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( I 3 t : : ! .-'l;' ? \1 > ,, * i % K-: HCNS 069^35 ft I 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 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 frac 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: Prom the beginning of ite wartime use u an insecticide the potency of dot ha* been the cause of both enthusiasm end grave concern. Some have come to con sider it a cure-all for insect pests; others are alarmed because of its potential harm. The experienced control worker realizes that DOT, like every other effective in secticide or xodenticide, is really a two-edged sword; the more potent the poison, mi MCNS 069437 IV PREFACE tin more damage It is capable of doing. Moet oiianic and mineral poieona are pacific to a degree; they do not strike the Innumerable animal and plant apadae with equal effectiveness; if theee poieona did, the advantage of control of unde table apeciea would be more than offaat by the detriment to datable and bene ficial forma, ddt is no exception to this rule. Certainly such an effective poiaon will destroy beneficial insects, fishes, and wildlife. Although many more investigations are needed in all these fields, it seems that the moat pressing requirement is a study to determine the effects of ddt m ap plied to agricultural crops on the wildlife and game dependent upon an agricul tural environment. About 80 percent of our game birds, ss well as a very high percentage of our nongame and Insectivorous birds, and mammals art largaly dependent upon an agricultural environment. In euch placet application of DDT will probably be heavy and widsspretd; therefore it i> not improbable that the greatest damage to wildlife will occur there. Because of the aenritivity of fishes and crabs to ddt, avoid as far as possible direct application to streams, lakes and coastal bays. Whenever ddt is used, make careful before and after observations of mam mals, birds, and fishes, and other wildlife. In the spring of 1970, the Committee on Oceanography estab lished the Panel on Monitoring Persistent Pesticides in the Marine Environment to study the impact of DDT and other chlorinated hy drocarbons, including those of Industrie! origin, on the marine envi ronment and to suggest courses of action based upon its findings. The Panel convened at WiUiamitown, Massachusetts, in July 1970, as par ticipants in the Study of Critical Environmental Problems (SCBP), arranged by the Massachusetts Institute of Technology. Through our studies and discussions, we see clearly 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 and 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 fish are still not clearly understood. This report is not intended to represent an exhaustive survey of the literature. It has bean prepared to alert the community of marine dentists 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 MOMS 069436 PREFACE V of CotUm and Higgins, made over 25 yean ago, hoping that a similar report will not be neceoary 25 years hence. The one-month Study of Critical Environmental Problems, which covered travel 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-line 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. These working papers, along with others prepared for scep, will be published in the forthcoming MIT Press publication Man's Impact on Terrestrial 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 a aeries 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 Commission, the Department of the Interior, the National Science Foundation, the National Oce anic and Atmospheric Administration, and the Coast Guard. PANEL ON MONITORING PERSISTENT PBST1C1DBS IN THE MARINE ENVIRONMENT Edward D. Goldberg, Chairman Philip Butler Paul Meier David Menzel Gerald Paulik Robert Rjsebrough Lucille F. Sticke! { *" I MQNS 069439 j. 'Ji.'i.iwfmijuwijmj. ^ 11 Contents CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT Summary and Recommendations, 1 U S. and World Production of Chlorinated Hydrocarbons, 2 Transport of DDT Residues and PCB's to the Marine Environment, 4 Distribution of Chlorinated Hydrocarbons in the Marine Environment, 6 The Ecological Impact, 8 Plankton, 8; Crustaceans, 9; MoUusks, 9; Fish. 10; Birds, 11 Biochemical EfTects, 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, 1S Recommendation: Removal of Obstacles to Public Access to Chemical Production Data, 17 1 vi RONS 0694h0 IliU HI IjJlini -1 .MB I.IUPff t f ?v. APPENDIX A: PROPOSED BASE-UNE SAMPLING PROGRAM 23 Wind Systems, 23 Ocean Current Systems, 26 Organisms, 26 Rivera, 31 Glacial, Rain, and Sediment Samples, 34 Summary, 35 APPENDIX B: IDENTIFICATION OF GLOBALLY DISTRIBUTED WASTES IN THE MARINE ENVIRONMENT 37 vii HONS 069441 EDWARD D. GOLDBBRG PHILIP BUTLER PAUL MEIER DAVID MBNZBL ROBERT W. RISEBROUGH LUCILLE F. 8TICKBL Chlorinated Hydrocarbons in the Marine Environment i SUMMARY AND RECOMMENDATIONS Hie oceans ere in ultimite 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 fiah-eatinc 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 at which such substances 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 069*42 [ 2 CHLORINATED HYDROCARBONS IN THE MARINE 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 a 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 1. 