those in the shell gland. Inhi bition of this enzyme by such drugs as sulfanilamide results in the production of thin-shelled eggs. The chlorinated hydrocarbons, including DDE and PCB, induce HONS 070594 14 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT mixed-function oxidase enzymes In the livers of birds and mammals that hydroxylate and render water-soluble any foreign, lipid-soluble compounds (Conney, 1967; Risebrough etol., 1968a; Street etai., 1969) . Induction is usually a temporary phenomenon, ending when the inducing materials are themselves metabolized. DDE and the more heavily chlorinated PCB molecules are comparatively resistant to deg radation by the induced molecules, so they may persist as inducers for some time. The induced enzymes may therefore become constitu tive. The steroid hormones, such as estrogen and testosterone (Conney, 1967; Peakall, 1970) and thyroxine (Schwartz et al,, 1969), are metab olized at higher rates when these enzymes are induced. Lower estro gen concentrations are present in pigeons fed p,p'-DDT (Peakall, 1970) . Birds may also show symptoms of hyperthyroidism when fed a chlorinated hydrocarbon (Jefferies, 1969; Jefferies and French, 1969). RECOMMENDATION: A NATIONAL EFFORT TO CURTAIL LONG TERM EFFECTS OF CHLORINATED HYDROCARBONS ON COMMUNITY STRUCTURE These well-documented changes in the earth's living systems are part of a larger pattern of changes in the structure of the natural com munities of estuaries, coastal regions, and the oceans. The pattern is familiar: it is the pattern associated with accelerated eutrophication and pollution of water bodies; it is analogous to the changes in structure of forests caused by a variety of disturbances, including ionizing radiation (Woodwell, 1970). The reduction of structure leads progressively to shorter food chains in which hardy, broadniched species with rapid reproductive rates predominate. On land, these are the simplified, eruptive insect and rodent communities of highly disturbed areas; in water, they are the equally simplified com munities of eutrophic lakes and estuaries, in which harvestable fish populations are often depressed and bird populations are dominated by scavengers such as the herring gull. The problem in water, how ever, is greater, since the reduction of consumer populations is ac companied by a shift in plant species to hardy algae that are not con sumed by grazers; their production instead accumulates, decaying anaerobically and further reducing the potential of the site for sup port of man. MGNS 070595 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT IS While such chances are caused by many factors, the accumulations of persistent chlorinated hydrocarbons in estuaries and in coastal waters have become a significant factor accelerating this pattern of change. The panel recommends a massive national effort to effect a drastic reduction of the escape of persistent toxicants into the environment, with the ultimate aim of achieving virtual cessation in the shortest possible time. Only in this way can we hope to curtail the deleterious effects of chlorinated hydrocarbons upon community structure. RECOMMENDATION: A CHLORINATED HYDROCARBON BASE-LINE PROGRAM FOR THE MARINE ENVIRONMENT The paucity of analyses of chlorinated hydrocarbons in materials from the marine environment and from those parts of the atmosphere and the continental hydrosphere that provide these chlorinated hy drocarbons to the marine environment limits our ability to make judgments about their present and future impacts upon ecosystems. Any predictions about the rates of buildup in a given reservoir are somewhat speculative. Yet, we cannot initiate an effective monitoring program until the present dissemination of these materials at the earth's surface is detailed. An entry to a reasonable monitoring program can be found in a base-Une study in which the concentrations of the chlorinated hydrocarbons in geological and biological components of the marine environment, as well as in their transporting agencies, are deter mined. Such an investigation can conceivably be carried out in a year. A carefully planned investigation is necessary in order to obtain a critical amount of data with the minimum expenditure of funds. By utilizing a single laboratory to manage the program, difficulties in standardization and in sample preparation and handling can be mini mised. In the detailed planning and sample collection, the inputs from a variety of disciplines are necessary not only at the beginning of the work but also on a continuing basis. A large-scale program dealing with such a broad area will digress from the initial schedule of analyses as unexpected results come in. The following outline indicates the types of samples to be ob tained. We envisage perhaps a thousand analyses during the first year's base-Une program. Temporal, geographic, and spatial sampling procedures wiU be formulated for each of the groups of substances. HONS 070596 2 16 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT Samples of transport paths Major wind systems (sample in dust and as vapors) Prevailing westerlies-the jets Trades Regional winds such as monsoons and harmattans Rain, snow, and dry fallout; glacial samples provide data on fall out in past (Windom, 1969) The major rivers of the world (dissolved, suspended and bed-load materials) Sewer outfalls draining directly into marine environment from major population centers of the world Material released either by intent (dumping of wastes) or inadver tently (PCB's from antifouling paints on ships) from vessels Samples from reservoirs in the marine environment Seawater (particulate and dissolved loads) Isolates from air-water interface, surface-active agents, slicks Sediments The major fisheries food chains, including plankton, the harvest- able material, and predators of the harvestabie material Selected estuarine organisms, such as oysters The frequency of samples, as a function of location, time, or type, will depend on the resources available. Reasonable emphasis should be placed on historical records of inputs to the environment through the use of glacial (permanent snowfiekl) samples that record the atmospheric transport of material removed by precipitation and dry fallout. Museum specimens may provide a most useful index of the past body burdens of organisms. A base-line program for chlorinated hydrocarbons will provide samples for investigating other materials being disseminated about the world ocean that pose threats