Document g20zyVEL0nQbwX9OvE9bZJM0J

f Dquisifinn of I>D^ and J*oIyvIiIc>riiialc(l Biphenyls in Oatcd Sediments of llic Santa Barbara Basin ^ f 1 19/4 Core 205 (32" I 2'N: i 20<-02'\V. 505 m) was selected for the chlorinated hydiocarhon slndy. It was obtained witli a box corer, designed to operate Abstract. /Analysts of datctl oceanic sediments from the Santa Uarbara llasin with the ship's wire slackened and to of llic Southern California flight has shown that deposition of polychlurinnial penetrate slowly into the sediment. The biphenyls (PCUI began about 1906 tmt! that DDE | /,/tlicliloro-2-2-liistp-chbiophen\l)elhvlcne] first appeared in sediments deposited about IV62. Concentralioio of both show a progressive increase tlnmtgh D>t>7: estimated deposition raid (in grains per square meter per year) in 1067 of DDE and PCU were l.o X 10--I and 1.2 X 10 respectively. closing arms of the coier were dirccilv attached to the collecting box, allowing a tight seal and minimizing disturbance during rccovciy mnl handling. Upon retrieval, the box and core were quick lAiimination of dated marine sedi ments deposited in basins of the south ern California coastal /one has shown dial the present flint of both lead and inerciny into the sediments exceeds di.it of die I9ih century. In the Santa llaihnia ll.isin, west of Santa Durham and southeast of I'oinl Conception, the anlino|io|:cnic least ihi\ is estimated to lie twice that deriving trom natural reduction _in_their residues_as input decreases. The varied anaerobic sediments of the Santa B.iibara Basin present an opportunity to determine the rale of deposition of these chlorinated hydro carbons in the sediments within an absolute time framework. T he lamina tions observed in the sediment arc a direct response to the seasonal rainfall ly frozen and placed in cold storage. Later the frozen coie was extruded and cut into longitudinal slabs from winch x-ratliograplis were obtained. These radiogiaphs were u.ed to construct varve pattern templates which allowed the sectioning ot (be frozen slabs into bulk subs.imples leprcsenlative of a specific set of years, 1 he stall analyzed was cut from the central part of ilv. core and sectioned, and siibsamplcs .sources. The incts'ase of the mercury of the southern California region. 1 lie were stored in glass jars, sealed with flux into the Santa Bnibnia llasin bepan low oxyp.en content of the bottom wa aluminum foil, both of which had been about 1900; the present anthropogenic ters of the basin excludes burrowing thoroughly washed with acetone known input is estimated to he espiivals'itl to organisms and permits the preservation to he free of contaminating substances. the natural input (/). Doth lead and of the line sediment structure. The ac The frozen samples were further mercury arc lapiilly precipitated intn curacy of the overall time framework chilled with liquid nitrogen and freeze- sediments upon entry In the marine en derived by die counting of ihc varves dried with a VirTis lyophiiizer over a vironment from rivers- or waste-water has been confirmed by the correspon minimum period of 12 hours. A sub outfalls (2, .?). In oceanic areas remote dence of rainfall and sedimentation pat sample of approximate!' 