Document YDxjL2QBXO7EX3kd9kvN6GRLk
GENERAL m s ELECTRIC
COMPANY
NILA >AKK. CIEVIIAND, OHIO 44112
Dr. E. M. Kline NEW YORK OFFICE Dear Ed:
Ana M 111 . 2 .6 6 - 3 3 7 6 . . .
*-I'
1 RECEIVED
MAR19 1969
EDWARD M. KLINE M. D.
LAMP DIVISION
March 17, 199
I have been in telephone conversation with Dr. Emmet Kelly and Ed Wheeler, Medical Director and Industrial Hygienist respectively of Monsanto Chemical Co. in St. Louis. They are concerned over some recent technical and newspaper articles relating to the presence of polychlorobiphenyl products in widely dispersed fish and wildlife. The increasing interest in the effects of pesticides, especially chlorinated ones, on the ecosystem has raised the question of what adverse effects, even the pico-graa quantities of the polychlorobi phenyl compounds found in birds' livers and eggs and in fish livers, can have on the normal development of these species. At present, there is little to Indicate whether these compounds have been dis persed atmospherically or have been waterborne.
The General Electric Co. purchases its chlorinated polyphenyls from Monsanto Co., modifies it, and uses it under the name of Pyranol. I believe the major application for this material in our Company is as a dielectric for certain types of transformers and capacitors. Dr. Kelly wss not sounding a tocsin, but thought that the proper .people in our organization should be alerted to the possibility that questions may be aimed at us, or that we may want to make some attempt to determine to what degree the Components using this material dis charge it as either liquid or solid waste, or as an air contaminant.
I am attaching several articles on this subject which you may wish to pass on to the proper person or persons. One individual who is highly knowledgeable about the uses of Pyranol is A. Raab at the Laboratory in Pittsfield, Massachusetts. Dr. Raab may be a good person to contact first.
Best personal regards,
G E N P O O H 05
s
IM:ejp Attachments cc: JW Loney, M.D.
I. Matelsky Industrial Hygienist
# 116. 20,
735881
SG7
. terminated and tho completed chain released attached by the phcnylalanyl /RXA simply by starving
* * . fjbosomo-tfiKNA complex to which it is bound for threonine. With this ho has been able to define the
iltNA molecule carrying the Inst amino-acid condition* necessary for termination; incubating the
1a>rili^d. There muat be a mechanism for reeling complex under suitable conditions with or without
^T iin terminating codon (three codons UAA, UAG, threonine or supernatant enzymes showed th at to get
* ViJA can co^ *0T c^a*n term ination) and cleaving. release it is necessary but not sufficient to complete the
**UaI ncptidyI-/RXA bond. In B iodam . Iiiophys, peptide by incorporating threonine and th at release
* t om*; 28, 773 (19G7) he describe* an experimental is not solely dependent on the transfer enzymes
* mdevised to give a rapid assay for chain tormina- required to move the ribosome from the thrconyl codon
in Ptoc. U S Nat. Acad. 5 \, 53, 1144 (1967) to the UAG terminating codon. Release docs, however,
* the discovery of an enzyme required for depend upon the presence of a supernatant factor. This
factor, with a molecular weight of between 40,000 and
' hr gmay for term ination employs the RXA from 50,000, sediments between 3*55 and 4*55. Because its
^niUr m uUnt of the coat protein gene of the RXA releasing activity is not affected by RXase, it cannot
luruiphagc /?17. This m utant has an amber codon, be an RXA-protein complex. Apparently the substrate
s( the position of the sixth amino-acid, a gluta- of the release enzyme is the ribosome-mRXA-peptidyl
miduc, in the J?17 coat protein molecule. In a /RXA complex so that it must act directly at the ribo
m* system the m utant RXA directs the synthesis some and not cleave the tRXA from pcptidyl-/RXA
\ *unall X-terminal peptide of th e coat protein with already released into the supernatant, which was the
ir Mf|urnce K-forraylm ct-ala-scr-aspn-phc-thr; the other possibility.
*it nuno-acid in the coat protein is glutamine, but Capecchi does not yet know whether the release
, iii the m utant RXA the am ber codon causes pre enzyme works alone or in conjunction with other factors,
plan* termination of synthesis an d the release of the in particular a hypothetical chain termination /RXA
-ujrptide. The great virtue of this system is th a t which reads the termination codon but docs not carry
> yuterminated peptide still attached to the peptidy] an amino-acid. Many people, including Capecchi, have
t \ \ can be distinguished from th e term inated peptide searched in vain for such a /RXA species, and although
from the /RXA and tho am ounts of each negative results can never exclude the possibility th at
^*irrd. Furtherm ore, starving th e system for any one such /RXA exists it is reasonable to think about
I the six amino-acids in the peptide arrests the trails- alternative models in which the terminating codons
*m machinery before it reaches th e UAG codon so arc read either by the ribosome or the release enzyme
%fminstion can be controlled.
or in which nonsense codons function simply because
Kiploitins this procedure, Capecchi isolated a they cannot be read at all. Further characterization
suplcx of ribosome, mRXA and pentapeptide of the release enzyme could well decide the inue.
i
Chlorinated Hydrocarbons in British Wildlife
0 C HOLMES > H. SIMMONS 1 0*C. TATTON
J |**0f>t0fy / the Govsramsnc O im lit,
Polychlorobiphenyl compounds have been detected in British wildlife, in birds* livers and eggs they are often in greater quantities than organochlorine pesticide residues. Polychlorobiphenyls are known to be toxic, and their detection in wildlife raises the question of the adverse effect they may have.
birds* egga o r th o liv ers o f B ritish w ildlife an **ftMiif'i2 b y g a s-liq u id c h ro m a to g r a p h y (G LC) u sin g `oiem -capture d o to c tio n , p e a k s c o rre s p o n d in g to su c h Jrf*ilorino poeticidee as B H C , d irld rin a n d D D T , a n d
* * m etabolites a n d breakdow n p ro d u ets, often appoar * , l" rtW iltan t o h ro m a to g ra m s. T h c o o p e a k s so m e tim e s
| I*!*"*11* a m o u n ts w in c h a re sig n ific a n t fro m a to x ic o lo |*int o f vio w , b u t th o s e n s itiv ity o f m o d e m in s tru H,#e o n ab le s c o m p le te ly in s ig n ific a n t a m o u n ts to bo
| A nalysts ooncomed w ith tho determ ination of ^rnwielilorine postieidos in w ildlife, how ever, liavo long f~n * * * * * t h a t i t is n o t u n u su a l f o r a n a d d itio n a l hoi ie*
<** >>>Any to n p o a k s, oo rra t p o n d in g to u n id e n tifie d L m ,""11**** also t o a p p o a r o n th o s e c h ro m a to g ra m * 1-4, u ^ nown o f th o structure an d origin of these com-
"# but R o b u rn 1 e sta b lish ^ th a t th ey ore organo-
chlorino in nature, with a substantial chlorine content, and consequently possess electron-capturing proportion.
On silicone or 'Apioxnn* GLC eolumns, the series of peaks for theso compounds normally begins at tho point at which pp'-TDE and pp'-DDT are emerging from tho columns and oxtonds. in terms of retention times, to four or five times that of pp'-DDT, which is the last of the commonly occurring pesticides to emerge.
Boforo examination by GLC, samples have normally boon subjected to a fairly rigorous cloan-up procedure, such as that of do Faubort Maunder tt at.*9which include* a dimothylformamidc-hexano partition and passage through a column of prepared alumina. Because the** unknown compounds are similar in nature and properties to tho orgunoehlorino pesticides, they also pass through this and similar clean-up procedures; consequently, they
735882
GENP001I06
28 NATURE. VOL. 216, OCTOBER g,
often interforo soriously with determination*
of pp'-TDE and j?p'-Dl)T in wildlife bocauco
of overlapping of the chromatographic peak**
Suitoblo procedures havo boon devised to
ovoroome this difficulty of interfering peaks.
Ono method is to oficct a better resolution of
thoeo particular peaks by choico of a suitable
stationary* phuso for GLC*. Another method,
which also demonstrates the presence of
these compounds in the somplo, is the uro
of a preliminary thin layer chromatographic
treatment9. The cleaned-up extracts are
examined on silica gel chromatoplatca using
a 1 por cent solution of acetone in hexano as mobile photo*. Spots corresponding to the
I
compounds' can then be found at Rp valuer
between 0*8 and 1*0, whereas tho com
monly occurring orgonochlorino pesticides
and their metaboiitos produco spots of lower
Rp values. A similar separation can also be
shown with reverse phAso paper chromato
graphy* whereby the unknown eompounds
move only a very short distonoe from the
base line compared with the pesticides and
their metabolites.