to marine organisms. The identification of a material that may endanger an ecosystem often occurs only after substantial disseminations have been made to the environment. A bank of samples, collected In sufficient quanti ties, will provide a historical record of invaluable use in such instances. Examples of other materials that might be sought are such metals as mercury, cadmium, lead, and arsenic; such industrial chemicals as methyl chloride and vinyl chloride; such widely used chemicals as dry cleaning fluids (perchlorethylene and trichlorethylene) and freon; and such dust components as asbestos and fly ash. More detail on this proposed program will be found in Appendix A. HONS 070597 CHLORINATEO HYDROCAR IONS IN THE MARINE ENVIRONMENT 17 RECOMMENDATION: REMOVAL OF OBSTACLES TO PUBLIC ACCESS TO CHEMICAL PRODUCTION DATA Among the causes contributing to the lack of available data on the chlorinated hydrocarbons is a legal structure that allows manufac tures of a given material, when there are no more than two pro ducers, the right to hold their production figures as privileged infor mation.* The Panel recognizes the economic rationale that deters the release of production figures by such manufacturers and understands that our government is charged by law with the protection of that proprietary interest. Indeed we approve the principle that governmental action should not artificially affect competition. However, we also feel that there are times when it is not in the public interest for government to maintain at privileged data that are necessary for research into the state of our environment and for an asseasment of its condition. In that regard, we recognize the possi bility that it is not always competitive concerns alone that determine the less than candid posture assumed by industry concerning produc tion figures. We recommend that the laws relating to the registration of chemi cal substances and to the release of production figures by the Depart ment of Commerce and the Bureau of the Census be re-examined and revised in the light of existing evidence of environmental deteriora tion. The protection afforded manufacturers by government is an artificial obstacle to effective environmental management, particu larly with reference to the polychlorinated hydrocarbons. In view of other impediments-technological, methodological, and financialsuch protection is clearly inappropriate. For exempts, the Monsanto Chemical Company has refused to release its pro duction figures for pci's, although requested to do so by many scientists and government officials. MQNS 070593 18 CHLORINATED HYDROCARBONS IN THE MARINI ENVIRONMENT REFERENCES Acree, F., Jr., M. Beroza, and M. C. Bowman. 1963. CodiatUlation of DDT with water. J. Agric. Food Chetn. 11:278-280. Anderson, D. W.r and J. J. Hickey. 1970. Ootofical data on efg and breeding characteristics of brown pelicans. Wilson Bull. 82:14-28. Anderson. D. W,, J. J. Hickey, R. W. Risebrough, D. F. Hughes, and R. E. Christensen. (969. Significance of chlorinated hydrocarbon residues to breeding pelicans and cormorants. Can. Field Nat. 83:92-112. Bailey, T. E., and J. R. Hannum. 1967. Distribution of peaticides in California. Proc. Sanit. Die. Am. Soc. Civ. Eng. 93:27. Banks, R. C. 1966. Terrestrial vertebrates of Anacapa Island, California. Trans. San Diego Soc. Nat. Hist. 14:173-188. Bitman, J., H. C. Cecil, and G. F. Fries. 1970. DDT*induced inhibition of avian shell gland carbonic anhydraee: A mechanism (or thin eggshells. Science 168:394-396. Blus, L J. 1970. Measurements of brown pelican eggshells from Florida and South Carolina. Bioscience 20:867-869. Bowman, M. C., F. Acree. Jr., and M. K. Corbett. 1960. Solubility of carbon-14 DDT in water. J. Agric. Food Chem. 8:406-408. Butler, P. A. 1969. Monitoring pesticide pollution. Bioscienee 19:889-891. Butler.P. A. 1966a. Fixation of DDT in estuaries, p. 184-189. In Transactions of tht 3ltt North American wildlife and natural resources conference. WUdUfe Management Institute, Washington, D.C. Butler, P. A. 1966b. Pesticides in tha marine environment. J. Appl. ficol. 3(Suppi.):2S3-2$9. Butler, P. A. 1967. Pesticide residues in estuarine mollusks. National Symposium on Estuarine Pollution, Stanford Univanity, sponsored by American Society of Civil Engineers, Sanitary Engineering Division, San Francisco Section; and Stanford Univ. Dept, of Civil Engineering. Distributed by Stanford Univ. Dept, of CivB Engineering. August 1967, 107-121. Butler, P. A. 1964. Commercial fishing investigations in effects of peaticides on fiah and wildlife. Fish and Wild!. Serv. Circ. 226:65-77. Butler, P. A., R. Childraaa, and A. J. Wilson, Jr. 1971. The association of dot residues with losses in marine productivity. FAO Technical Conference on Marine Pollution end Its Effects on Living Resources and Fishing, Rome, Dec. 9-18, 1970. in press, (preprint) Chemical Economics Service, Department of Business and Industrial Economics, Stanford Research Institute. 1951. Chemical economics handbook. Stanford Research Institute, Menlo Perk, Calif. Conney, A. H. 1967. Pharmacological implications of microsomal enzyme induc tion. Pharmacol. Rev. 19:317-366. Corradlno, R. A., R. H. Wamrman, M. H. Pubols, and S. I. Chang. 1968. Vita min Dj induction of a calcium-binding protein in the uterus of the laying hen. Arch. Biochem. Bfophys. 125:378-380. Cottem, C.. end B. Higgins. 1946. DDT: Its effect on fiah and wildlife. U.S. Dep. lot., Fish Wildl. Serv. Circ. 11. 14 pp. HONS 070599 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT 19 Davis, Harry C. 1961. Effects of some pesticides an eggs and larvae of oyatara (Critiottrt* wrylnice) and clams (Fenur mtrcttwia). Commer. Fish. Rev. 23(i2):8-23. Duka, T. W., J. I. Low*, and A. 1. Wilson, Jr. 1970. A polychlorinated biphenyl (Aroelor 1254) In lha watar, eedlment, and bJota of Eacambla Ray, Florida. Bull. Environ. Contain. Toxicol. 5:171-180. Food and Agriculture Orgaaiietion. 1969. Froduction yearbook, 1968. Vol. 22. Roma. Heath, R. G. 1969. Nationwide reaiduea of organochlorine petticidea In wing* of mallards and black duck*. Pastic. Monit. J. 3:115-123. Heath, R. G., 1. W. Spann, and I. F. Kreitxer. 1969. Marked DDE impairment of mallard reproduction in controlled studies. Nature 224:47-48. Hlekey, J. J., and D. W. Andaiaon. 1968. Chlorinated hydrocarbon* and eggahell chanfaain raptorial and fiah earing bird*. Science 162:271-273. Holden, A. V. 1976. Source of polychlorinated biphenyl contamination in the marine environment. Nature 228(5277): 1220-1221. Jefferiea, D. J. 1969. Induction of apparent hyperthyroidism in bird* fed ddt. Nature 222:578-579. Jefferies, D. J., and M. C. French. 