2.5 g was from those outbids, a significant hut as terns (71 and by -'"I'b and --v rh/'- '-l h Soxhlcl-cxlractcd with 500 ml of Nnno- yet undetermined fraction of die flux radiometric age measurements (ft. 9). grado (Mallinlsi odl) hexane fur 14 into the basin sediments is assumed to derive from ncrial fallout (/. !). We report here on the deposition of Table I. Orpanochlorinc concentrations ||>arix |>ci trillion (npb) of 1 lie dry 'nip,till in ihlcd two primps of synthetic orpanoclilurincs sediments. in the sediments of the Santa Barbara llasin. Both the DDT (5) compounds, principally /i./j'-DDK (5), and the poly chlorinated biphenyls (I'CBl have be come significant components of the. m..line food v.cbs of southern Cali fornia It has been found lh.it DDL ficipicntly constitutes more than 0.1 percent nf die fai of li.sh-ealinp birds such ns the brown pelican (Peleeunus oceidcntalis) and of sea lions (/.aluphus ralifornianus). Hoili DDT. anti BCD are associated Year IKMtl 1905 1917 1925 m7 mo m2 1935 IV37 Dry weight nnjily/cd (g) 2.61 2.72 i.:>4 2.33 2.01 2 59 2.55 2.67 2.64 /i,p'-DDH (ppb) ; 25 r--2 --A Group A -JO -ilO -21 Group li -'-2.6 5:2.s r-T.O p.p'-mv) (pph) pen (<1iy weij-.lil anal) ml) (ppP) r: <) r<<,\ --WR ' 4.K -4.4 ' 29 0.52 r.) ' 21 (7.M r.) with a hiph incidence of premature hirliis amonp. these sea lions, and DDT, accounts for most if not all of the in creased variance in the calcium car bonate content of the dun shells of eggs of the fish-eating biids (6). I be 1iip.fl ctmcenli aliints of both DIM: and om 19 12 ms WJ7 m<i i *>52 2.61 2.58 2.00 2.25 2.09 2.71 (if (flip C. . r.3.7 <1 Giottp 1) r.4 ?:4 : .S < 1.0 < t (1 < to '2.0 : 2 9 '31 (7.US 49 (7.75 pi l'CB encountered in these and other dial inc ocos) stems supitesl dial die rates of deitradalion in the marine en vironment are slow; however, deposi tion i:t die sediment:, provides a p.ifhw.iy foi die rciiiov.il oT these pollorrmis from die, marine Iiininasx and for the 1955 1957 IVf.O 1W.5 Group 1:.:-5 24 2.02 ?< 2,72 47 Gtoup / 2.05 52 2.0`> I2K 1,7.1 1M) M.9 v.o 66 (7.-H pi 7.0 7.5 11.3 |(11 (7 vr. r) 18.4 It MINT 1974 DSW 026370 STLCOPCB4010331 hours. A 10.2-cnt column of Florisil (14 g). Irtcubalcd at 700C for 5 hours to remove compounds producing inter fering peaks, topped by 2.5 cm of an ' hydrous sodium sulfate, was used for cleanup. Chlorinated hydrocarbons were eluted with 200 nil of 6 percent diethyl ether (Nnnogradc) in n-hcxanc. Vol umes were reduced to H) ml or less with a three-hall Snyder column for analysis by gas-liquid chromatography. Blanks consisting of 500 ml of /(-hexane were refluxed in lire S'oxhlct apparatus for a minimum of 14 hours and then carried through all subsequent steps. These contained less than the equiva lent of 5 parts per billion (ppb) of DDE and 30 ppb of PCB in u 2.5-g sample. Concentrations of 10 ppb of DDE and 30 ppl> of PCB were assumed to repre sent the background within the an alytical procedure. Since PCB has a lower electron-capture response than an equivalent mass of DDE. samples were combined after analysis for the DDT compounds to determine PCB concentrations, according to the group ings in Table I. The profile of the PCB peaks rctcnThlcd that of Aroclor 1254, wineh was used as a reference standard. Iden tification of /r./r'-DDD TT) was con firmed on the basis of the disappearance of the peak with saponification (10) and the appearance of a peak with the characteristic retention time of the cth ylcnc derivative, //./i'-DDMU (5). Hie results of the analyses tire pre sented in Table I and in Fig. I. Con version of these concentrations, which arc expressed on a dry weight basis, to an aluminum basis to correct for the salt content in the interstitial wafer of surface sediments shows no devia tion from the curses depicted in Tig. I. 1 lie deposition of PC 11 began about 1945, following the rapid increase in I'Clt use dining World War II as elec trical insulating fluids, as paint addi tives, and in a vatiely of miscellaneous applications which result in the release Fig. I. Deposition of (A) DDF. anil (11) PCtl in ilaleil sediments itf tlie Santa Bar bara Basin. of these compounds to the environment (II). Measurable amounts of DDE ap pear only in the sediments deposited after 1952. We attribute the higher DDE concentrations in the 1930 sam ple to spurious contamination during