Gas-liquid ohromatography using dual
channel detection systems with separate eloctron*capture and fiomo-ionization detec
i
tors has also been used to demonstrate the
0
pretenco of large amounts of weakly electroncapturing material, in addition to known
l
pesticide rosiduos, in the eggs of oyster
catchers (Hacmatopus osiraUgui)*.
Experience in this laboratory has shown
that those compounds occur most frequently
and in the largest proportions in the livera,
fat and eggs of birds, particularly terrestrial
predators such as sparrow-hawks (Accipiisr
nisus) and kestrels (Faleo hnnunculus) and
marine feeders such as guillemots (Uria
aalgt) and kittiwakes {RUsa tridaclyla);
they also oommonly occur in freshwater
fish. We have dotccted small amounts
in human and animal fat samples, but less frequently and in much smaller proportions
Tig. 1. G*liquld ehromatoeram of () txtrert of lenire) liver Mid ( polychioroMptenyl ratUu
than in avian samples. A similar series of chromatographic peaks has been properties. In tho prescribed extraction and GLC o-
(observed by Holden1**11 when examining extracts of seals tions, these mixtures produce a series of ch ro m a te jpi
and fish taken in Scottish waters. He found that the poaks given by the extracts of fresh and sea-water fish represen
peaks of tho typo in question. The compounds occurring in British wildlifo comp* `
1
ted fairly low* concentrations, but thoeo given by extracts to tho moro highly chlorinated biphenyl compound *'
o f sool blubbor corresponded to much larger proportions, than the moro lightly chlorinated types The*' !*
o f the order found by this laboratory in birds' eggs.
chlorinated biphenyls also occur to some extent *
Despite considerable curiosity about the identity of theee analogous polyclilorotorphcnyl preparations whirl) I*
oompounds, little progress has been made in identifying commercial uses similar to those of polychlon>hi|!r them, but there has long been a general supposition that It is possiblo that some of tho oompounds with vny !
they were oithor further breakdown or condensation rotention times occurring in British wildlifo arc 1*
products o f tho organochlorine pesticides or possibly chlorinated polyclilorotorphcnyl compounds.
loose compounds of theee with natural preduots such as Fig. la sliows tho gas-liquid chromatogram ^
protein matter.
extract from a kostrrl liver. The peaks eomwpond" *
Jenson, howevor, sueoeeded in identifying a sories of pp'-DDK (0*43 ng). hota-BHC (0*33 ng) and ganim*
such poaks as corresponding to polychlorobiphenyl com (0*03 ng) are labelled. The othor poaks form tls*
pounds, in 200 piko taken in different parts of Sweden, roforrod to abovo and until now w-ould have been ^
and in an eagle1*. We have now boon aWo to show that simply as "unknown organochlorine eom|**,"*J ^
the long retention timo oompounds occurring in British corn**ponding to any known poaticido or its
wildlife are also polyohlorobiphenyi oompounds.
Fig. 16 sliow-s tlio analogous chromatogram of a r*11**^
Polychlorinated biphonyi has boon in oommon commer cial potychlorobiphonyi resin. So far as retorthim
cial use for some timo os a plasticizer in points, resins and aro concornod and apart from the poaticido
^
, plastics. It also has eloctricol insulating properties and is oxart matching for all but a fow peak* m
can bo uxod for a number of other protective purposes. chromatograms.
%i
Commercial preparations o f this material are usually Tho chromatograms siown were obtained by ,|9>
gradod according to tho degreo of chlorination, but all of silicono gum (C E -SE 32) oolumn, but this Pn'r^
tnoro are substantially oomplox mixture* of polychloro- pondonoo botwoon tho retention times o f la* \
biphonyi oompounds that could be oxpociod to rescmblo tho unknow*n compounds and thoeo from the p v
the organochlorine post*oido* in their chomical and physical biphonyi resin has also boon domonstmtod on 'Al"**
G E N P 001107
735883
'vT^ IURE- v 0 t- 216- OCTE E R 2 , ` 1957
. .ELAtrrs irrxrno* n x tt ou this* orrrzzurz quo oclctxi i * * (Bsduding (ise for kao^m pctUcuir)
to which they bear a strong roaembianeo chemically and physically.
0 62
*Apicion L ooluma
CyaootlUeone OF.-XK 60 c&lumn
|U PCB
I4t I* If ! I** 4*1 Tl
1*42
I1S*W7I3 3-
3 70 4*6* 662 Ml
BLE PCD 231 2*30 3-67 2-67 304 206 6*06 6-06 6CC 6*05 6*67 6-66
LEj
1*21 i-:. 2C j 2C2 207 2 00 4C3 611
P t 1-21 1-33 2 15 '2-M 2-95 SCO 4W. 6 11
|LL B*it**l !!** *s tn c ( ( PCB. polychlorobiphenyl reta.
j fyuiiosilicono columns. Tho actual retention times for the poaks on those three typos of column are
. .. _ . 1 \ 'arttier confirmation as to the identity of these com-
imU has been obtained by a study of their behaviour f thin-layer chromatoplates, alumina and silica gel ^irption columns and reverse phase paper chromatoraui. In addition, these compounds have been shown
pomblo the polychlorobiphenyl compounds in their -mien! inertness. Thus they are not easily modified by
chemical reactions to produce readily identifiable '.Us in their retention times on GLC as can bo done, for unco, to pp'-DDT by hydrolysing it to pp'-DDE or to inn by oxidizing it to dieidrin.
A number of livers and eggs taken from birds in the TWituh Isles or thoir coastal waters havo boon examined m this laboratory with results similar to those obtained f r(Inkestrel liver referred to earlier. While the identificam of these compounds in British wildlifo may solve the >**icry of these peaks on GLC chromatograms, it raises, lautvcr, many other questions. Why. for examplo, do Um compounds seora to be accumulated, most frequently +A in the largest proportions, in certain* types of wildtU vurh as birds, seals and fish, and only at the most in trymall proportions in man or his domestic animals such m row or sheep ? In this respect they seem to differ rkrdly from the organochlorine pesticides which soem have invaded nearly all aspects of our environment and
Some of the samples of birds examined in this laboratory have Boomed to contain higher proportions of poiychlorobiphenyl compounds than organochlonno pesticides. For example, the peaks on the chromatogram for tho kestrel liver shown in Fig. 1 were estimated to bo equivalent to about 12 ng of polychlorobiphenyl compounds. This m ust lx* contrasted against the orgnnochiorino posticide residues listed above. These total only about 0*8 ng of which 0 33 ng is beta-BHC, an isomer of BHC which ia generally regarded as non-toxic to wildlife.
Great concern has often been expressod by conservation ists about the effects of posticides on wildlife, particularly birds. The identification of these other organochlorine compounds in wildlifo prompts enquiries as to the possible toxic effects they may be having. That these compounds aro toxic is generally agreedU*M; the polychlorobiphenyls are in fact regarded as an industrial hazard and threshold limits for them ia air have been advised11.
\V* thank the Nature Conservancy for samples of wildlife and Monsanto Chemicals Ltd. for samples of polychlorobiphenyl resins.
Received October 3,1967.
1feature. 3..A*alyUt 10. 467 <1066). Haititon. R. B.. J. Sri. Food Afne.,11.10 (1066). 9Report of Uu Gorrrmwtnd Chrmitt, 70 (KM Stationery Office. London, 1063). 4Walker. C\ R.. HamUtoo, G. A., sad Rarriaoa, R. B.( J, Sri. Food Afrit.,
13. 123 (1067). 4de Faubert Maunder. M J.. Esn. B.. Godly. B. W.. Ramaoad. B. W.
Roburn, J.,sad Tbotaaoa. J.,AoaJyU. 1 0 .16c (1064). Simracaa. J. R.. sad Tattoo. J. 0*G.. J, Ckrommtof..Z7, 263 (1067). 9Abbott. D. C.. gaa. H ..sad Thoaaoa, J., J. Chromaray.. 16.461 (1064). Evans, H.. Aootyat, 7. 660 (1962).