1969. Avian thyroid: Effect of p,p'-DDT on lire and activity. Science 166.1278-1280. Jefferiea, 0. J., and I. Preatt. 1966. Post-mortems of peregrines and lanners with particular reference to organochtorine residues. Brit. Birds 59:49-64. Jehl, J. R., Jr. 1969. The brown pelican, a vanishing American. Environ. South west, no. 425,4. Jenssn, S., A. G. Johnela, M. Olsson, and G. Otterlind. 1969. DDT and PCI in marine animals from Swedish waters. Nature 224:247-250. Keith, J. 0., L. A. Woods, Jr., and B. G. Hunt. 1970. Reproductive failure in brown policens on the Pacific coast, p. 56-63. In Transections of the 35th North American wildlife and natural resources conference. WttdUfe Manage ment Institute, Washington, D.C. Koeman, J. H., A. A. G. Osksmp, J. Veen, E. Brouwer, J. Booth, P. Zwart, E. Ven den Broek, and H. Van Genderer. 1967. Inaactiddaa as a factor in the mortality of the sandwich tern (Sttrru MJitfWrrnrfr). A preliminary communi cation. Medad. RRksfnc. Lendbouwwet, Gent 32:841-853. Koeman, J. H., J. Veen, B. Brouwer, L. Huisman-deBrouwer, and J. L. Kooitn. 1968. Reridues of chlorinated hydrocarbon insacticidea In the North Sea en vironment. Heigoitodor wise. Meeresunters. 17:375-380. Koch, R. B. 1969. Chlorinated hydrocarbon insecticides: Inhibition of rabbit brain atpuo activities. J. Neuroehem. 16:269-271. Kranti, W. C., B. M. Mutilans, G. E. Begley, A. Sprunt, IV, F. J. Ligai, and W. B. Robartson. Jr. 1970. Organochlorine and heavy metal residues in bald eagle *Ka. Pestle. Monit. J. 4:136-140. Lichtenstein, 8- P., 9. P. Anderson, T. W. Fuhremann. and K. R. Schulte. 1968. Science 159:1110. Manifold, D. B., and J. A. Sehulsa. 1969. Pesticides in sslected western streams progfeie report. Pestle. Monit. J. 3:124-135. Matsumart, F., and K. C. Patit. 1969. Adenosine trtphoephetem eencittve to ddt in synapses of rat brain. Science 166:121-122. HONS 070600 t 20 CHLORINATED HYDROCAR RONS IN THE MARINE ENVIRONMENT Menxel, 0. W., J. Anderson, and A. Randtk*. 1970. Marine phytoplankton vary in their reaponee to chlorinated hydrocarbon*. Science 167:172^1726. Mount, 0.1., and G. I. Putnicki. 1966. Summary report of the 1963 Mleaieeippi fish kill, p. 177-184. In Transactions of the 31 si North American wildlife and natural resources conference. Wildlife Management Institute, Washington, D C. Mulhern, B. M., W. L. Reichel, L. N. Locke, T. G. Lamont, A. Bsiisle, 6. Cromartie, G. E. Begley, and R. M. Prouty. 1970. Organochlorine residues and autopsy data from bald eagles 1966-68. Pestle. Monlt. J. 4:141-144. Nash, R. G., and M. L. Beall, Jr. 1970. Chlorinated hydrocarbon Insecticides: root uptake versus vpor contamination of soybean foliage. Science 168:1109 1111. Nimmo. D. R.. A. J. Wilson, Jr., and R. R. Blackman. 1970. Localisation of dpt in the body organa of pink and whita shrimp. Bull. Environ. Contain. Toxicol. S:333-340. Peakall, D. B. 1970. P.p'-DDT: Effect on caleium metabolism and concentration of estradiol in the blood. Science 168:592-594. Peterie, T. I. 1969. DDT In antartic mow. Nature 224:620. Porter, R. 0.. end S. N. Wlemeyar. 1969. Dleldrin and DDT effects on sparrow hawk eggshells and reproduction. Science 165:199-200. Ratcilffe, D. A. 1967. Decrease in eggshell weight in certain birds of prey. Nature 215:208-210. Reichel, W. L., end C. E. Addy, 1968. A survey of chlorinated pesticide residues in black duck eat* Bull. Environ. Contain. Toxicol. 3:174-179. Reinert, R. E. 1967. The accumulation of dleldrin in an alga (Scsnedeimui obUquut), daphnia (DcphnJe megne), guppy (Lehirres r*ticvl*ntt) food chain. PhD. theais, University of Mlchlgin. University Microfilms, Ann Arbor, Michigan. Risetrough, R. W., J. D. Davis, and D. W. Anderson. 1970. Effects of various chlorinated hydrocarbons on birds, p. 40-53. In J. W. GUlett (ed.J, The btological impact of pesticides in the environment. Environmental Health Sciences Series 1. Oregon State University, Corvallis. Risetrough, R. W., D. B. Mints), D. J. Martin, and H. S. Olcott. 1971. ddt reNdues in Pacific marine flah. Pestle. Monit. J. (in preparation) Rlsebrough, R. W., P. Reiche, D. B. Psakall, 5. Herman, and M. Klrvan. 1968a. Polychlorinated biphenyls in the global ecosystem. Nature 220:1098-1102. Rlsebrough, R. W., R, J. Huggett, J. J. Grinin, and B. D. Goldberg. 1968b. Pesticides: Transatlantic movement in the northeast trades. Science 159: 1233-1236. Ryther, J. 1969. Photosynthesis and flah production in the see. Science 166: 72-76. Schwarts, H. L., V. Koayreff, M. I. Surks, end J. H. Oppenheimer. 1969. In* creased deiodination of L>thyroxins and L*trllodothyronins by Ever micro* some* from rats treated with phenobarbitol. Nature 221:1262-1263. Sticks!, L. F. 1968. Organochlorine pesticides in the environment. Fish and WUdUfe Service Special Scientific Report-Wildlife No. 119. Street, J. C., F. L. Mayor, and D. J. Wagstaff. 1969. Ecological significance of pesticide interactions. Indus. Med. Surg. 3S(11):91-96. HONS 070601 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT 21 Sverdrup, H. V., M. W. Johnson, end R. H. Fleming. 1942. The oceent. PrenticeHell, Inc., New York. 1087 p. Terrene, K. B., end J. Tetton. 1968. Organo-pestlcides in rainwater in the British Islet. Neture 219:725-727. Ukelee, R. 1962. Growth of pure cultures of merine phytoplenkton in the pres ence of toxicants. Appl. Microbiol. 10:532-537. Wiemeyer, S. N., end R. D. Porter. 1970. DDE thins eggshells of ceptive Americen kestrels. Nature 227:737-738. Windom, H. L. 1969. Atmosphere dust records in permanent tnowfields:. Impli cations to merine sedimentation. Bull. Geol. Soc. Am. 80:761-782. Wolmen, A. A., and A. J. Wilson, Jr. 1970. Occurrence of pesticides in whales. Pestle. Monit. J. 4:8-10. Woodwell, G. 1970. Effects of pollution on the structure and physiology of ecosystems. Science 168:429-433. Wurster, C. F. 1968. DDT reduces photosythesis by marine phytoplankton. Science 159:1474-1473. Wust, G. 1936. Oberflacben Salzgehalt, Verdunstung und Niederschlag auf dem Weltmeere, p. 345-359. In H. Louis and W. Panten [ed.], Landerkundliche Forschung: Festachrift Norbert Krebs. J. Engelhorns, Stuttgart. Yates, M. L., W. Holswade, and A. L. Hlger. 1970. Pesticide residues in hydrobiological environments. 