collection, storage, or analysis. Neither DDE nor PCI! shows nnv succcstipn ~5T a leveling olV in rate of rtoprsy- lion un tin ouch 1967. Koidc cl nl. (8) estimate from 2,"Pb dating a deposition rale of 0.39 cm/ year, in agreement with the stratigraph ic estimates of 0.4 cm/ycar. The mass of dry sediment per cubic centimeter of deposition was determined to be 0.3 g. The 1907 DDE concentrations of 160 ppb is therefore equivalent to a deposition rate of (160 X 10-") times (0.3 g per cubic centimeter of deposit) times (0.39 ent/year) times ( 101 cm2/ nr2) = 1.9 X 10'p nt--' year-1. The rate ofVc'B deposition during the same time--interval Is 1.2 X 10-^ g fiv1 - year These figures may be as sumed to he minimum cstimaUs of the fluxes of these compounds into the overlying waters. The flux of //.//'-DDE + />,/i'-DDD, both of which may derive from p.p'-DDT. is approxi mately twice the atmospheric fallout rale of the DDT compounds in precipi tation over Britain during the period from August 1966 to July 1967 (12). T he mean concentration of DDT coin pounds (//.//'-DDE -f- //.//'-DDT + />.//'- DDD) in rainfall at seven collecting stations in Britain of M0 parts per 10'-1, assuming an annual rainfall of 100 cm, is equivalent to h deposition of X x 10 g m- 2 year1. From global pro duction figures it is known that this value must he considered a maximum estimate of ihc flux of DDT com pounds into oceanic systems from the atmosphere (/.*) Local sources for most of Ihc DDT compounds in the Santa Barbara Basin are therefore sug gested. "I lie measured deposition rate of DDF compounds in 1967. if typical of other areas in the Southern California Bight, would represent a total deposilion of 10 metric tons per year over an area 200 km by 200 km. This figure greatly exceeds the estimate of 2 metric tons of DDT compounds entering San Francisco Bay from the drainage wa ters of the principal agricultural areas of California in 1967 (14). The esti mated yearly input of DDT compounds from the atmosphere ihlo the Southern California Bight in 1971-1972, after cessation of most DDT use in Cali fornia, was 2 metric tons (.?). The rales of atmospheric fallout during the mid1960's, when local use of DDT was extensive, may have been several limes higher. Substantially higher concentrations of DDT compounds arc present in sedi ments adjacent to the outfall of the Los Angeles County Sanitation Dis tricts' municipal waste-water treatment plant (.?). Input to the sea from that source in 1971 amounted to 19 metric tons (3). A subsurface current, mov ing northwnrd from the Los Angeles area at a depth of approximately 200 m through the Channel Islands (15), might therefore also be a source of the DDT compounds in the Santa Barbara Basin sediments. The annual inputs of PCB into the Southern California Bight from wastcwalcr outfalls and Irom surface runoff in 1970-1971 have been estimated to be 10 and 0.25 metric Ions, respective ly. Waste-water treatment plants in the Los Anprtrs--Or:|m>c County Basin pro vided most of this l'CB (.?)! ~ The high rale of local input of both DDT and PCB compounds into the waters of the Southern California Bight precludes extrapolation to other oceanic areas. Some recycling of chlorinated hydrocarbons from sediments into boi- tom-feeding organisms can be expected (16). but the concentrations reported in the Santa Barbara Basin suggest that a substantial portion of the chlori nated hydrocarbons entering the sea from diverse sources is being deposited in the sediments. Wii.son Hum ', Roman W. Kimuuiouou Itoilepa Marine l.iihonitory. University of California, i\0. lto.