).4Rep1o0r6t6 of Uu Gorommtol Chamiot, 102 (BM Stationery Offlo*. London,
19Holden. A. T., sad Vsndea. X.. J. Froe. loot. Sam. F*nf.. 296 (1066). Koldea, A. V.. J, AjfX. loot.. 1. Hupp!.. 46 (1066k 19Jeoaes. ft., .Var So., 32, 612 (1966). 19Sax. X. Irving. Dooftrona Proptrtiaa of Imduoinoi hitftnoit, 607 (Reis-
hold Publuiung Corporation, Sow York. 1063). 14Brown. R. 14.. Ckrmiot-AmaJyot. 16.33 (1947). 19 DoevminUaiim of TkroohoU Limit Fs/um, 41 (CoemlUee on Tbmbold
Limit Valor*. 1066).
Quasi-stellar Sources, Supernovae and Novae
F F. BROWNE of Manchester Institute ofi
act sad Technology
By considering the opacity of 'surface layer of a star, the author concludes that quasi-stellar sources, supernovae and novae may be different manifestations of the same mechanism.
r Musually considered that the outbursts of novao and
P'tnovao aro fundamentally different proocssee, but I
hore propose a mechanism whlgh can account for
pltcnomena, and which at the tame time can account
* 4far problems concerned with quasi-stellar eouroee
rMAirs). In particular, I suggest that theto outbursts
* liM y to be anisotropic (as indeed thoy aro observed
' laNfur novae). Bocauso the enorgy released during a
M*n*iiva outburst is comparable with tho stellar rout
~*nry, an anisotropic outburst could mean that the star
^^leratod to relativistic velocity in order to conservo
'mium, thue affording a Doppler explanation of the
f# **11-shifts of the quasi -stellar sources.
`dor opacity of a layer, L , at t ho surface of a
&R be the thickness and R the radius of and
w,| *
plasma at temperature, T, with electron
I**1**vo ion donaitiea X# and .V< respectively. L will
to radiation of wavelength >. provided that t is
tT*11-** w^oru T the optical depth of L. A major con ion to t is *//, the optical thieknemi duo to froo-froe
absorptions. It is known that T//oc
(eef. 1),
where induced emissions are included. Suppose, now, that
L is compressed or dilated without changing the total
numbers of ions; that is, AR is varied under conditions
which maintain constant titif' AR.Y,, so that R1Y#
constant. Evidently T /yceN ^ A J?cc^ i l/AJ?. Thus
compression of L increases its opacity, while dilation
reduces the opacity.
Of course, the total number o f ions will not remain
constant in practice, because the recombination rate is
proportional to .Y#A*i. If the percentage of atoms ionized
is large, tho density of unionized atoms, A\ will therefore
be proportional to 'A'. This means that the contribu
tion to the opacity made by bound-bound and bound-free
transitions within unionized atoms is also proportional to*
N 'X t R . This effect, recognized to*be important for
stellar pulsation1*, farther increases the opacity of L on
compression.
Some consequences of this variablo surfaeo opacity will
now lie examined. Under equilibrium conditions the
735884
GENP 00)108
127 4
NATURE. VOL. 21 fi. DECEMBER 30.
Frictions sod M ultiples
fraction
prtTx
symbol
10-* I0-* O-* 10-* 10-* 10-* 10-u
10-*s
deci coati
Bkilli micro B&ao pino lesto atto
d e m
A n
?
a
multipla
pref.x
10 deka 10* hccto 10* ko 10* mcC* 10* gc* 10 te a
To be restricted so aacb u pocsfbit.
symbol
da4 h* k M O T
Compound prefixes should not be used. Thus 10-* metre is represented by 1 nm, not 1 mfua. The attaching of a prefix to a unit in effect constitutes a new unit, so that
1 km* - 1 (km)* - 10*m* not 1 k(m*) m 10*m*.
Where possible any numerical prefix should appear in the
numerator of an expression.
physical quantity length
.area
volume man density force
preesure
Examples of Units Contrary to $1, with their Equivalents
unit
angstrOm inch foot yard mile nautical mile square inch square foot square yard square mile cubic inch cubic foot U.K. gallon pound lug pound/cubic inch pound/cubic foot dyn. m poundal * pound-force kilogramnve-foroe atmosphere torr pound (f)/sq.in.
quivdent
10- m
0-0251 m 0-3018 m M id m 1-000 34 km 1-853 18 km 045-16 mm* 0-092 903 m* 0-836 127 n>> 2-589 99 km1
1-038 71 x lo *in* 0-028 316 8 n.* 0-004 546 092 m* 0-453 592 37 kx 14 593 9 kg 2-767 99x 10* kx ... 10-0185 kg m * 10-N
0-138-255 K 4-448 22 N 9-806 65 N 101-326 N m * 133 322 K m * 894-76 K m
Organochlorine Pesticides in Seals and Porpoises
*>y
A. V. HOLDEN K. MAfcSDEN
Freshwater Fisheries Laboratory, Pitlochry. Perthshire
Seals and porpoises in Scotland and Canada, far from the siici application of pesticides, can accumulate high concentration <' residues in their blubber. These chemicals are spreading throuf* the long food chain which ends with seals and porpoises and obvious cannot be confined to their place of discharge.
Tb s presence of organochlorine residues in marine lifo in many areas of the world, including the Antarctic, has been reported recently1**. In British waters the accumulation of residue in the eggs of sea birds* and the process of oonoentration of pesticides through oert&in food chains in the marine environment4 have been studied. Analyses of various speoies o f marine fish and mammals from Scottish waters during the past 5 years* havo shown that organochlorine residues are now a normal occur* rsnee, the highest concentrations being found in organs or tissues with the highest lipid content. Thus the muscle tissue of salmonids, the liven of ood and the blubber of seals act as storage sites for these residues.
The aquatic mammals, saeh as whales, seals and per*
poises, have a relatively high proportion of the body weight in the form of subcutaneous fat (blubber). Seals feed ohiefiy on gadoids and salmonids, and porpoises chiefly on small gadoids and dupeoida The prooess of oonoentration o f pesticides through their food chain might be orpoctod to result in high pesticide levels in the fat o f these mammals, and samples analysed at this laboratory confirm thie expectation. In reoent years, specimens o f the grey seal {xaJtetocmr prypus), oommon seal (Phooa viiulxna) and
porpoise (Phocacna pkooaena) havo been sampled from the ooasts of Scotland. Semples o f blubber wore available for all the specimens examined, and in a fow eases other organs wore also available. As well es recognized pesticido residues, other electron^spturing substances have been detected by gas-liquid chromatography and, in order to istabliah whothor such subetanoes are as widely distributed es the pesticides, blubber samples from grey seals and
harp seals {Phoca grotnlandioa) on the Canadian All*"1
ooast have also been examined and tho results of iL -
analyses are reported here. Examination of sani|J' 1
seal blubber from othor areas is continuing in <nirf 1
assess the variation between different regions of tl* *-
environment.
All tissue samples from Scottish waters wen* (""
at --18 C until required for analysis. Thu i'anail***
samples wero preserved in 10 per cent formalin.
showed no evidence of any influence on tho ai>*Jt*
procedure, and in this and other oases involving <''
has not affected the efficiency o f recovery of i'***'
residues. Aliquots of tho samples (fig) were gnum!
powder with anhydrous crystalline sodium sulpl*11' 4
grade) and extracted in a Soxhlei apparatus
f*
distilled AR grade n-hexane (previously tested and -- ^
to be free of electron-capturing materials by gw r
togrmphy). The hexane extracts were msdo up to !<"'
and 25 ml. aliquots were subjected to cltwn^up ^
the hoxane-dimcthyiformamido partition
*
Faubcrt Maunder cf al.v, followed by oolumnri,J ^ \
using alumina containing fi per oent water. 1 "? *
pesticido rcsiduos from fat extracts so
H
20 per cent, but, as is customary in poaticida s*** ..
no correction has been mado for such losses in tl*
presented here.