159th ACS National Meeting, Houston, Texas, Feb. 1970. Water, Air and Waste Chemistry Section of the American Chemical Society Abstract, p. Watr-032. HONS 070602 EDWARD D. GOLDBERG GEIRMUNDER ARNASON JOSEPH L. REID M. GRANT GROSS FRANK LOWMAN Appendix A Proposed Base-line Sampling Program There ere few data on the preient concentration! of potentially toxic pollutants in the marine environment. Such baae-line data are essen tial in identifying areas of needed research. However, while perhaps desirable in the future, a global monitoring program requiring great expenditurea and technological advances is an inexpeditious approach to acquiring data that are needed immediately. A simplified base-line sampling program meeta that need without unreasonable financial and technological strains. Moreover, such a program can provide a basis for a more ambitious monitoring system. Guided by such concerns, we propose a one-year program to gather approximately one thousand samples from wind systems, ocean cur rent systems, organisms, rivers, and glaciers, rain, and sediments. This proposed program would begin implementation of our recommenda tion for a chlorinated hydrocarbon base-Une program for the marine environment. WIND SYSTBMS To design a network of sampling stations for measuring concentra tions of gaseous and particulate pollutants in the atmosphere, the 23 MCNS 070603 24 APPENDIX A prevailing global wind systems must be considered in relation to the major sources of pollutants. It Is also necessary to identify mecha nisms by which pollutants are transported laterally and vertically and to estimate the vertical boundaries of the atmospheric layer within which appreciable vertical mixing takes place. Most sources of airborne wastes are located on those parts of North America. Europe, and Asia (including Japan) over which there is a predominantly westerly flow. Furthermore, effluents are usually released near the ground at low speeds and, unlike emissions from volcanos, are unable to penetrate high into the atmosphere. We are primarily concerned here with the atmospheric part of the biosphere, a very thin layer bounded by the earth's surface. The prevailing wind systems are The tradewinds, 30"N-3Q*S: These easterly winds near the earth's surface decrease in strength with increasing height and become westerly except near the equator, where they retain the same direction at all heights The westerlies, 30*N-70*N, 30*S-65*S: The westerly winds in crease in strength to a height of at least 10 km The polar easterlies, 70*N-90*N, 65*S-90*S: These shallow winds decrease in strength with height and reverse their direction at about 3 km These major wind systems are modified by seasonal changes associ ated primarily with the warming and cooling of the continents (these changes result in such phenomena as monsoons) and by north-southoriented mountain ranges that cause large-scale meandering of the otherwise zonal flow. The lateral and vertical transport mechanisms within these wind systems are small-scale turbulence, local circulations such as ordinary convection and severe storms, extratropical cyclones within the westerlies, and easterly waves, tropical storms, and hurricanes within the tropical easterlies. The layer within which appreciable mixing takes place may be estimated by observing the concentration of sea-salt particles at altitudes from sea level upward. Toba (1965) reports that the number of these particles of 1-lChj* radius decreases quite rapidly with alti tude; for the smallest of these particles (1 -#i radius), the decrease is HONS 070604 APPENDIX A 25 approximately tenfold from the sea surface up to an altitude of 6 km. For submicron-aixe particles, the rate of decrease with altitude is pro bably somewhat lower. Because of the scarcity of particles at 6 km, this appears to be an appropriate ceiling for the mixing layer. For our immediate purpose, it is probably not necessary to measure particulates within the westerlies above an altitude of 5 km. The cor responding altitude is somewhat lower in the trade winds and the polar easterlies. Major sources of pollutants are the United Stales, western Europe, the Soviet Union, China, and Japan, all located within the westerlies. Minor sources are Africa (located within the trade winds and, to a les ser extent, within the westerlies). South America (located within the trade winds and the westerlies), and Australia (located within the trade winds). Based on this distribution, we suggest the following sample network. Location Surfaoa 500 m 1,500 m 5 km par yaar North America Europe and Asia Africa South America North Atlantic South Atlantic North Pacific South Pacific Australia Arctic Antarctic Subtropical hifh'prciaura calls 15 20 3 3 5 3 7 3 1 1 i 2 74 10 5 03 03 03 03 04 00 01 00 00 00 22 32 3I 31 3I 31 4l 31 11 11 11 21 Total Total 56 76 9 9 li 9 15 6 3 2 2 4 202 Additional measurements should be obtained near the sea surface by means of research and commercial ships and at greater altitudes by means of pedal-purpose and commercial aircraft. Aircraft obser vations are, perhaps, the only observations needed above 5 km. HONS 070605 26 APPENDIX A OCEAN CURRENT SYSTEMS Since the pollutants of potential importance In the ocean may take a variety of forint (such at gates, solutes, particles, oils) and may enter by various paths (e.g., atmosphere, rivers, ships), a set of base-line water samples should be spaced both horizontally and vertically in such a way as to detect any of these forms. Both the physical circula tion of the ocean and the distributions effected by biological trans port must be taken into account so that a proper framework for as sessment of the ultimate distributions in the oceans can be established. Sampling methods, means of treatment for preservation, and trans port for analysis are not discussed at this time. When such problems are confronted and the suggestions for sampling of other parts of the environment compared, some modifications in sampling methods can be expected. In establishing a tentative framework for base-line sampling of ocean water, three kinds of vertical spacing are suggested. The fust is simply a sample of surface film. The second is surface film, mixed layer, and pycnocline. The third replicates the second, except that it includes samples from about 1,000 m, 2,000 m, 3,000 m, and near the bottom. The three tpadngs will be referred to as surface film, shallow array, and deep array and will involve one, three, and seven samples, respectively. Surface film A set of 30 surface film samples should be collected, spaced generally over the ocean but with emphaais on the maior zones of precipitation and