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 are exported (Stickel, 1968). It is difficult to collect world production data for these materials because the information available is inadequate. Although some *Inciudet sldrio, chlordane, dleldrin, endrin, beptachlor, and toxaphane. MGNS 069443 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT 3 TABLE 1 U.S. Production ofChlorinetod Hydrocarbons, in Unit! of 109 g/yr Yur 1968 1967 1966 1965 1964 1963 1962 1961 I960 1959 1958 1957 1956 1955 1954 1953 1952 1951 1950 1949 1948 1947 1946 1945 1944 Tots! 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 39.4 45.4 48.2 35.5 17.2 9.2 22.5 20.7 15.1 4.4 1.220.0 AJdiiiv-Toxsphene 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 35.0 20.5 -- - 670.0 FCB* 5 _ - 5 "OMafcd Boooortcs Ssrvka, Dsfrtiait of Brntom tad IodmtrU Economic*, JliNM RwareE laatltoM (ml). *EatimM band opoa cbimbhw tafawtisa. yearly figures may be found for a given country, comprehensive data for the major producer, hare not yet been compiled, hampering manbalance calculation, for diapenion of then material, around the earth and making an undemanding of their behavior in nature difficult. An urgent need for auch data ia dear. Even more pressing i> the need for the production figure, for the polychlorinated biphenyl,, which have been in use since the early 1930',. An impaction of the production and utilization figures that were available to us (Pood and Agriculture Organization, 1969) suggests HONS 069444 4 CHLORINATED HYDROCARBONS IN THE MARINS SNV1RONMSNT that the total world production of DDT 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 X I0,a g, and the production of the aldrin-toxaphene group is 1.0 X 10,J g. The production rate used in calculations, both for DDT and for the aldrin-toxaphene group, is 10" g/yr. TRANSPORT OP 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 at 3.7 X 101* cc. The maximum concentration of DDT rest* 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 107 g annually (Risebrough ti al., 1968b). The total river transport of DDT residues from the continental United States might be ten times that of the Mississippi, approaching 10" g. Domestic U.S. use of DDT between 1961 and 1968 has ranged between 5 and 8 X 10' g/yr, thousands of times more than can be carried in the riven; 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 residues is s tern defining DDT, DDE, and ODD. odd snd dob ire me tabolites of DDT, and ODD is also s pesticide in its own right. N0NS 069445 CHLORINATED HYDROCARBONS IN THE MARINS ENVIRONMENT 5 suiting in the discovery thst approximately I ton of PC B 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 wattes 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 el at., 1970). DOT residues enter the atmosphere by several routes, including aerial drift during application by rapid vaporization from water sur faces (Acree el el., 1963) and by vaporization from plants snd soils (Nash and Beall, 1970). Once in the atmosphere, dot 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 el at.. 1970). Total annual precipitation of water over the oceans has been esti mated at 3.0 X10" cc (Sverdrup era/., 1942). If this precipitation had an average concentration of ddt residues of 80 parts per trillion, a total of 2.4 X10" g of DDT residues 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 el of., 1968), has been found in airborne particulates over the ocean (Risebrough el of., 1968b) and in rainwater (Tarrant and Tatton, 1968). Polychlorinated biphenyls have also been detected in rainwater (Tarrant and Tatton, 1968). ret hat not yet been measured in river waters, but there it 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 ret into the tea remains to be determined. MOWS 069446 6 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT DISTRIBUTION OP CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT Few data are available to document the concentration of chlorinated hydrocarbonc (including PCb'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. Gray 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, tnd 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 fish (tuna) carry 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 S.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 paudty 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 I0}5 g (Menzel, unpublished data). 2. The standing crop of fish is 6 X 10>4 f, 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 DDT residues in fish averages l .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. HONS 069**7 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 gand fish 6 X 10* gof Ddt residues, both insignificant fractions of the total annual input of these residues to the environment <I0M 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 al., I960) and the volume of the mixed layer (upper 100 m of the ocean) as 0.02S X10* ml, the surface waters of the ocean are capable of ac commodating a load of 7.5 X10IJ gof DDT,or approximately 38 times the total production to date. There is no indication, however, that DDT introduced into the marine environment is uniformly dis tributed in the mixed layer. Enrichment is likely to occur in the sea's surface Him, which contains fatty adds and aloohols. 