. p,
Tho cluancd-up hexane oxtracts were snidywjil
liquid chromatography on a Varian ^Aerograph ^ ^^
instrumont employing two gloss columns 6 ft*. V .U
outor diameter. Ono column w u packed
^
orb W A WJDMCS 80-100* stmh to d with 1011"
735885
v o l . a te . De c e m b e r 30. 1967
1275
tilicono oil, and tho othor w ith the u n u support, contained w ry low levels of both dirldrin and the DDT
with 5 por cont DC-200 + 7-5 per cent (/M group, uhih* m*u1s from the Cabot Straits (Gulf of St.
silicon. Tho oven tem persturo was 200 C. the Lawrence) contained little dicldrin but higher DDT
>vn gas flow 60 ml./min an d tho column resolution group residues, similar to those of Scottish seals. Of the
jft`ldrin equivalent to ],G00 theoretical plates. TLcro fow porpoises examined, that from Orkney was the least
ll0 gigiu^cant degradation o f DDT on tho columns. cor.i~m:n.ucu, but tho three taken on the cast coast of
y complete separation of th o common pesticide Scotland had markedly higher contents of all the rcsidircs
I,** is possible on ono or oth o r of these columns, measured. One specimen contained a total residue con .frronce by polychJorinatod biphenyl (PCB) residues4** centration (dieidrin and DDT group) of 73*3 p.p.m.
f p,p'.TDE and p.p'-D D T peaks necessitated a fu n her Analyses of a few tissues other than the blubber have
yticol stage. Aliquots (5 m l.) o f some of tho extracts been mode, but concentrations in the blubber have always
'evaporated to dxynoss in a stream of cold filtered air, been found to be the highest (Tablo 2). Concentrations in
the residue refluxed w ith 2 ml. of 2*5 per cent other tissues seem likely to be consistent with their lower
'.frilio potassium hydroxide for 15 min on a warm lipid contents.
r-bath. A fter oooling, 5 ml. o f n-hexane was added,
, taixing, followed by 40 m l of 2 por cent sodium
rhste solution. Tho su p ern atan t hexane layer was analysed by gas-liquid chrom atography. By this
noique, quantitative conversion of p,p'-D D T to ?,?' K. and of p,p'-T D E to p.p'-L ID E (-D D Z dU ), is oblRd, and the conversion product* confirm th e identity of original residues. The residual peaks in the p.p'-D D T
TAbk 2. Scapk
Ore*/ t-ii CC rtezv7 trs.! C.-t/ .*1 Ferpoas
TOTAL DDT ooxcxsTEATiost CE.p.m.) Dr VAAJOOI TLtSCTB
Bobber Liver Brsis Xfalaar I p k n KukU
S-8 0-2
*O7Z7Z
*23 *15
14 & 0*07 6 4 0*44 2-4 O il
*24 *17 *07
*33 *13
_
*03
S3 *S3 *02 *04 *10 *34
ij.p'-TDE positions, where present, eon bo subtracted m the values of tho pesticides originally determined hrso positions. Hydrolysis alao destroys a and*r*BHC,
present, b u t polychlorinated biphonyls are un* A cyanosilicone (AD-GO) colum n1* has also
e used to separate p.p'-D D T and p,p'-T D E from PCB 'erenee, confirming the la tte r,
ft principal pesticido residues found in all samples ained were those of the D D T group, with dieidrin such smaller quantities. Canadian seals contained er concentrations of dicldrin th a n Scottish seals, while Uiih porpoises contained refxiarkabiy high concontra-
of all posticide residues (see T able 1). Interferoneo on DC-200 silicone column in th e p,p'*TD E position caused s non-hydrolysable residue was responsible for about per oent of tho total estim ated p.p'-T D E in tho adion and Scottish samples exam ined. In tho p,p'-
position, the non-hydrolycable residue constituted <at 10 per oent in the C anadian samples and about per oent in the Scotti&h sam ples examined for this
erence, tho total am ount of non-hydrolysable being smaller in th e Canadian samples. The
lues in Table 1 have not been corrected for this internoe, for only a proportion o f the samples were hydro-
The pro;>crtinn of blubber extractable by hexane was determined for some samples* Values ranged from 72 to 56 per cent (mean 50 per cent) for the Canadian seals, and from 8S to 98 per cont (mean 93 per cent) for Scottish goals samples on the breeding grounds off the west coast. (Values for other seal samples were not estimated. ) Con* cent rat ions of pesticides in terms of extractable fat for these samples would thus be up to 40 per cent greater than the values in Table 1, but the general comparison is not significantly affected. The lower extractable fst values for the Canadian samples may possibly be a result of being preserved in formalin.
Concentrations of pesticide residues in tho extractable fat of various organs and tissues of one porpoise show sn im portant relationship (Table 3). While the concentra tions of tho DDT group in the original tissues vary widely, those expressed in terms of extractable fat are in much closer agreement, with the sole exception of the brain. A similar anomaly for tissues of trout was described by Holden11. I t seems likely th at a large proportion of the lipid fraction of the brain may not contain pesticides, and the brain lipid composition is known to differ considerably from th at of depot fat.
4. Results from th e various species o f seals were not
tioeably different in a given area, and have been TaW# 3. COSCECTBATXOXS 07 TOTALEOT(p.pXL) 9 TISSUES Of A70*701*1
lined in Table 1.
TttAue or or9 & Blubber Xucte liver Spines e u m ? Bsms
OoooentrAtloB is tiMU 38 *34 *34 *12 004 002
VtraeotAS ezmet*
L ooHCBirnuTiox a u ro ra ov oeflixocELOtrrE I B D t n S IA7
Able fet
670 *1 112 *1
1*4 I S
0 9 SEALS AVD 1 ems (p.pjn.)
CoBcsntrAtloB In
*4 *2 40 2*4 20 *27
(M saatia
a t n c u t l i fni
im isd
Ko.Ib
Uw of Miapl sa mpte Dkldrls
; v^Uw>d. adult IS * is -m
l r*<l&CS-60)
(*70)
r **d W. Sootland. *06-*30
<dteaU(10&-6S)
(0*20)
j ** W. Scotland, s *06-0*44
I ^pupo (IMS)
i v^4i ASaitdal^n It.,
t
*0(10-*0100)4
"*4 Adult Mala
(0*03)
. w,5Ia7.>Cabot StralU. s *03-0-10
| ".nun. and adult
(*07)
*?*U947)
V**d. Orkner.
1 *30
norpolaeOMT)
adult
s 4-0-18*0
> <*0)
* * '-DDX 9 f -TDE
1*0-11*1 *27-30
1<*1*-'7 0 *17-0*->33
(3*4) <*41)
1*0-40 *1 3 -* SO
#0<7*-1>-3
(*S2) *0 8 -* 14
(11) <*12)
10-17*3 * 3 6 0 1 C*0) <*7S)
1*1 *31
*0-13*3 *2-14*3
03*3)
C*0)
*y*DDT 1*3-23*3 (7*3) 10-7*7 (3*3) 1*1-30 (23) *08-*33 (*3S) 21-15 4 (* 3) *2 13-1-23*7 (21*1)
Tho unidentified peaks on the chromatograms seem to be similar to those produced by polychlorinated bi phenyls and, to enable comparison to be made, the ratios (Rx) of the retention times of all regularly occurring poaks (relative to dieldrin * 100) have been calculated for the operating column temperature of 200* C, these values boing temperature-dependent. The R x values of PCB compounds from commercial PCB formulations wore I** determined for both types of oolumn (Tablo 4). At least seven PCB-type peaks were found, including those which interfere with p.p'-TDE and p,p'-DDT. Hcptachlor epoxide and p.p'-MDE could not be confirmed on both
eolumns and aro not therefore recorded.
'ontomination by pcsticidea is greater in tho seals on The m att significant aspect of tho results is th at,
>east coast of Scotland (token in an area roughly from although seals and porpoises inliabit an environment far
I "wdeon to the T ay estuary) th a n in specimens from the removed from the sito of application or discharge of
1*^ and north coasts, including th e Orkney Islands. pesticides, they can contain much greater concentrations
[^ pups from tho Orknoy an d H arris (west coast) breed- of dieldrin and DDT group residues than thoso rooorded
* grounds contained only slightly lower residues than for most other upccics, including man. Robinson and
^ from tho same areas. B y comparison, th e Canadian H u n ter11 found n mean concentration of dicldrin of 0*22
f ^plcs from the Magdalen Islands (Gulf o f St. Lawrence) p.p.m. (range 0*10-0*73 p.pjn.) and a mean total con-
GENP 001110
735886
1276 NATURE. VOL. 216, DECEMBER 30.
ocntration of DDT of 4*0 p.p.m. (range 1*0> 1M p.p.m.)
in samples of human depot fat m England in 19v4. No evidence of any significant change uuti found during 19&-(>5.