evaporation and along the major shipping routes (especially for oil). Shallow arrays Samples should be taken in the major eastern and western boundary currents (about 16 positions) and at the eastern and western edges of the three oceans at the equator. This totals 22 arrays with 3 samples each, or 66 samples. Deep array Samples should be taken in the centers of the major gyres and in the major mediterranean seas (Arctic, Gulf of Mexico, Mediterranean, Okhotsk, Bering, and Sea of Japan). With a central equatorial array for each ocean, the total is 20 deep arrays of 7 sam ples each, or 140 samples. ORGANISMS The expense of marine sampling limits the number of organisms that can be collected for a worldwide program designed to provide MQNS G70606 APPENDIX A 27 baseline measurement of the amounts of man-made pollutants in the marine biosphere. The following are considerations of significance for a selective sampling program: Geographic distribution of primary biological productivity Geographic distribution of world fisheries Sites of major river outflows General air-circulation patterns Sites of major downwelling and upwelling of water Sites of centripetal centers of major water gyres Desired coverage of marine populations of organisms Ease of sampling Cost The collection of adequate samples of marine organisms is impor tant in areas of high primary productivity and major fisheries since several of these areas are near sites of dense human population and pollution production, support relstively large marine biomasses that may serve as reservoirs with slow turnover rates for pollutants, and provide food pathways leading to man through his utilization of marine fishery products. The world catch of marine food is not evenly distributed through out the seas and is composed of a great variety of marine species. In addition, many pollutants toxic to man are concentrated in unknown degrees in many marine species. These factors complicate the prob lem of collecting adequate and representative samples within the lim itations of manpower end budget. Further complication is provided by the log-normal frequency distribution of amounts of trace pollu tants and other trace materials that occurs in apparently homogeneous populations of organisms, including those from the marine biosphere (Ting and deVega, 1969). Because of these problems, edible parts of 10 to 20 individuals of each selected species collected et a given site (demersal and pelagic fish, mollusks, and Crustacea) should be com bined into a homogenized, pooled sample. Also, net plankton should be collected at selected sites. The geographic distribution of primary productivity and world fisheries, shown in Figure A-l, are based on reports of Isaacs (1969) and Holt (1969). The major areas of high productivity include the Antarctic oceans, the North Atlantic banks, other shallows, and, of less Importance, the outflows of rivers. The location of major fisheries depends upon the biological productivity and resulting food webs in HONS 090fc0? HONS CJC6C8 (O 00 Very htgh tajlogical productivity 9 Medunn t*akxpa) p'oductnwty O low tmogca< oroductovUv FIGURE A-l Productivity of minte fidieritt. The number that appears within each oceanic subdivsion indicates the quan tity (in metric tons) of Ash landed in 1967. ArrENotx a 29 the foraging trees. In addition, the catch is dependent upon the fish* ing effort. The landing of fish, in millions of metric tons, during the year 1967 were as follows: Area MUUoni of Tons %of Total Catch NW Atlantic NB Atlantic W Central Atlantic E Central Atlantic SW Atlantic SB Atlantic 4.0 10.2 1.3 1.6 1.3 2.3 7.6 19.3 2.5 3.1 2.5 4.S Area Million! of Tons %of ToUl Catch N Pacific W Central Pacific E Central Pacific SB Pacific SW Pacific W Indian Ocean E Indian Oeaan 6.4 10.5 0.7 11.2 0.4 1.3 O.S 12.2 20.0 1.3 21.5 0.8 2.5 1.5 The fisheries of the northeast Atlantic, west central Pacific, and southeast Pacific accounted for 61 percent of the 1967 marine fish ery and, with the north Pacific and northeast Atlantic, for more than 80 percent of the total. More than 65 percent of the Atlantic catch was taken above 3(PN; the major sources of pollution in the Atlantic are also located north of this parallel. Most of the major fisheries described above are found on or near the continental shelves. The stations of the sampling pattern shown in Figure A-2 are located mainly on the continental shelves at sites of high productivity, major fisheries, the outflows of major rivers, and at the sites of downwelling and upwelling of water. In addition, sam pling stations are placed in the Mediterranean Sea and off the south ern shores of Africa, Australia, and South America. This plan calls for the collection of 42 composite samples each of demersal fish, mol- lusks, and pelagic fish and 12 composite samples of benthic Crustacea- a total of 138 samples. . Except for two sampling stations in the central Pacific, downcur* rent from upwelling areas off the Pacific coast of South America, the central oceanic areas are not sampled because of their great average depth, which precludes sampling of demersal organisms, and the greatly reduced populations, and sporadic occurrence, of pelagic fishes. Although tunas and other fishes are sometimes taken in these areas, the lack of appropriate catch data from fishing boats operating in the central oceans and the limited knowledge of the migration habits of these fishes complicate the interpretation of data derived from these samples. HONS 070609 l HONS 0 7 0 6 1 0 FIGURE A-2 Fnh. moUMric, --d awicti nwpbt wn Derirad from Holt (1969) and bancs (1969). (Copyright Ollaa cfcomtts Institute of Tec*aotoy 1970. Reputed with peemiam from Stndy of Critic* Eanroomcaui Piobfems (SCEP) 1970] APPENDIX A 31 Net plankton and flying fish, however, may be collected from the central oceanic regions (Figure A-3). Plankton may be taken on a predetermined grid, and sufficient flying fish normally come aboard research vessels operating in these regions at night to supply adequate samples for these areas. A total of 142 plankton samples and 40 fly ing fish (or more, if available) should be collected from the Atlantic, Pacific, and Indian oceans and the Mediterranean Sea. In summary, the suggested program for marine organisms would consist of the following samples: Fish Molluiki Cruitacaa Plankton 124 42 12 142 Total 320 RIVERS Various types of wastes are carried to coastal oceans by riven. Identi fication of major routes and reservoirs requires that river water, riverborne