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 oodistills with water or is objected back into the atmosphere as aero sols and it 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 it 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. Its aerial distribution is 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 10ia g (one quarter of total production) should be present in solution snd in the bottom sediments. In order to balance input with accountable fractions, the surface mixed layer volume (0.025 X10* 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 X1011 gof DDT per year. 'Saturation totals of ODD and DDE have not yet been measured. MChS 069446 8 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT THE ECOLOGICAL IMPACT The acute and chronic toxicity of 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 (Butter, 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 it available demonstrating inhibi tion of photoaynthesis in single-celled marine plants by DDT, dieldrin, and endrin (Wurater, 1968; Menzel et a/., 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 (1 ppb) in water. One species tested was insensitive to concentrations of all three pesticides up to 1 ppm. Therefore, toxic ity may vary interspedflcally, 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 HONS 069449 f. CHLORINATZD HYDROCARBONS IN THE MARINS ENVIRONMENT 9 from murine ipeciet but have been estsbUshed ee spproximslely 1,000 in the case of dieldrin for e freehwater Riga (Reinert, 1967). These or ganisms are available as food to grazing 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 S parts per trillion. These concentrations of DDT are lower than expected in rainwater falling on the tea surface (80 parts per trillion). These observations cannot be applied to the open oceans, because, as noted earlier, no measurements of D D T concen trations are available from these waters. Crustacean] Bioassay 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 a1970). Concentrations of this magnitude have been detected in Texae river waters flowing into commercially important shrimp nursery areas (Manigold 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 Dungeness crabs may be associated with observed DDT residues in the developing larvae. Polychlorinated biphenyls (Arodor 1254) at a concentration of 5.0 ppb caused 72 percent mor tality in 20 days to test populations of pink shrimp {Penaeui duororum); these shrimp had accumulated 33 ppm of the PCB in their tis sues (Duke */ a/., 1970). Molluske . The chlorinated pesticides and PCB's characteristically interfere with the growth of oysters. One ppb of the PCB Arodor 1254, for MOMS 069450 10 CHLORINATXD HYDROCARBONS IN THE MARINE ENVIRONMENT example, causes a 20 percent decrease in shell growth (Duke et a/., 1970). Many pesticides interfere with oyster growth at levels as low as 0.1 ppb (Butler, 1966b), in the ambient water. Mollusks 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 mollusks 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 S 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 Sea Trout in Laguna Madre* Year 1944 1965 1966 1967 1968 1969 Number of Sea Trout Captured per Acre 30 25 12 a 2.7 0.2 From Butter et at. (1971). *No data exiit for 1967, aa harrlcanM destroyed all the fliNnageer. The decline in the (Idwy has been only is the juvenile trout, which eUndnatee um possibility of over.nailing. The DDT residue! in the gonads of the adult trout reach a maximum of 8 ppm prior to pawning. HGNS 069*51 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT 1 1 carbons. However, the sale of some California mackerel has been prohibited because DOT 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 from an insecticide-manufacturing plant (Mount and Putnicki, 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 fcb 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 dieklrin 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 asaociation 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-1940'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 (Ratdiffe, 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, DDE in the diet of mallard ducks resulted in thin eggshells and reduced hatching success; p,p'-DDT produced MOWS 069452 12 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT the nine effects, but to e lesser degree (Hesth ctal., 1969). Both ODE slone and a combination of p,p'-DDT and dieldrin in the diet of American kestrels resulted in thin eggshells; the test of DDT 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 (Krantz tt al., 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 predpitiously. On the basis of museum series, it has been determined that shell thinning has occurred in all areas (Blue, 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 ef al., 1971), a disastrous reproductive failure occurred in 1969 among brown pelicans on Anacaps Island as a result of egg shell collapse (Jehl, 1969; Keith tt al., 1970; Risebrough elal.,1970). In this area, the brown pelicans and double-crested cormorants are no longer able to reproduce. At most, 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 (Gress, 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 caaes 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 Anacape Island, the Ialas de Coronados in Mexico, other localities in Bala California, and four colonies in Florida (Risebrough, Gress, Anderson, and Schreiber, unpublished data). By compering pelican eggs from California and Florida, where the relative amounts of DDE and PCS are very different, the same investi- MGNS 069453 .i CHLORINATED