Table 4. bklativs scrssn o ic vali cs (lUt or m a in s * (duslujus - ICO)
7/C-3O column
lUautue
Sample
/>C-2X.'Qi'-l colurr..-.
lLuiJue
* sul Jr
tub - 63 i
v.s* l>DR Ilieldrin
. t
-100
VCB -121
v.p'-TDK -129
TUB -146
*V1>DT -170
rea -174
VCB -205
VCB
-232
i*cb --339
C3 100 125 123 K9 171 175 205 237 33*
PCL - 6-5
p.p'-DDX -- 64
b.eiJria -103
p.p'-7D& -121 -
-123
pc s -14C 5
. R.P'-DDT -147
1\B
-224
PUB --2*2
TO . &3'5
UK) 121 122 147 222 276
The seals and porpoises from the east coast of Scotland were usually more seriously contaminated than those from the north and west coasts. This, at least in respect of seals, may be because, os is believed, the populations in the two areas come from different breeding sites. The seals x>uth of Aberdeen breed principally on the Fam e Islands, off the north east coast of England, while the seals of north and west Scotland are primarily from the breeding grounds of the Orkney Islands in the north, and other islands off (ho west coast of Scotland. The sra off eastern Scotland is also likely to receive more con tam ination from estuarine discharges than that ofT north And west Scotland. Similarly, the two separate seal populations sampled off the cast coast of Canada may inhabit areas with different levels of contamination. Pups contain pesticide residues in concentrations only slightly
lower than in the parent population. Common seals in Holland have been found with concentrations of residue similar to those of seals on the Scottish east coast1*.
While the residue concentrations in subcutaneous fat are high, those of other tissues and organs arc found to l>c much lower. This suggests that there is no risk of physiological effects, unless the metabolism of much of the fat in times of stress leads to a considerable increase in the concentration of the residue in circulating lipids, and thus in residue concentrations in other organs or tissues.
(rvy miiU on th e coast of the Scottish vnainliiNi *
prir:..:n!y on salmon (Sultrw solar) and end u; '*
nvorrLuu :`4. Tho highest concentrations of
*
in the marine environment have so fHf l '
fout.d \u oil front (S. trutta) on tho ca^t coiut with , **
0*2 p.p.u.. fdiiidnn + total DDT) in musclo
'
from tho same area would probably hav*
co:;;vn:.s. Cod examined from tho east coast h a \0
taiuod up to 0-35 p.p.m. (dieldrin + total DDT)in n ,,^
tiaauc (.can C-12 ]>.p.m.) and from the west coast u,
0*5Cp.p.m. (moan 0*22 p.p.m.) while cod livers ennui,,*!
up to 4*0 p.p.m, and 12-0 p.p.m., respectively. Unv
are estimated to ra t about 15 lb. of food daily, ami t
adu.lt seal could consume its own weight in food in L`u >
days. Assuming a high proportion of the pestieadr im*,
to be stored in body fat rather than to be exen>t<| ..
metabolized, an increase of two orders of magititudr ,
pesticide concentration f;om food to body fat with,,, .
few years is feasible. This degree of accumulation .
residue in an environment not deliberately contaniiiuu..i
and in speeies ecologically far distant from th* tsr^
organisms of persistent pesticides, underlines tbv
possibility of confining such chemicals to the are .
application.
\Ye thank Dr B. B. Rae for obtaining the Srtiit..
samples, and Dr C. J. Kcrswill for the Canadian sampU.
Eeerivcu D um ber 15, 1967.
*Up. 1`reiJsnt't Sri. A ir. Comm. (US Govt. Print inf Otte, Via><< . 19&3*.
*T*t;on, J. O'C.. and RuiickA, J. If. A.. Xmlnre. 215. 346 (1967). *Xoot*. X. W.. and Tatton, J. 0*0.. .Nature. 20?, 42 (IMS). 4Rubiiiftdn. J., RirharUiton. A.. Crabtree, A. X., Coulaoa, J. C- aa4 iw .
. It., .Vffitir. 214. 13u7 (1967). 4Drparun^c: of Agriculture and Kithcrie for Scotland, FicWrin uf **
Report for 1965. * Department of Agriculture aod Kiftheriet for Seotlaod, TWwIri mi
iur.J. Report for I960. *De K&*.:trri Maand^r. M. J., Egan. H.. Godly. R. W.. HanuM d. I*. *
indurr.. J.. and Thomon. J.. AnaiyU, 69, I6 (1964). *Jentrn. ?.. Xne SrirmlUt, 32. 612 (1966). 4 Kohne. D. Simmon. J. H.,anl Tatton, J. 0*0.. A'alwr.Dt 227 fiw Simmon, J. U.. and Tatiou. J. 0*0., J. Ckrommlo$.t Z7. 253 <t*7). 11 HoiJen. A. V.. An*. Appi. Liei.. 60. 467 (1962). 14Krfd'.&af'&. J.. and Hunter, C. O.. ArcA. Knriron. HtnUA. 11. U* (iwe 14Ko^mac. i. }(..anl van Gcndercn, H.. J. Appi. Xesf., 6 (Ssr*U. 14 Ran, B. h . Msr. he.. Xn. 2. 39 (1960). 44litmicu. A. V.. J. Appi. Aro/.. 6 (Suppl.). 45 (1906).
The North Pacific: an Example of Tectonics on a Sphere i
by \
d . p. McKe n z ie R. 1. PARKER.
\ \
Institute of Geophysics and ftsneary Physics. University of California at San Q^ejo
Individual aseismic areas move as rigid places on the surfacr o* sphere. Application of the Mercator projection to slip vectors h * ` that the paving stone theory of world tectonics is correct and app*" to about a quarter of the Earth's surface.
a
T ax linear magnetic anomalies'** which parallel all active ridges can only be produced by reversal* of the Earth's magnetio field1 if the oooanio crust ia formed close to the ridge axis*. Models4 have shown that the anomalies cannot bo obsorved in the North Atlantic unless most dyko intrusion, and honco crustal production, occurs within 5 km of the ridgo axis. Tho spreading sea floor* then carries these anomalies for groat horizontal distances with little if any deformation. The epicentres of earth quakes also accurately follow the axis and arc oflset with it by transform faults*-*. The structure of aland arcs is I ons door, though tho narrow band of shallow earthquake* auggesta that crust is consumed along a linear feature.
These observation* are explained if the sea fl** ms a rigid plate, and interacts with other pi*!** M* mically active regions which also ahow rrrent ,rrf#^ , activity. For tlio purposes of this article, trenches are respectiveJy defined as lines aWebg ^
crust is produced and destroyed. Tliey wel ***
topographic features. Transform faults and aro line* of pure slip. They are always panui^^ # fore, to the relative velocity vector between t* 441* ^ most useful property. Wc have tested this P****1? . theurj* of world tectonic* iii the North Pacdw, ^ ^
works well. Imm detailed studi** o f otlwf W * 1
support the tlicory.
735887
Pesticides: Trzzzztlzr.tiz Movements
b the Northeast T rziaz
Abstract. Concentrerons of chloric noted hydrocarbons in airborne dust carried by the trade winds from the European-African land areas to Bar bados range from less than l to 164 parts per biliion.*77* lower limit o f the average content of 1 cubic meter of air is 7.8 X J0 ~ i4 gram. The contributions o f river-borne end atmospherically transported pesticides to parts of the marine environment are calculated approximately and compared. The amounts of pesticides contributed to the tropical Atlantic by the trade winds appear to be comparable to those car ried to the sea by major river systems.
The transport and distribution of pesticides through the world ecosystem have been attributed to a combination of atmospheric and hydrospheric (oceante and fluvial) currents ( J ) , yet their relative contributions remain unclear. The high concentrations of residues of pesticides found in shearwaters Puffinus ienuirostris and P. griseus from the Pacific Ocean and skuas Catharacta skua from Antarctica suggest that coastal areas are not the sites of in gestion ( / ) .
Various lines of evidence indicate air transport: (i) the codistillation of chlorinated hydrocarbons with water (2 ) , and (is) their detection in air and rainwater (5) and in atmospheric dust originating in Texas and subsequently deposited in Ohio (4). These observa tions, however, are not sufficient to support the hypothesis that much of the pesticides present in marine organisms was atmospherically transported to the oceans from the continents.
Complementing such work is the ob servation that the mineral talc that is used as a carrier and diluent for pesti cides occurs in the solid-mineral phases of rains, glaciers, and rivers and in dusts recovered from the atmosphere in con centrations much higher than expected from natural occurrences (5); its exist ence in airborne particulate matter over
the sea (6) suggests a link with the gy asl dispersion of pesticides.