sediment, and related sediment deposits be sampled during base-line studies. For the initial study, a limited number of areas are suggested. Criteria used for their selection are listed below: Rivers Large river Extensive human activity Industrial Agricultural Different climatic zones Different stages of industrial development Continental Shelf Areas Accumulation areas for modem sediments Areas used for other activities, such as fisheries Near riven affected by man's activities, either industrial or agricultural Samples of water and sediment should be composited in space and time. This procedure permits an estimate of concentrations for quasi steady-state releaaes and should work well for dissolved (or dispersed) constituents. For rivers, two sampling periods are suggested-highflow and low-flow stages-each of 6 months' duration. MONS 070611 l HONS 0 7 0 6 1 2 FIGURE A-3 Net plankton station* (Copyright C Massachusetts Institute of Technology 1970. Reprinted with [ii iniwiiiii from Study of Critical EnriroamenUl Problea*($CEF), 1970.J AffENOIX A 33 The amount of sediment transported by rivers is extremely vari able. In most rivers, sediment moves primarily during a few weeks of maximum river flow. Hence, composite samples provide minimal data on annual sediment-transport phenomena. River water and sediment samples should be collected in volumes proportional to river flow and composited over a 6-month period. One sampler near the river surface (perhaps on a float) would collect river water. Another near the bottom would oollect water and sediment. Four samples a year from 19 river systems should be collected, to taling 76 samples per year. The number of samples taken in rivers could profitably be doubled to provide more information about time variability in such systems. The 19 river systems to be included in the study are listed below. North America Hudson Mississippi St. Lawrence Columbia South America Orinoco Amazon Plata Africa Nile Congo Niger Europe Rhine Danube Po Thames Asia Ganges-Brahmaputra Yellow (Hwang Ho) Amur Ob Indus Floods are probably a major factor in flushing sediment out of estuaries. The proposed composite samples will not provide adequate samples of these Important periods. Special samples should be col lected from recently deposited sediments at the head of the estuary. For example, a sample might be taken from navigation channels farthest from the ocean. The sample should be typical of riverborne sediment end wastes accumulating in the estuary (the materials most likely to be removed by dredging or washed out by floods). To understand the movement of sediment particles away from a river mouth, it is necessary to study deposits on the adjacent continen tal shelf or associated delta. Eleven areas, including four delta systems, are suggested for inclusion in the base-line study. HONS 0706X3 34 APPENDIX A Yellow Sea Mississippi Delta Nile Delta Baltic Sea Sea of Japan Ganges-Brahmaputra Delta Tokyo Bay Osaka Bay North Sea Black Sea Rhone Delta Several are associated with the major rivers included in this study. Others (such as the Sea of Japan or the two Japanese bays) were se lected because of the importance of the regions as highly industrial ized areas. The limited number of samples (approximately 30) should be composited to permit estimates of concentrations in recently de posited sediment. GLACIAL, RAIN, AND SEDIMENT SAMPLES An important record of the changed rates of waste injection into the atmosphere over the past several hundred years is contained in the permanent snowflelds (glaciers). The glaciers occur over a wide range of latitudes, permitting an examination of fallout from all of the major wind systems. Time marks can be retrieved from the glacial record by lead-210 geochronologies, firn stratigraphy, or oxygen iso topic stratigraphy. The variations in oxygen isotopic compositions of glacial waters allow the yearly sequences to be subdivided into summer and winter periods. Such a subdivision may be useful in isolating the sources of introduced materials, as wind directions vary from one season of the year to another. At the present time, there are no welldocumented techniques for making such historical studies on river influxes of materials. The following examples of glaciers that might be assayed, and the winds they monitor, have in most cases already been studied experimentally as recorders of atmospheric transport: Glacier Wind System Greenland Yukon Territory or Mount Olympus, Washington Mt. Orizaba or Mount Popocateptl, Mexico Andean glaciers Tasman glaciers, New Zealand Antarctica Northern hemisphere poler easterlies Northern hemisphere Jett Northern hemisphere trades Southern hemisphere trades Southern hemisphere jets Southern hemisphere polar easterlies HONS 07061** APPENDIX A 35 A sampling program of these six zones is proposed to collect glacial ice samples representing 1970 summer and winter, 1969 summer and winter, 1968 summer and winter, 1965,1960,1953,1943,1930, 1900, and 1800. For each of the trade and jet systems in the northern and southern hemisphere, composite rain samples (perhaps, a year's collection of rainwater) collected at single locations in both the Pacific and Atlan tic oceans would be most useful for comparison with the glacial re sults and for measuring precipitation washout. We propose that 78 permanent-snowfield samples and 48 rain samples be gathered. Deep-sea sediments accumulate at extremely slow rates, fractions of a millimeter to centimeters per thousand yean. These deposits are composed of rock debris from the continents, volcanic materials snd their degradation products, oceanic precipitates such as the ferro manganese minerals and barite, snd animal and plant frustules. Often, sediment surfaces are disturbed by burrowing organisms or near bottom currents, phenomena that can introduce long time-period smears into the record. Thus, the utility of an extensive sampling program for deep ocean sediment is questionable. On the other hand, fossil remains, including calcareous and sili ceous tests, provide a measure of the removal of materials from sur face waters to the sediments by biological agencies. A suite of four samples each of siliceous and calcareous ooze from the Pacific, Indian, and Atlantic oceans can provide a most reasonable set of base-line materials. SUMMARY The proposed base-line sampling program outlined above is, of neces sity, intuitive. However, even before attempting to collect and ana lyze all the samples, it would be worthwhile to look at a much smaller number of samples as soon as possible, with the expectation that a more effective, and leu expensive, base-line grid oould be derived. Although the program suggested is relatively simple and within reasonable financial and technological bounds, it can produce needed data on concentrations of potentially toxic pollutants in the marine environment. With this date, we can better judge the present and future Impacts of chlorinated hydrocarbons upon marine ecosystems. HONS 070615 36 APPENDIX A REFERENCES Holt, S. J. 1969. The food mouicM of the world, p. 93*106. In Scientific Araeri- cut cdlton, Tbc ocean. W. H. Freeman and Co., San Frandeeo. laaace,). D. 1969. The nature of oceanic Ufa, p. 65-10. In Scientific American cdlton, The ocean. W. H. Freeman and Co., San Frandeeo. Study of Critical Environmental Problems(ICIP). 