HYDROCARBONS IN THI MAXINE ENVIEONMENT 13 (Eton concluded th*t DOE 1e the major cause of shell thinning in the brown pelican eggs. Pelican eggs collected on Anacapa in 1962 showed a critical level of riiell thinning, but lest than the thinning observed in 1969 and 1970 (Anderson and Hickey, 1970). Young pelicans were still produced on Anacaps in 1963 and 1964 (Banks, 1966). From the observed relationships between DOB concentration and shell thinning it can be concluded that between 1962 and 1969, accumulations of chlorinated hydrocarbons in the southern California marine ecosystem passed a level critical to the brown pelican. Shell thinning has also been detected in marine and coastal birds in northern California, including the common murre (Greas, unpublished data), the ashy petrel (Riaebrough and Coulter, unpublished data), and the American egret (Pratt and Riaebrough, 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 (Cortadino et of., 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 era/., 1969), and herring gull (Hickey and Anderson, 1968). DDE has also been found to inhibit the enzyme carbonic anhydraae (Peaks!), 1970; Riaebrough at a/.. 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 drop as sulfanilamide results in the production of thin-shelled eggs. The chlorinated hydrocarbons, including DDE and FOB, induce HONS 069454 14 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT mixed-function oxidise enzymes in the livers of birds and mammals that hydroxylate and render water-soluble any foreign, lipid-soluble compounds (Conney, 1967; Risebrough et al., 1968a; Street et al., 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 LONGTERM 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. KONS 069455 CHLORINATED HVDROCARRONS IN THE MARINE ENVIRONMENT 15 While such changes 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 s 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-line study in which the concentrations of the chlorinated hydrocarbons in geological and biological components of the marine environment, at well as in their transporting agencies, are deter mined. Such an investigation can conceivably be carried out in a year. A carefully planned investigation it necessary in order to obtain a critical amount of data with the minimum expenditure of funds. By utilizing a tingle laboratory to manage the program, difficulties in standardization and In sample preparation and handling can be mini mized. 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 at 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-line program. Temporal, geographic, and spatial sampling procedures will be formulated for each of the groups of substances. HONS 069456 16 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT Samples of transport paths Mgjor wind systems (simple 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 pest (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 (FCB'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 harvestable 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 snowfield) 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 u 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 069457 . frir CHLORINATED HYDROCARSONS 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 taw 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 as privileged data that are necessary for research into the state of our environment and for an assessment of its condition. In that regard, we recognize the possi bility that it is not always competitive concerns alone that determine the leas than candid posture assumed by indvntry 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 affective environmental management, particu larly with reference to the polychlorinated hydrocarbons. In view of other impediments--technological, methodological, and financialsuch protection is dearly inappropriate. For Minpto, tbs Monsanto Chemical Company has refused to release its pro duction figures for rci'i, although requested to do so by many scientists and government officials. 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V. 1974* Source of polychlorinated biphenyl contamination in the marine environment. Nature 228(S277):1220-1221. Jefferies, D. J. 1969. Induction of apparent hyperthyroidism in birds fed DDT. Nature 222:578-579. Jefferies, D. J., and M. C. French. 1969. Avtan thyroid: Effect of p.p'-DDT on size and activity. Science 166:1278-1280. Jefferies, D. J., and I. Prestt. 1966. Post-mortems of peregrines and lanners with particular reference to organochlorine residues. Brit. Birds 59:49-64. Jehl, J. R., Jr. 1969. The brown pelican, a vanuhing American. Environ. South west, no. 425,4. Jensen, S., A. G. Johnels, M. Olaeon, and G. Ottertind. 1969. DDT and res in marine animals from Swedish waters. Nature 224:247-250. Keith, J. O., L. A. Woods, Jr., and B. G. Hunt. 1970. Reproductive failure in brown pelicans on the Pacific coast, p. 56-63. In Transactions of the 35th North American wildlife end natural resources conference. Wildlife Manage ment Institute, Washington, D.C. Koeman, J. H., A. A. G. Oakamp, J. Veen, E. Brouwer, J. Rooth, P. Zwart, E. Van den Broek, and H. Van Gendtrer. 1967. Insecticides as a factor in the mortality of Uw sandwich (era (Sterna tandricentis). A preliminary communi cation. Meded. Rijksfac. Landbouwwet. Gent 32:841-853. Koeman, J. H., J. Veen, E. Brouwer, L, HtUsman-deBrouwer, and J. L. Koolen. 