\ 247. Dotlepa Da) 64623 Anuri w Soil i ah Scripps limitation of Oceanography. La Jolla, California 92037 Davih R. Yoono, Southern California Comtni tl'iifur Kesenirh I'tojeei, 1500 Ln\t Imperial lliphwnx, /./ Sepnntlo 90243 I19K ' DSW 026371 SCtl'.NCIl. VOl.. HI c11 > aijMiiKao! i> i 11 j"ah STLCOPCB4010332 Reftrtom * KoU% a* I p, R. Yoiini, t. N. JoIhimmi. A. Soucw. J. D. liaaci, Nature itAnid.I 144. 173 (197J); T. 1. Chow. 1C. W. Breland. K. Rcrllnc. A. Sou- Ur. M, Koiifc, E. 0. Gofi/ber*. Svirner III. 2. r>.SM 0973). D. !!. Kkitl *od F.. Goldbftf. Environ. Sri. Trehnot. 4. 745 <1970); K. K. Imrklan. In Impingement of Man on the Oeeatm, U. W. flood, lid. (Wiky-lmcifccJcBcr, New Yofk. 1971), p. 9. The Ecology of the Soiuhrtn Cahfornta Bight: ImpUeationt for Water Quality Management (SouthTM n CMifornU Cna\ul Water Research Proffft. 1500 East Imrenal Hiehy, El Sr- (undo, 1973). 4. II, V. Well*. M. Koide, fi. D. Goldbcfp. Selencr 174, 691 (1971); M. Murnaiiml. T. J. Chow, C, C. Pallet son, Gruchim. Cosmuchltn. Aria yy I2<3 (1949). t. Abbreviation*: DOT. I,l,l-lrlchk'm 2.2bk(p- chlorophenylkihanc: /.r'-OI)F.. I.l-dichlnro- 2,2*bU(p-chlorophen>l'eilykne: I. I - dlchloro-2,2-bts(/-i hlof ophrn> Ire.hane: p.p'- DDMU, hchlino2.2-biv/p;hknopltcnyl)cth)J- erw. 4. R. NV. Rlicbrouph. (o prutredingx on Sixth Berkeley Symposium of the Mathematical Sia* tittles and i'tohahllitc. I.. M. Le Cam, J. Ney- man, li. L. Scoil, tidv (Unlv. of California Press, Berkeley aod I .os Anpefcs, 1972). p. 443; R. L. Dcl.onp. W, 0. Gllmartin, J. O. Simpson, Science Ibl. H6t> (1973), 7, A. Soular and i. I). Isaacs. Dept. Comm. Nett. Mar. Flth Xcrr. Frilt HiiM. 72. 257 (1974). I. M. koldc, A. Soutar. E. I). Goldberg. Earth rienrt. Sri. f.rii 14. 442 (197:). 9. M. koidc, k. W. Bruland. E. 0. Goldberg, Gtochmt. Cvtntoclihn. Acte .77, H7| (1973); S. Krishnavwaml, B. 5. Amin. I). Lai, A. Soular, f.hutnit. Otfitnugr. IS, 7b) (1973). 10. R. W. KNcbrouph, P. Kcrcbe. H. S. Olcolt. Butt, Emirttti. Cnnrarn. Toxicol. 4, I9J (1969). 11. M. G. BroadhutM. Environ. Health Frrspeci. 2, SI (1972). 12. K. R. T:urani and J. OO. Taitnn, Nature (Loud.) 219. 725 (I96R). 13. E. D. GoJdl*cip. I*. Duller, P. Meier. D. Men* rel. G. Patihk, R. W. Rivcbrotigh. 1.. |\ St:k- cl. Chlorinated //rdrocvr/Mmi 6i the Marine Emirontnent (National Academy of Sciences, Washlnpion. D.C., 1971). 14. R. NS' Kimbrough, R. J. Hogged. J. J. Griffin, E. l>. Goldbcrp, Science l$9. 1233 <I96H): T. E. Bailey and i. R. Il.innuin. J. Sanlt. Eng. Dlv. Am. Sue. Civil Eng. 93. 27 (1967). 15. J. II. Join's. General Circulation ami Water Choractrri\ticx in the Southern California Bight (Southern California Coastal Water Research Projrr(. El Scgundo, 1971). 16. 13. R. Ninuno, P. D. Wilson. R. R. Blackman. A. J. Wilson, Jr., Nature ll.onitj 231, 51) (1971). 17. Supported by NSP pram GX-32RK3 to the Bodcpa Marine Laboratory and NSE pram CA*27J06 to Scripps Institution of Oceanogra phy and by ihc Southern California Coastal Water Research Ptnjrcl (Contribution No. 16). Prrsenl address; Department of Os'caitoprnphy, Univertity . of Washington. Scutilc 9R1H.V 70 Janttary 1974 ft Curvature Detectors in Human Vision? McCollough (/) showed that a strikaflcrcffcct was produced by adapta- lioiN(pr several minutes to a vertical is adapted to the opposite condition. The McCollough effect is, in facr/tpccific to retinal locus (J. 4). Now; with gralinjKpf black and orange stripes allcrnalin)!\wilh a horizontal grating of black and bmc stripes. Black and white test gratings with retinal orientations gaze at the center of the tcM pniiern (Fig. ID), concnvc-up lines appear pink due to adaptation to^ green lines of positive slope to the/right of gaze similar to those of^lhc adapting pat and negative slope leyfhc left of gaze. terns were tinged with colors opposite Similarly, concnvcylown lines appear to the adapting colorsS^Shc ascribed these effects to "color adaptation of orientnlion-specific cdgc-dclcclprs." green. The cxpcrpiicnts I describe here show that this/hypothesis accounts for Riggs' observations. Riggs (') has observed similar ef High-cp/urust adapting patterns (Fig. fects with patterns of curved lincsNFig. 