1970. Mnn't Impoct on th* Globol Bnvironmtnt: AlHtimtnt ond Rteommtndoiton* for Aetton. The mit Prase, Cambridge, Maes. 319 p. Ting, R. Y., and V. R. da Vega, 1969. The nature of the distribution of trace elements in long-noee anchovy, Atlantic thread herring and alga, p. 527-534. In Proceedings of the Seoond National Symposium on Radloecology. uiaic Document Conf-670503, National Technical Information Servlca. Toba, Y. 1965. On the giant saa-salt particles in the atmosphere. Tellus 17:131 145. MQNS 070616 EDWARD D. GOLDBERG II. GRANT GROSS Appendix B Identification of Globally Distributed Wastes in the Marine Environment We propoee let of base-line meaiurementi to identify dietributkme and concentration! of man-introduced material! in the atmoiphere and ocean. Such a program can define preaent or potential threat! to the continued survival and well-being of marine ecoiyitemi. Already, mercury, halogenated hydrocarbon!, and oil have been widely recog nized. We seek to identify other material! of comparable aignificance. Attention ia focuaed primarily on atmospherically transported ma terials for several reasons: River-carried solids are extremely diverae in type and are deposited primarily near the river mouth Background concentrations of natural riverbome particles are large and variable and can therefore mask man's contributions Airborne materials are widely dispersed over oceanic arses within days or weeks after injection into the atmosphere To simplify the difficult problem of designating those materials that may pose problems to the marine environment, we have grouped them into three categories: 37 HONS 070617 38 AfFENDIX B Particles from the combustion of fossil fuels and from industrial activities Elements introduced to the atmosphere in amounts comparable to those brought to the world's riven by natural processes Synthetic organic chemicals Table 1 makes it clear that a modem industrial society can now compete with natural processes as a source of materials in the envi ronment. Although the available data are poor in quality, they suggest that burning fossil fuels will have a significant impact on the marine environment. Energy production is accompanied by emission of many other materials that may be detrimental to the environment; there fore, some measure of fossil-fuel combustion seems essential. Further, by tracing the paths of materials introduced to the atmosphere by energy generation, we can more readily ascertain the fates of other materials simultaneously introduced. Elemental carbon (released as toot and cokey balls) formed by fossil-fuel combustion is disseminated by winds over the earth's sur face. Rains over England contain elemental carbon that covaries with their sulfate contents in appreciable amounts (Gorham, 1933); both materials apparently came from the burning of coal. Atmospheric dusts collected over the Atlantic Ocean also contain elemental carbon, attributed to fossil-fuel burning (Folger, 1970). TABLE B-l Particles Injected into the Atmosphere by Natural and Artificial Processes Procose Particles Interned Into Atmosphere (i/yr) Natural processes Continental rock debris Set sett lOW-lO1** 10'** Volcanic emanations 10l--c U.S. Industrial, aplculrural, and social releases* Total Transportation 10** 2 x I0`* Fuel combuation 36 x 10'* Induatrlal 15 10'* Agricultural 54x10"' -rf jgtt. hMy orCMtM luvifonmratel Problem* <9CSP), 1970, p. 271. fWMMSffeMM?. "Nattonal Air Mutton Control Administration (NAPCA), 1970. HONS 070618 APPENDIX B 39 Elemental carbon can be determined in atmotpheric dusts and rains as part of the base-line program. Further, the historical record of fossil-fuel burning probably is held by the annual ice strata pre served in glaciers. The simultaneous measurement of sulfate and carbon would give a broad picture of the fates of fossil-fuel emissions in the atmosphere. Sulfur initially introduced as sulfur dioxide and later oxidized to sul fate may have a somewhat different path in the atmosphere than that of carbon. To confirm the fossil-fuel origins of the elemental carbon and sulfate, isotopic analyses of sulfur and carbon could be used. The contribution of gas and oil relative to that of coal may be found in assays for the aluminosilicate muUite made during the burn ing of coals. This mineral is detectable in fly aah (fine-grained ash) and is not normally found in rocks (Gross, 1971). Being rare in the environment, it may well be useful as a tracer of coal-combustion products. Most of the particles generated by processes included in Table B-l are large and therefore fall out close to their sources. Smaller particles with dimensions of microns or less may have long residence times in the atmosphere and may travel great distances before entering the ocean, where they can affect plant and animal populations. Another group of chemicals encompasses those elements that are injected into the atmosphere at annual rates comparable to those in the major sedimentary cycle. In the latter caae, compounds of the element are brought to the oceans by rivers. The chemical forms in troduced by man may be different from those naturally present, and they may have an unusual size distribution or shape if they come in as solids. In any caae, they can create new chemical surroundings for the marine organisms. The five metals included In Table B-2 fall within this classification. The lead emission to the atmosphere results primarily from the combustion of lead tetraethyl and lead tetramethyl in gasoline; this accounts for about 20 percent of the total world usage of lead. Vana dium and nickel come from burning of fuel oil, where they are natu rally bound in porphyrin complexes. Mercury