1968. ReMdues of chlorinated hydrocarbon insecticides in the North Sea en vironment. HelgoUnder wise. Meeresunten. 17:375-380. Koch, R. B. 1969. Chlorinated hydrocarbon insecticides: Inhibition of rabbit brain ATPaae activities. J. Neurocbem. 16:269-271. Krantz, W. C., B. M. Mulhera, G. E. Bagley, A. Sprunt, IV, F. J. Lisas, and W. 8. Robertson, Jr. 1970. Organochlorine and heavy metal residues in bald eagit eggs. Peetie. Monit. J. 4:136-140. Lichtenstein, E. P., J. P. Anderson, T. W. Fuhremaiui, and K. R. Schultz. 1968. Scienoe 159:1110. Manigold, D. B., and J. A. Schulze. 1969. Pesticides in selected western streamsa progress report. Pestic. Monit. J. 3:124-135. Matsumura, F., and K. C. Patil. 1969. Adenorine triphosphatase sensitive to ddt in synapses of ret brain. Science 166:121-122. M0NS 069460 [ 20 CHLORINATED HYDROCARBONS IN THE MARINE ENVIRONMENT Menul, D. W., J. Anderson, tod A. Randtke. 1970. Marine phytoplankton vary in their response to chlorinated hydrocarbon*. Science 167:1724-1726. Mount, D. I., and G. J. Putnicki. 1966. Summary report of the 1963 Miariseippi fish kill, p. 177-184. In Transactions of the 31st North American wildlife end natural resources conference. Wildlife Management Institute, Washington, D.C. MuUtem, B. M., W. L. Reichel, L. N. Locke, T. G. Lamont, A. Belirie, C. Cromartie, G. E. Begley, and R. M. houty. 1970. Organonhiorlnc residues and autopsy data from bald eagles 1966-68. Pestle. Monit. I. 4:141-144. Nash, R. G., and M. L. Beall, Jr. 1970. Chlorinated hydrocarbon insecticides: root uptake venue vapor contamination of soybean foliage. Science 168:1109 1111. Ntinmo, D. R,, A. J. Wilson, Jr., and R. R. Blackman. 1970. Localisation of dot in the body organa of pink and white shrimp. Bull. Environ. Contain. Toxicol. 5:333-340. Peakail, D. B. 1970. P.p'-ddt: Effect on calcium metabolism and concentration of estradiol in the blood. Science 168:592-594. Peterie, T. J. 1969, DDT in istutk mow. Nature 224:620. Porter, R. D., and S. N.lnemeyer. 1969. Dieldrin and ddt effects on sparrow hawk eggshells and reproduction. Science 165:199-200. RatcUffe, O. A. 1967. Dacteaae in eggshell weight in certain birds of prey. Nature 215:208-210. Reichel, W. L., and C. E. Addy. ] 968. A survey of chlorinated pesticide residues in Mack duck eggs. Bull. Enriroa. Contain. Toxical. 3:174-179. Reinert, R. E. 1967. The accumulation of dieldrin in an alga (Scenedermur obttqvtu), daphnia {Dtphnia mtgm}, guppy (Ltbistt* mtcuknu) food chain. PhD. thesis, Uitiveirity of Michigan. Ushenity Microfilms, Ann Arbor, Michigan. Risebrough, R. W., J. D. Daria, and D. W. Andenon. 1970. Effects of various chlorinated hydrocarbons on birds, p. 40-53. In J. W. Gillett [ed.l, The Mological impact of pesticides in the environment. Environmental Health Sciences Series 1. Oregon State University, Corvallis. Risebrough, R. W,, D. B. Mental, D. J. Martin, and H. S. Olcott. 1971. DDT reriduee in Pacific marine fish. Peetic. Monit. J. (in preparation) Riaabrough, R. W., P. Reiche, D. B. Peakall, S. Herman, and M. Kirven. 1968a. Polychloriitated biphenyls in the global ecosystem. Nature 220:1098-1102. Risebrough. R. W,, R. J. Huggett, J. J. Griffin, and B. D. Goldberg. 1968b. Pesticides: Transatlantic movement in the northeast trades. Science 159: 1233-1236. Ryther, J. 1969. Photosynthesis and Ash production in the saa. Science 166: 72-76. Schwartz, H. L., V. Kozyreff, M. 1. Surka, and J. H. Oppenheimer. 1969. In creased deiodinatlon of L-thyroxine and L-trilodothyronine by Uver microaomes from rate treated with phenobarbitol. Nature 221:1262-1263. Sticks!, L. P. I960. Organochlorine pesticides in the environment. Piah and Wildlife Service Special Scientific Report-Wildlife No. 119. Street, J. C., P. L. Mayer, and D. J. Wagataff. 1969. Ecological significance of pesticide interactions. Indus. Med. Surg. 38(1 l):9i-96. w0NS 069461 NPPIIBBPIP^^ : 7? iiiifrn CHLORINATED HYDKOCA*ON8 IN THE MARINE ENVIRONMENT 21 Sverdrup, H. V., M. W. JohiMOO, and R. H. F1naio|. 1942. The ocean*. Prentice Hall, Inc., New York. 1087 p. Tamnt, K. B., and I. Tattoo. I960. Oiganopettiddes in rainwater in the British Idea. Nature 219:725-727. Ukalea, R. 1962. Growth of pure culture* of marina phytoplankton in the pres ence of toxicants. AppL Microbiol. 10:532-537. Wiameyer, S. N., and R. D. Porter. 1970. DDK thine eggriielD of captive Ameri can kestrels. Nature 227:737-738. Windom, H. L. 1969. Atmosphere dust records in permanent snowfields: ImpUeations to marine sedimentation. Bull Gaol. Soc. Am. 80:761-782. Wolman, 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. Wurstef, C. P. 1969. DOT reduces pfaotoeythesis by marine phytoplankton. Science 159:1474-147S. Wust, G. 1936. Oberflachan SaUgehait, Verdunstung und Niederechlag auf dem Weltmeere, p. 345-359. In H. Louie and W. Pansen (ed.l, Landerkundlicbe Forachung: Festachrift Norbart Krebs. J. Engethoms, Stuttgart. Yatea, M. L., W. Holewede, and A. L. Hiper. 1970. Pesticide retidues in hydro* biological environments. 