1A) were projected from the rear on a I, A and B, shows his stimuli. Tfyc dilfiiyrtg screen in magenta light (Wrat- observer views lines that arc concavc\ (cn,.uia filter) and green light (Wialtcn up in green light and lines that arc \i.Jf filler). These colors (4) produce concave down in red light, always keep very strong McCollough effects. The ing his gar.c near the center of each pattern (Fig. I A). The lest paUpfn (Fig. ID) then appears pink on/'con- cave-up lines aird green on concavedown lines. Adaptation tc/' weakly curved lines produces aftc-tcHecIs that re most vivid on patlcrptf with sharper 111 curvature. Riggs postulates curvature detectors, which prefer strong curva ture. y \\ - McColloughysimpIcr idea (Ihc ori- cntcd-line hypothesis) can explain these effects. While looking at the center of flic ndapting patterns, the retina to the right of gaze is exposed to green lines of positive .slope and red lines of nega tive slope; the retina to the left of gaze Fig. 1. (A) Adapting puttervs viewed in magenta light and giten lighlVl licsc pat terns hitvc n inditis of ciirvatn)^ of 4.5" when the patterns subtend about 5.5' across. (It) Test pallet it wiilt a radius of cm future of 4..S'. ICourtesy of L\A. kicasl mean luminance was approximately I (0 millilambcrts. The test paitcrns wdre high-contrast prints viewed in while fluorescein room tight. All pat- IcnA were about 5.5 wide, as were RiggsV j ThrVe observers adapted for 20 min utes to\hc concavc-up pattern in' green and the Vnncavc-down one in magenta; the patterns were interchanged every 10 secondiv The observer scanned up and down the vertical midlind of each pattern. Wiln\gazc nt the ccmcr of the test pattern \(Fig. IB), concavc-up tines appeared pink and concnvc-down lines green. But, with gaze about 1 beyond the left or right edge, the colors definitely reversod--concave up lines now appeared green and concave-down lines pink. Riggs onservea that the col ors did not reverse when gaze was moved somewhat off the midlinc. The orienlcd-linc hypolhdsii predicts that Ihc colors will nppcnrWcaker as gaze moves off the midlincAbul the clearest color reversal will occur only when gaze falls about 1* iicyond the edges of the pattern. No reversal is expected even when gaze is/as much as 1.5 from the midlinc. TJic concavc-up lines will still predominantly stimulate re gions to Ihc right of gaze With lines of positive slope ana regions! to the left of gaze with lines of negative slope, and the concavc/down lines will have the opposite effect. (These \ properties may be seen bv sliding a tracing of Fig. IA across Fig. IB.) \ Riggs observed that cacli 'panel of Ihc lest pattern (concavc-up or con cave-down lines) appeared pink or green throughout. This spread of color along contour/ within each panel, espe cially to the horizontal tangents of the curves, rcflculs a general propctly of the McColiCjUgh effect (4), andt docs not support j\hc curvature detector hy pothesis in particular, contrar^ to Riggs' argument. \ Truly oin vature-spccific adaptation was not observed here. Three observers adapted for 20 minutes us described above while fixating a single point on a horizontal train of lighted points that moved leftward across Ihc adapting pattern]/ at approximately 1.5 per sec ond. Tjic train subtended 20 centered on each pattern, and Ihc observer trucked repeatedly from far right to far left. Two other observers adapted for ,i hour to the opposite color con dilion, and Ihc patterns were inter changed between each track fiom right to left. No aftereffects were seen, livery U JUNI! 1974 DSM 026372 STLCOPCB4010333