Ahiough tale n perhaps diagnostic of tbs presence of insecticides, its use 6 a quantitative traces is not fully war ranted; it is gradually being displaced fc pesticides by water or light petroleum tacas. Furthermore, some insecticides ere dispersed in Fuller's earth, a mixC=c of minerals not readily analyzed by x-ray diffraction.
Large-scale tropospheric transport fccm continents to oceans can best be approached by investigation of the three cain zones of movement of air masses: the equatorial easterlies, the temperate westerlies, and the polar easterlies. Cram quantities of airborne paniculate cutter carried by the equatorial easterEss, the trade winds, over 6000 km from Europe and Africa across the At lantic to Barbados were collected (7). Pronounced seasonal variations in the magnetic and biological fractions cor related with wind patterns off the Afri can coast. Mineralogical and biological observations pointed to a continental origin of the solids, with Europe and Africa as the most likely sources. Each sample comprised a Urge fraction of the paniculate material in several milEon cubic meters of air. An input rate of solid phases to the tropical Atlantic sediments of 0.6 X 10~4 cm /year was suggested (6). Knowledge of the pesti cide levels in such materials would per mit similar calcuUtions of their inputs, for which purpose the Barbados sam ples have bees analyzed.
The collecting screens (6 ), facing the wind, were made of 0.5-mm-diamcter monofilament nylon woven to give about SO percent voids; they were coated with a SO-perccnt water solution of glycerin for our work; collection efficiency was about SO percent for particles larger than 1 p. Rigorous standards of cleanliness minimized con tamination by local dusts, which has always proved to be trivial. For blank runs for the pesticide analyses, acetonewashed dust was applied to screens, with subsequent treatment as for the ----real samples. Less than 100 pg of any Of the DDT compounds (8) or other pesticides per gram o f sample was found.
The dust samples were Soxhlet-extraded for 6 hours with a 2:1 mixture of hexane and acetone. Blank runs, using the same solvent volumes, extrac tion times, and glassware, *cre made before and several times ouring the course of the analyses; less than 250 _
735888
Fig. 1. X-ray diffractosram (CuKa radiation) of atmospheric dust collected over the Coral Sea, with talc predominating.
pg of any pesticide per gram of sample was present in the controls.
The extracts were concentrated and analyzed with a Micro Tek-220 gas chromatograph equipped with Ni63 and H-3 electron-capture detectors. Two columns, a 5-percent QF-1 and a 10percent DC-200, both on hexamethyl disilazane-treated Chromosorb W, $0to 100-mesh, were used simultaneously. Differences in retention time between the polar and nonpolar columns, com bined with occasional spiking of ex tracts with standards, initially confirmed the identities of several of the peaks observed. Peaks of unknown com pounds fluctuating in intensity over the year were present in all Barbados ex
tracts and occasionally interfered with determination of p,p'-DDE and o,p'DDT.
Extracts of samples between January and September were pooled and placed on a thin-layer plate covered with silica gel G that had been washed until chromatographically clean. A small fraction of the sample extract, mixed with stand ards, was applied to another area of the plate. After development with 10 percent ethyl ether in hexane, the plate was divided into two sets of 13 1-cm strips which were scraped off and washed with petroleum ether. A con centrate of the petroleum ether was then injected into both columns of the gas chromatograph.
D& dria, p.p'-DDT, and p.^-D D D were quantitatively recovered from the corresponding areas of the plate occu pied by the standards. In several ex tracts the interfering peaks made mea surements of p ^-D D E and of o,p'-DDT impossible; the thin-layer recoveries of these compounds were 150 percent. A trace amount of a compound having the retention times of o.p'-DDE was also recovered, but a small peak provision ally attributed to heptachlor epoxide in one extract was not confirmed by thinlayer techniques. None of the uniden tified peaks had retention times equiv alent to those of the polychlorinated biphenyls (PCB), industrial pollutants widely dispersed in marine ecosystems (9). No attempt was made to isolate chemically pure pesticides from the thin-layer extracts in order to obtain infrared spectra; instead, several of the thin-layer extracts were treated with alcoholic KOH under conditions such that p.p'-DDT, o.p'-DDT, and p.p'DDD are convened to their dehydrochlorinated derivatives, which have characteristic retention times on QF-1 and DC-200 columns.
The thin-layer extracts containing most of the p.p'-DDT, p.p^DDD, o.p'DDT, and dicldrin peaks were evapo rated almost to dryness in a graduated test tube to which 1 ml of 10 percent KOH in ethyl alcohol was added. After heating for 5 minutes in a steam bath, water and hexane were added and the solution was swirled. Analysis of the hexane layer showed that the p.p'-DDT, py-D D D , and o.p'-DDT peaks had
Table 1. Pesticides ia airborne particles over Barbados. Concentrations in air are based on 50-pereest efficiency of the conectini net; ND, not detected.
Date ' (1965-66)
Material dry wt (g)
Pesticide cooccstratioos
volume <X HP**) Total.
Analysed
Ia samples (ppb)
py-D D T p^'-DDE of'-D U T DDD
Dicldrin
Tout ia tir
. 1 (s x
Total
1<>*"/ )
4-6 Oct. 26-21 O ct 7-21 Nor. ' 1-15 Dec. 23-25 Dec. 24-21 Jen. 15-17 Feb. 17-19 Feb. 25-27 Mar. 12-14 Apr. 14-16 May 11-13 June 21-23 July 14-12 Aug. 13-15 Sept
23
032 52
12
S3 173 7.70 < 1 3 ND
163
CJ 237
71
19
16.1
53 232
10
ND
XJ . t 7 133 at
49
23
13 037
30
ND
33
13 332
U
13
.1 3
14 142
67
ND
2 4 13 134 14
2.1
2 3 . 4.7 3.10 11
ND
13 9 3 543 X7 ND
3 ! 23 239 73 ND
13 3 239
54 34
13 S 3 439 4 3 3.1
1.7 7 3 4.15 03 13
Total Cry wtifhi mat w iw n d . t Zero Cm eeUrcieC o* 12 prtloM day*. M*.
1234
13 7 3 4 C7 1503S0*
ND ND ND . <13
<13t
ND ND ND 90
99
ND ND ND 40
63
13 1 4 164
2<2
ND
10.7.
XI
49
42
6
ND ND
37
77
17
ND 43
96
931
ND 63 23 25
27
ND ND ND 11
37
ND ND 13
43
41
ND ND XI
1X7
2S
0 3 1.1 13 1X1
110
4
14 13
104
90
1.1
10
13 *
134
120
: fees, villi raciuioa te e ef WpudUoc epea44# also e m i t 73
SCIENCE. VOL. 159
o> CO CO LO CO h-
a--
m 2 o o
--Sv-:r
disappeared, but peaks having the re*tentioa times of DDE, p.p'-DDMU,
and o ^ -D D E had appeared in the re spective extracts. The recoveries of these dehydrochbrinated derivatives were equivalent to those obtained in the saponification of chromaiogrzphically pure standards. No other breakdown products producing peaks in the cicctron-capture detector were identified. The dicldrin peak was not affected by the alkaline-alcohol treatment but could not be found after concentrated sulfuric acid was added to the evaporated ex tract.
All extracts were analyzed with both DC-200 and QF-2 columns, and each value* presented (Table 1) is the aver age from two or more injections of a sample. The total concentrations of the chlorinated hydrocarbons in the dust were higher during the winter months, but the total pesticide content cf the air displayed no evident seasonal changes during 1 year. A relatively high content of magnetic dust had been re ported (6) for September, October, and April when the wind circulations suggest that the dust originates in Morocco; on the other hand, the content was less be tween October and March, when the dust probably comes from tropical Africa south of the Sahara. Most of the biological material was present in the winter samples; fungal hyphae abounded, and bacteria, fragments of vascular plants, and marine and fresh water diatoms were observed. Among the last were Melosira granulate, which a worldwide in distribution, and Denticula elegans, which is found in the running waters of cold mountainous regions. There was no correlation be tween the pesticide content of the air and either the magnetic content or the number of fungal hyphae reported
(6). The pesticide concentration in air
averages 7.8 X 10- 14 g / m \ o r 41 ppb (parts per billion) by weight in the d u st Utilizing the sedimentation calculations on this dust (d ), we can calculate the introduction of pesticides to the equa torial Atlantic by atmospheric transport in the following way. We assume that the area involved in dissemination by the trade winds lies between the equator and 30*N latitude, covering 1.94 X 101T
m*. The reported (6 ) rate of sedimen.lion for this area is 0.06 cm / 1000 yean, equivalent to an annual input of dust solids of 9.70 X 101S g (density of dust, 2 S g/cm a; water content of the sediments, SO percent). The value of
ts MAXCIt IMS
41 ppb of nscc:ic`.J*: ir. ihc dust yields 600 kg/ye-r.