139th ACS National Meeting, Houston, Texas, Feb. 1970. Water, Air and Waste Chemistry Section of the American Chemical Society Abstract, p. Watr-032. EDWARD D. GOLDBERG GE1RMUNDER ARNASON JOSEPH L. REID M GRANT GROSS FRANK LOWMAN Appendix A Proposed Base-line Sampling Program There ire few data on the present concentrations of potentially toxic pollutants in the marine environment. Such base-line dsta are essen tial in identifying areas of needed research. However, while perhaps desirable in the future, a global monitoring program requiring great expenditures and technological advances is an inexpeditious approach to acquiring data that are needed immediately. A simplified base-line sampling program meets 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-line program for the marine environment. WIND SYSTEMS To design a network of sampling stations for measuring concentra tions of gaseous and particulate pollutants in the atmosphere, the* 23 *CNS 069463 24 ArriNDix a prevailing global wind systems must be considered in relation to the major sources of pollutants. It is alto 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 aouroes 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-30*S: These easterly winds near the earth's surfaoe 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-?0"N, 30*S-6S*S: The westerly winds in crease in strength to a height of at least 10 km The polar easterlies, 70*N-9Q*N, 65S-90oS: 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 sons! flow. The lateral and vertical transport mechanisms within these wind systems are small-scale turbulenoe, local circulations such as ordinary convection and severe storms, extratroptcal 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 (196S) reports that the number of these particles of 1-10-ju radius decreases quite rapidly with alti tude; for the smallest of these particles (1 n radius), the decrease is HONS 069464 APPENDIX A 25 approximately tenfold from the tea surface up to an altitude of 6 km. For submicron-aize particles, the rate of decrease with altitude it 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 S km. The cor responding altitude is somewhat lower in the trade winds and the polar easterlies. Major sources of pollutants are the United States, western Europe, the Soviet Union, China, and Japan, alt located within the westerlies. Minor sources are Africa (located within the trade winds and, to a lea ser extent, within the westerlies), South America (located within the trade winds and the westerlies), and Australia (located within the trade winds). Baaed on this distribution, we suggest the following sample network. Location Numb*? of Sample* Surface $00 m 1,500 m S km Frequency per year Total North America Europe and Ada Africa Smith America North Atlantic South Atlantic North Padfk South Pacific Auftraiia Arctic Antarctic Subtropical highrpressurt cells IS 20 3 3 S 3 7 3 i l i 2 74 10 S 03 03 03 03 04 00 01 00 00 00 22 32 31 31 31 31 41 31 11 11 1l 2l S6 76 9 9 11 9 IS 6 3 2 2 4 Additional measurement* should be obtained near the sea surface by means of research and commercial ships and at greater altitudes by means of special-purpose and commercial aircraft. Aircraft obser vations are, perhaps, the only observations needed above 5 km. HONS 069465 26 APPENDIX A OCEAN CURRENT SYSTEMS Since the pollutants of potential importance in the ocean may take a variety of forms (such as cases, solutes, particles, oils) and may enter by various paths (e^., 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 first 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 spacing* will be referred to as surface film, shallow array, and deep array and will involve one, three, and seven samples, respectively. Surface fUm A set of 50 surface film samples should be collected, spaced generally over the ocean but with emphasis on the major 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 temples. 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 WO*S 069466 . .. imit-Tir,ilnr''lTlnMiBmiiiii n ' m appendix a 27 base-line 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 downwelllng and upwelling of water Sites of centripetal centers of major water gyres Desired coverve 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 maior fisheries since several of these areas are near sites of dense human population and pollution production, support relatively large marine biomasses that may serve at 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 seat 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 and 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 at a given ste (demersal and pelagic fish, mollusks, and crustaoea) 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-1, 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 MCNS Q6946J HONS 0 6 9 4 6 8 FIGURE VI Productivity of mime fuh.nct The number Out .PP -ithrn eech oceernc mbdimion indict,. the qu.ntity (in metnc ion*) of fuh luidcd in 1967. APPENDIX A 29 the foraging areas. 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: Axes Millions of Tons %oi Total Catch MW Atlantic NE Atlantic W Central Atlantic 6 Central Atlantic SW Atlantic SB Atlantic 4.0 10.2 1.3 1.6 1.3 2.5 7.6 19.5 2.5 3.1 2.5 4.B Ana Millions of Tons %of Total Catch N Pacific W Central Pacific B Central Pacific SB Pacific SW Pacific W Indian Ocean E Indian Ocean 6.4 10.5 0.7 11.2 0.4 1.3 0.8 12.2 2a 0 1.3 21.S 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 30* N; 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 shelve* 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 comporite samples each of demersal fish, mol* lusks, and pelagic fish and 12 composite samples of benthic crustaceas total of 138 samples. Except for two sampling stations in the central Pacific, downcurrent 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. MONS 069469 HONS 0 6 9 4 7 0 1 \ -iwltfill J- 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 MoUusks Crustacea Plankton Total 124 42 12 142 320 RIVERS Various types of wastes are carried to coastal oceans by rivers. 