is introduced to the atmosphere primarily through stack gases from caustic-chlorine plants where it is used as an electrode in the dissociation of saline solutions. Some mercury escapes during its use ss a biocide in agricultural and industrial applications. It Is estimated that about half of man-induced emissions of cad mium to the atmosphere result from processing cadmium ores; 070619 40 APPKNDIX i TABLE B-2 Mobilisation of Elsmsnts ( (1m Earth'* Surfacs (g/yr). (Marwnads smlsrioM for mtrcury and toad art on a worldwide bad*; for (ha other metal*, UB. valutt ara |hrtn.) Blsmant Natural Bminion1 Cd 3.1 x 10* H* 3.0 x 10* HI 2.0 x 10" Pb 2.1 X 10" V 2.6 x 10" Industrial Bmiarion Approximate Valus (j/ 2.0xI0* 4.0 x10** 7.0 x 10* 4.0X10" 5.0 X 10*' 10,000,000 $0,000,000 13,000.000 20.000.000 2,000,000 *NattowlAlr PoButtoa Control AdmMMmttoa, impoMinii* doewnent. yitto mM OaMbtu. im *C. C. hmnw. pwwiil oowwainUon. *V. 1. HadMjitnet, pnsonal oomiwileattow. fU.S. Httou of MIbm, IMS. cadmium U alto lost in the mining and processing of zinc, lead, and copper ores. Another source of cadmium to the atmosphere is inciner* ation of cadmium-containing waste products. This probably equals the loss resulting from the original processing. The quantity of sulphur released to the atmosphere may be approx* imated from the following argument: Of the synthetic organic chemi cals. 95 percent are produced from petroleum and require 5 percent of the annual world production of petroleum (SO million tone per year in the United States). In addition, there is t substantial lota of hydrocarbon* through fuel combustion, transportation, industrial processes, end solid waste disposal (TaMe B-3). Several criteria are suggested for use in selecting synthetic organic substances for inclusion In a base-line program: The material is produced and may enter the atmosphere or ocean in large quantities. The material (or its degradation products) interferes with meta bolic activities of one or more forms of life. The material It concentrated by one form of life on which it may have no discernible effect, but which is food for another form of life on which it can have a most deleterious effect The passage of dot and its residues through the food chain and their subsequent effect upon bird and fish populations illustrates such a case. Its physical form interferes with an organism's growth, activity, or HONS 070620 appcndix 41 TABLE B-3 Organic Chtmlcclt-Soim Production and Potential Einlaalon Data for United Statta* Subttaae* Total imoustt of fyothvtic orftsici DDT rca'i Diy<lMBlng boIvmci. porehtoro*tbyl*M and trichlorathtyltn* F*on-I2(CClaF,) OmoUim Into *tmo*phr Hydrocarbons tost to tmuportation, fool oombuattou, Industrial proow--, olid wart* dtopod. te. hudna totroduoed dinelly into marina nrinm**nt by man'e idivitiN Pnmt Production Rat* it/yr) 5xlO' 2x io" 5 x 10* 2X 10" 1x10" - - BmlMloo Rat* (g/yr) _ _ _ 2x10" 1 x 10" 2x10" 3x10" 3 x 10" CeMtarg. xepeMlam feu. well-being. For example, eebeatoe fibera and aiUceoui particles cauac damage to man'i lunge. The material or iti deeompoaltion producti is alien to the marine environment but similar to lubtUncea that have known teratogenic, mutagenic, toxic, or carcinogenic efTecta For example, the dry cleaning aolvent, trichloroethylene, may affect enzyme ectlvitiea aa do the heavier chlorinated hydrocarbon. A aaiue of priority for the inchraion of aynthettc organic chemkala In a baae-Une program may be eitahliihed by wing auch criterie in combination with the chemical and biochemical characteriatica of a given aubatance. Thla auggeata that special attention be given halogenated organic oompounda. The 2.1 million tone per year of petroleum Introduced directly Into the marine environment [Study of Critical Environmental Problem (SCEP), 1970, p. 267] provider a apedal caae of a aubatance to be meaaured. Much of thla material. Introduced into coaatai waters, estuaries, harbors, and shipping lanes, may accumulate in the airwater interface to form slicks. Such a veneer over the ocean may be HONS 070621 42 APPENDIX late of uptake of nonpolar organic materials transported about the atmosphere or the surface ocean. Hydrocarbons appear to constitute a major emission of organic compounds to the environment and can be globally dispersed by wind systems. Since northern hemisphere emissions vastly exceed those from the southern hemisphere and since most industrial activity is at midlatitudes, It is necessary to focus Attention upon midlatltudinal oceanic areas in the northern hemisphere. With halogenated hydro carbons, entry through the atmosphere to the ocean probably involves reservoir at the air-water interface. Natural substances forming such surface films include fatty adds and their alcohols; man-introduced materials constat of oil from leakages and spills. Such s surface film may pick up many of the other organic compounds translocated from the continents to the oceans via the atmosphere. Thus, in preparing a set of base-Une measurements to identify die* tributions and concentrations of man-introduced materials in the atmosphere and ocean, attention should be directed to the analysis of a variety of organic compounds in surface Aims, such as dot and its residues, freon, and gasoline hydrocarbons. REFERENCES Folgsr, D. W. 1970. Wind transport of land-derived mineral, blogsntc and induo trial matter over the North Atlantic. Deep-Sea Rea. 17:197-352. Goldberg, B. D. 1965. Minor elements in eea water, p. 163-196. MJ. P. Riley and O. Skirrow led.), Chemical oceanography, Vol. 1. Academic Prern. London. Gorham, E. 1955. On the aridity and salinity of rate. Geoehem. Cosmochim. Acta 7:231-239. Grom, M. G. 1971. Oceanography. 2nd ed. Chariac B. Merrill Publishing Co., Columbus, Ohio. 150 p. Klein, D. H., and B. D. Goldberg. 1970. Mercury in marine environment. Environ. Sri. Teehnoi. 4:765-760. National Air Pollution Control Administration (nafca), (1970). Summary of emissions in the United Ststee, 1970 edition. Public Health Service, U.S. Department of Health, Education, end Welfare. Raleigh, North Carolina, (mtmeo) 49 p. Study of Critical Environmental Problems (SC8P), (1970). Man's impact on the global environment: Amc--mint and recommendations for action. The mit Press, Cambridge, Mamachuaetts. 319 p. U.S. Bureau of Mines. 19dS. Minerals Yearbook, 1967, U.S. Government Print ing Office, Washington, D.C. Window, H., 1.1. Griffin, and B. D. Goldberg. 1967. Talc in atmospheric dusts. Environ. Sri. Teehnoi. 1:923-926. HONS 070622