The input of pesticides into Saa Francisco Bey, mcesurcd by the aver age total cooccntmti::. in the San Joa quin River a: A r.^z:. ( /0) (0.1 ^g/ liter) and the rr.~ . outflow of 18.9 X IG!- liter/year, amounts to 19C0 kg/ycar. A similar calculation for the Mississippi yields an input into the Gulf of Mexico of 10 kg/ycar (11).
These rates cf input indicate the rela tive significance of wind and river trans port to the marine environment. The atmospheric rate is clearly an underes timate inasmuch as the method of col lection of the dusts fractionates against materials carried on particles of less than several microns or as vapors. We must conclude that the atmosphere can transport significant quantities of pesti cides to the open-ocean ecosystem; where ocean currents and river drain ages cannot explain the presence of residues, wind systems may provide conveyance from continents.
Similarly we have examined samples of airborne particulate matter from the central Pacific collected on glycerincoated nylon nets mounted on the mast of R.V. Argo (2) at 12 stations be tween 17N and 18S near 180 longi tude during the summer of 1967. No sample carried a detectable pesticide residue, but the weight of each sample did not exceed 1 or 2 mg, and less than 1 part per million or 1 ng of a pesti cide would have been undetectable. However, the presence of talc, the most important diffracting mineral, suggested the presence of pesticides (Fig. 1).
Dust collected from an oceao pier at La Jolla, California, between June and October 1967 yielded total pesticide contents in air ranging from 6 to 270 X 1 0 - ,s g/m* and averaging 7.0 X 10~n g/m*; the prevailing, winds are landward, with an unknown admixture of air from neighboring agricultural areas. This average value is 1000 times greater than its Barbadian counterpart. Such is the difference in pesticide load between marine air adjacent to agricul tural areas in which pesticides are used intensively and marine air remote from sites of application.
Extracts of the La Jolla dust samples were pooled, concentrated to a volume of about 1 ml, and refluxed for 10 min utes in 100 ml of 5 percent KOH in ethyl alcohol before 100 ml of hexane and 300 ml of concentrated aqueous solution of NaCl were added. The hex ane layer, after concentration to a small
volume, was then analyzed for PCB,
Such treat e r a of extracts of marine fish from cssal waters in California reveals the cfbractcrbtic profile, on gas chronutograzs, of the PCB peaks (9); PCB are posent in higher concentra tions in e e rb e birds, and the profile of the v arias peaks is usually evident in unsapom=d extracts. No PCB, how
ever, was detectable in the La Jolla dust samples; if PCB was present, its maximum cccaccutration in the airborne particulates was 5 ppb-- 10,000 times lower than that of total pesticides. The PCB are tesc compounds widely used in industry b the manufacture of plas tics, paints, and many other products, and are components of industrial air. Unlike the chlorinated-hydrocarbon pes ticides, which they resemble somewhat in chemical structure, they apparently persist to a greater extent in the vapor
phase. The coocentration ratios of total PCB to tcCsl DDT in many seabirds, including two species of Pacific shear waters that nest in Alaska, and in petrels and resident peregrine falcons from remehs areas of Baja California are of the same order of magnitude (9 ); this fact suggests that PCB. and
pesticides art similarly dispersed. With other polluants, including products of atomic explorions ( / J ) , they are prob ably universally present in air; thus their distriburion in marine and terres trial ecosystems remote from sites of application o n be expected to depend on the prevsSng patterns of wind cir culation and the rates of fallout.
SL W . R isebrougu
Institute of Marine Resources,
,Department of Nutritional Sciences
University of California, Berkeley R. L H uggett, J. J. G riffin
E. D. G oldbero
Scripps Institution o f Oceanography, University of California at
,San Diego La Jolla 92037
1. J. 0 * a T M a a d l R A. Ruxlcka. NoMV SIX MS 0 * 7 ) ; JL W. Riiebrouh. DB. M o o d , Dl I . BUrtm. Jr,, H. S. Olcou. Ibid. U K SB 0 * 7 ) ; W. 1. L. Sladen. C. 1C M ode, W. L. Rcfclttf. Ibid. 217. S70 (1 * 6 ); J. L. Gcorgo a d D. L H. Fxear. J. AwfL LmL SmppL X 133 (1 * 6 ).
X M. C I n w n , F. Acts*. Jr,, C. S. Lofgrra. M. Reran, M ra ra 166. I4S0 (1 * 4 ); F. A o n , Jr 1C Rer a n , M . C. Bowman. J. A ft. Fmmd Cktm. IS, 27S (1739); M. C. Bowmao, F. Acrac. Jr C H. Schmidt. M. R eran, J. f m . Coxomol. 52. 1031 (1739); C. R. Mania and E. F. Ucbtenatcio. ibid. K 1032 (1*1X
X F. A n to n w h , M. Cora. 1 . DcMaio. Sri* m e t ISA, 1676 (1 * 5 ); D. C Abbott. R. R. Karrboo, X 0*0. Tattoo. J. Thomson, Se ttee 262. 131? ( 1 * 3 ); ibid. 211. 237 (1766); G. A. W bntlry lotf J. A. Ilardmao, ibid. 297, 424 (t*S > .
ms
735890
Om
-a o o
-.'si
* 4. J. M. Cohen and C. Pinkerton. In Onanie m PtUitUrs in the P.nvironmcmt {American
Chemical Socirtf, I W ) , p. 163. J. II. WinJom. J. i . Orillia, l>. Cokfterg.
Envkon. Sei. Technol. I. 923 (1967). 4 A. C. Dclanr et ml.. Gtoehim. Cmsmochlm.
Aetm 51. MS (1 * 7 ). ?. lIf a mm in of the Science R n ra rrtt Coun
cil, U.K. W# thank A. C. Dcianjr fur them. 4 KcmUucs oI DDT include iU iv o homers
P^'-D D T and o^'-D D T tad the metabolic derivatives of p y -R D T ; ^ ^ `-DDE, *.*' DDO, and p^*-DDMU. p.p '-DDT, I.U lrtchloro-2J-btt(/-cWorophcnyl)eihae; DDT, l,l,Mrk:hloro.2-(o-chloropbenyl)-2-(/-
Cfelorophenyt)ethane; jr^'D D E, l tl^ichloro2 J-b it (p-chlocophenyl)ethylene; pj*`~Dl)D (also kiKMfl a T D E ), l,l-<lichlor^2.2?fca(/H
Chlorophenyl) ethane; p^*-DDMU, l<hloro 2 -bfe(fc h4k> rophcnyl) cthyleoc.
9. D. C. Holmes, J. 11. Simmnnj, j. o*G. Tai tn, Nature l i , 227 (l% 7 ); G. Widmark, J. Nature Ofrc. A tr. Chrm. SO, Ihn <IM7); A. V. Holden and K. Mariden, Nmturt 214, 1274 (1967); R. W. RiwbruuHi, M. N. Kirven, S. C. Herman, P. L. Ames, in prepara tion; R. W. Kitcliruukih, in preparation.
10. T. E. Dailey and J. R. lljnnum , J. Sonit. Hat. Die. Amer. Soe. Cm / tn g n . 95, 27 ( 1967).
11. A. W. Breidcnbach. C. C. Gunnersoa, F. K. Kawahara, 2, 2. .Lklttenu*re. K. S. Green, Public Health Rept. 02, 139 (1967); H. P. Nicholson, Science 15S, 171 (1967).
12. Scrip? Institutiop of Oceanography.
13. G. M. Wood well. Sel. Amer. 216, 24 (1967),
14. Supported by NSF (grant GP 4362) and ONR.
7 February I960
Microstructure of Sediments: Investigation with Ultrathin Sections
A bstract Examination o f ultrathin sections o f "undisturbed" murine sediments from the Gulf o f Mexico indicates that they are characterized by a loose, open, random arrangement o f particles. The microstructures do not appear to conform Sfintiirrely to either cardhouse or honeycomb structures.