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: Riven 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 quasisteady-etate releases and should work well for dissolved (or dispersed) constituents. For riven, two sampling periods are suggested-highflow and low-flow stages-each of 6 months' duration. MGNS 069471 I MOhS 0 6 9 4 7 2 ATPENDIX A 33 The amount of sediment transported by riven 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 oollect river water. Another near the bottom would collect 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 I study are listed below. ; i. North America y !' Hudson r Mississippi St. Lawrence Columbia South America Orinoco Amazon Plata Africa Nile Congo Niger Europe Rhine Danube Po Thames Asia Ganges-Brshmaputrs Yellow (Hwang Ho) Amur Ob Indus Floods are probably a mgjor 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 riverbome sediment and 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. WWflPMPWa-IWIf.wr* MQNS 069473 1 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 SO) should be composited to permit estimates of concentrations in recently de posited sediment. GLACIAL, RAIN, AND SEDIMENT SAMPLES An important reoord 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 polar easterlies Northern hemisphere jets Northern hemisphere trsdei Southern hemisphere trades Southern hemisphere jets Southern hemisphere polar easterlies HONS 069474 i ! 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-snowfieid samples and 48 rain samples be gathered. Deep-tea sediments accumulate at extremely slow rates, fractions of a millimeter to centimeters per thousand years. These deposits are composed of rode debris from the continents, volcanic materials and their degradation products, oceanic predpitates such as the ferro manganese minerals and barite, and 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 remain*, including calcareous and sili ceous tests, provide a measure of the remoral 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 Parific, Indian, and Atlantic oceans can provide a most reasonable set of base-line materials. SUMMARY The proposed base-line sampling program outlined above it, 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 ts possible, with the expectation that a more effective, and less expensive, base-line grid could 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 data, we can better judge the present and future impacts of chlorinated hydrocarbons upon marine ecosystems. J!'-.'I ............ *CA(5 06947s [ X 36 APPENDIX A REFERENCES Holt, $.). 1969. The food resources of the world, p. 99-106. tn Scientific Amarieta editors, The ocean. W. H. Freemen and Co., Sea Francisco. Isaacs, I. D. 1969. The nature of oceanic Ufa, p. 65-40. tn Scientific American editors. The ocean. V. H. Freeman and Go., San Frandeco. Study of Critical Environmental Problems (scar). 1970. Men i tmpmei on th* Globol Environment: Au*tim*nt end Rgcommtndnthnt for Action. The MIT Frees, Cambridge, Mass. 319 p. Ting, R. Y., and V. R. de Vega, 1969. The nature of the distribution of trace elements in loag-ooee anchovy, Atlantic thread herring and alga, p. 527-334. In Proceedings of the Second National SyapoMum on Radioecology, usaic Document Conf*670S03, National Technical In/ormetioit Service. Toba, Y. 1965. On tha giant sea*aalt particlaa in the atmosphere. TeUna 17; 131 145. 1 | ' MONS 069476 EDVARD D. GOLDB8RG M. GRANT GROSS Appendix B Identification of Globally Distributed Wastes in the Marine Environment We propose set of hue-line measurements to identify distributions nd oonoentntioni of man-introduced materials in the atmosphere and ocean. Such a program can define present or potential threats to the continued survival and well-being of marine ecosystems. Already, mercury, lalogenated hydrocarbons, and oil have been widely recog nised. We seek to identify other materials of comparable significance. Attention is focused primarily on atmospherically transported ma terials for several reasons: River-carried solids are extremely diverse 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 areas 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 38 APPENDIX 8 Particles from the combustion of fossil fuels and from industrial activities Clements introduced to the atmosphere in amounts comparable to those brought to the world's rivers 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 soot 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, 19SS); 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 Process Particles Injected Into Atmosphere (g/yr) Natural processes Continental rook debris See salt 10* Volcanic emanations 101*' U.S. industrial, agricultural, and social releases" Total 101* Transportation 2xl01J Fuel combustion 96X1011 Industrial 15xl0,J A^icultural 54 x101' "Goidbsn. anpnbUshad data. fWindom er*l.,lUl *Nationid Air Pollution Control Administration (NAPCA), 1970. HONS 069478 m AFFENDIX a 39 Elemental cubon can be determined in atmospheric dusts and rains as part of the base-line program. Further, the historical record of fostil-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 fomil-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 mullite made during the burn ing of coals. This mineral is detectable in fly ash (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 Ihe 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 case, 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 at solids. In any case, 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 tetramethy) 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 as 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; PONS 06997*9 i 40 APPENDIX B TABLE B-2 Mobilisation of Elements at tha Earth's Surfaoa (|/yr). (Man-made miaatons for mercury and laid art on i worklwida buii; for tha other metals. US. values are given.) Element Cd H* Nl Pb V Natural Emiarion* 3.1 X 10* 5.0 x 10* 2.0 XIO11 2.1 X10" 2.5x10" Industrial EmUon Approximate Vaiua (I/ 2.0x10'* 4.0 X 10'' 7.0 X 10' .0x 10,,'< 5.0 X 10'* 10,000,000 50,000,000 13,000,000 20,000,000 2,000,000 "GoUton, IMS. ^NattoasuAk PoOntfon Control Adml gitoMMGoM>n. 1970. i.V Ni. Ihnh of Ukm, 1941. cadmium it alao 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 lots 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 woiid production of petroleum (50 million torn per year in the United States). In addition, there is a substantial loss of hydrocarbons through fuel combustion, transportation, industrial processes, and solid waste disposal (Table B-3). Several criteria are sugpsted 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 is 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 D DT and its residues through the food chain and their subsequent effect upon bird and fish populations illustrates such s case. Its physical form interferes with an organism*! growth, activity, or HONS 069460 [ I HP iV,, a.* \ riririll itu APPENDIX * 41 TABLE B-3 Organic CbemteaU-Sonw Production and Potential Emhrioe Data for United State** Substance Total amount* of lymtfeatic organics DDT PCS'* Dry*daaninc aohmntt, parcUoroatkylona and triehlorotbaylans Pf*o^l2(ca,Pa) Gaaolin* into stmoepber* Hydrocarbons lost in transportation, fuel eombustton, industrial patin, solid waste dfepoml, etc. Petroleum dlractly mtrlw wdrmuiMt by man's nilldUu Present Production Rate (i/yr) 5xl0*> 2x10" S x 10* 2xl0n l xIO11 BbMob Rata (t/yr) 2 x 1011 I x !0n 1 x 10,a 3 x ID1* 3 X !0ia Geldtiq. aapatunad data. well-being. For example, aabeatos fibers and riiiceoua partidea cauae damafe to man'i lungs. The material or ita decompoaition product! U alien to the marine environment but rimilar to eubetancee that hare known teratogenic, mutaienic, toxic, or carcinogenic effect!. For example, the dry cleaning solvent, trichloroethylene, may affect enzyme actiritiea aa do the heavier chlorinated hydrocarbon!. A team of priority for the inchiaion of fynthetic organic chemical! in a bese-Une program may be established by uring such criteria in combination with the chemical and biochemical characteriitic* of a given aubatance. Thii niggeiti that ipecial attention be given halogenatad organic compounda The 2.1 million tom per year of petroleum introduced directly into rite marine environment (Study of Critical Environmental Problem! (iCBP), 1970, p. 267] provide! a ipecial caae of a aubatance to be measured Much of thii material, introduced into coaital waters, estuaries, harbors, and shipping lanes, may accumulate in the airwater interface to form alicki. Such a veneer over the ocean may be HONS 069401 42 APPENDIX B a site 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 diverted 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 midlatitudinal oceanic areas in the northern hemisphere. With halogenated hydro* carbons, entry through the atmosphere to the ocean probably involves a reservoir at the air-water interface. Natural substances forming such surface films include fatty acids and their alcohols; man-introduced materials consist of oil from leakages and spills. Such a 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-line measurements to identify di* tribution* 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 films, such as DDT and its residues, freon, and gasoline hydrocarbons. REFERENCES Folgsr, D. W. 1970. Wind transport of land-derived mineral, biogenic and indue* trial matter over the North Atlantic. Deep-See Res. 17:337-332. Ooldbetf, E- D. 1965. Minor elements in see water, p. 163-196. in J. P. Riley and G. SUrow (ad.). Chemical oceanotraphy, VoL 1. Academic Prase, London. Gorham, E. 1953. On the acidity end salinity of rain. Geochem. Cownorium. Acta 7:231-239. Grow, M. G. 1971. Oceanography. 2nd ed. Charles B. Merrill PublhhlngCo., Columbus, Ohio. 150 p. Klein, D. H.. and B. D. Goldberg. 1970. Mercury in marine environment. Bnviron. Set. TechnoL 4:765-768. National Air Pollution Control Administration (naPCa), (1970). Summary of emiisionf in the United States, 1970 edition. Public Health Service, U.S. Department of Health, Education, and Welfare. Raleigh, North Carolina. (mimeo) 49 p. Study of Critical Environmental Problems (SCEP), (1970). Man's impact on the global environment: Aeralament and recommendation! for action. The mit Pram, Cambridge, Memechusette. 319 p. U.S. Bureau of Mines. 1968. Minerals Yearbook, 1967. U.S. Government Print ing Office, Washington, D.C. Windom, H., J. J. Griffin, and E. D. Goldberg. 1967. Talc in atmoepheric dusts. Bnviron. Sd. Teehnol. 1:923-926. , ; J i t HONS 069482