TjThe microstructure ("fabric") of marine sediments has received little at tention from geological oceanographers. Two popular theories prevail as to the n a tu re W the particle arrangement in the sediments. Tcrzaghi ( / ) suggested a "honeycomb" structure, with adhesive forces causing the particles of clay min eral to sticl^togcther on contact; each
Fig. 1. (A) Hone; Terzaghi (/)]. (B) ture (tiler Ltmbe (J) bouse structure (liter Tin
11 of the structure consists of many adhering particles (Fig. 1A ). Later was suggested (2, 3) a somewhat different structure in which the day-mineral ag gregates, having a platy morphology, were arranged generally in an edge-tofacc fashion forming a "cardhouse" structure (Fig. IB). Tan (4) presented a three-dimensional idealization of cardhouse structure (Fig. 1C).
While some orientation studies, using polarized light and x-ray diffraction techniques (5 ), can reveal gross trends toward preferred or random orientation of particles, they do not reveal details of the microstructure. Most informa tion has come from the electron mi croscope. Rosenquist (6) used the elec tron microscope and the replication technique to obtain stereomicrographs
showing the microstructurc of undis turbed marine days; he concluded that the microstructurc of such clays "cor responds to the cardhouse structure sug gested by Goldschmidt and later by Lambe, and in fact exactly corresponds to the imaginative drawing of Tan." Use of the same technique for studying illitic Pleistocene days Jed to a similar conclusion (7 ).
Whereas the electron microscope of fers the best means available for study of sediment microstructure in detail, the replication technique does not pro vide easily} interpretable results. My purpose is io illustrate the microstruc ture in samples of sediment from the Gulf of Mexico as revealed by ultrathin sections V)f the sediment, and to point out that this technique provides more easily interpretable results.
The samples (Table 1) came from cores taken by R.V. Alaminos (8 ). Only cores were selected that had. been properly scaled and stored to preserve as well as possible the natural state of the sediment. From each core a cubic sample of 2 to 5 cm was carefully cut with a thtn-bladed knife or spatula. A larger portion was cut initially in order to retain an undisturbed portion in the center of the sample; likewise, the sam ple itself was taken from the center of each core. From each sample, smaller samples (1 to 2 cm by to 3 mm-) were cut with a taut, very thin wire; the outer, disturbed portion of each large sample was first trimmed with the wire to expose the inner, undisturbed portion. The small samples were freezedried; this technique is recommended (6, 9) because it entails less particle disturbance due to effects of surface tension than do standard oven- or airdrying techniques.
735891
Fig. 2. Ultrathin sections showing the microstroctures of undisturbed sediments from an abyssal plane (A), a continental slope (B),
and a continental shelf (C).
*
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i /{y David I'riimmi
'S c ic i'rc Currc'l">: <!' Ht
Tho peregrine falcon, ?. highly poisonous. : r.d ckcmi-
b i r d of prey that once cals closely related to it arc
abounded all over Amor;- known cancor-cau.-ors.
ca, is b e a r i n g a b itter Ia calliorr.ia the pollutant
warning to man:
widcioreaii: in the San
A 'newly-identified chemi-;Francisco Bav Area, where
cal pollutant has arisen o n . ,VlSRy jminstriws use many
our planet: it threatens not1varioiics* o: the compound.
tonly the existence of falcons t;lt. chemicnls have cancer.-
!and countless oihv.* birds, b u t; u-.-.rc: heavily.
its molecules are already en-'
........
tering`the bodies c.f hum,ans. ,!Ia c1lassncc't oPrg`a,un\i,conch,**e*1mCi"c1alss Its long-term nnzarcs ; c Ri ; c c polychlorinated bi-
low levels to the human spe- jp%eriyls. Few laymen have
cies arc wholly unknown -- ; CVCi-'heard of them, yet they althougn in concentrated gas
eous form the chemical is l
See Deck Pn'jc
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t:: J j [j
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1 )&
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l
l'rm Paso 1
Tho Berkeley scientist Is! tic came upon it.
Ichemical pollutant. E i g h t y ;
are a major boon to indus
try: they arc used in making ouii:; form (lie chemical is
prints and plastics, electrical inviil.-livs and rubber tire, waxes, sealants and epoxy
Dr. Robert W. Riscbvougli, a * The tale Is an Ironic ouc, li percent of Califerain's breed*!
researcher at the Institute of} for it all .parted with the per- jing peregrine falcons, D r.'
Marine Resources in the Uni c g r i n c falcon. That bird, iRisc'rrnugh estimates, have
versity of California's De once described by an emi now been destroyed.
}
partment of N u t r i t i o n a l n e n t ornithologist as " the It was barely two y ea rs:
Scientists.
embodiment of noble rapaci ago that Dr. Risebvoagh, o i |
t
I
r
c a r, v
resins.
Dr. lliscbrough and a team ty and lonely freedom," is an expedition to Baja editor- ' g
Despite lli.'ir widespread ue, in America they arc in:>lc o.ily by ?.[ on s a u t e Chiniral Co., which markets m;:- y f o r :n $ of (he com-
poi!.\?:f iMKlir lie trade naMO
of colic :;gi:es from Davis, San Biego raid Cornell Uni versity in New York, have been .aleit hi ecologists to li.w- h i t h e r t o uninspected prevalence of the byphc-nyl compounds and to their inva
now extinct as a breeding species in tho eastern Uni'ed States and southern Canada.
Its rapid population decline dtu-ing tho years right after World War ll -- when DDT was first introduced as a m a
nin, found an v u h a t c h e d . ! abandoned eg? of a pc citrine' falcon, lie analysed the g's contents, found DDT ia it. and also found il cmit'dr.*.!* another unid.-niifkd chemi
cal. I
ot Aroelors.
sion of man's environment, jor pesticide -- first served
ICB
}
They apparently ter the al'i'i:. ;,i,eie r.:iJ racuir.e er.virenment by vapoi king, vent ing fioiv, fr-etory stacks, by waste (vl.arjc into waterv r.ys end ever, by tbs abra sive wearing cf tires on free ways.
Ti >iv cl'.r iiiic i! : .'rii'tine f
very similar to that tf DDT, the potent V.ivl U>ig-l:.sHng
ioM.tJ'.cide. Both DDT anti die 5;ipi: myls are kii'iv.ri as i '0 - j.;,.rctJ bydrocarba.is,
and ir. Pie weeds of a Berke
of men's environment.
FALCON
They have published t'nejr findings in the British sci ence journal Nature, in its American counterpart S c i ence, sad have discussed it
at conferences on environ mental poisons. 11isei.rouli will be presentin'* more evi dence on the problem at a La
-folia scientific meeting on the " Chemical Invar.ion of the Ocean."
to rlcrt ecologists that a r,ev: poison might be damtig'i.g the environment.
DDT
Investigations showed the falcon was succumb'iig by prej ing on birds (iivt bed in g e s t e d large quantities of DDT, a chemical that con centrates in animal fa it. So the falcon, in a sense, was m an's first messenger to car ry the warning Hint DDT was befouling the wurtd.
And just as Spartan kings
Later lhat sam-j c l j u l c r l ;
was Ionr.d <n the fc.t cf ;Su`a*
pcan birds and S w e d i s h
scientists identified it as a .--
polychlorinated b Ip h o n y 1, '
which was to gain its selen-l
lific notoriety as PCS.
I
Dr. Kisebrough ar.J Ids col-1
leagues (hen began an
liuuslivc btiiil for P IR h r
birds aud fish a'ong the West "
Coast. Tliey are still at il.
They have fonr.*l, for ex*
ample, that PCB is p;c..'nt
In almost all birds cf prey.
b
c ti b It f< o n
b b h U . a 'r *t V a
fr
ley researcher they arc now In an interview* with The .slew their messengers who but its qinntitics a**, largest I)
"Ike most .I'indant synlbel Chronicle recently, Dr. Rise- ! bore Inal news, so die falcon in those birds that feed on 4;
ie polin'mi: ? jvOicnl in t!ie brough described the new j is being slain today as It car- j fish or fish-eating birds. Tho tf
>!ki1cm ire meat."
pollution menace, nrd how .r'c s the news of the new I material, lii.o DDT,
t
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: i j h l y ; e- - starts concciiliiiliii" in leagues point out tiiat all the not survive os a species In an Icause they remain tocalte-.d,
s breed-
I' lowest links cf llio nta- chlorinated hydrocarbons, e n v i r o n m e n t altered by Dr. [.-ebrough s a y s , a r t
its, Ur. n T..-.U chain" -- U`C ml- like DOT, cause e n z y m e m an's new chemicals.
"misleading, irrelevant and
s, bavCj
i \cflvs; ash, on; Caliiort c Uc- d .' i. c:.;ii'0
<v 4's * in il.; ml sire'!' chci-tl-
! !
*M W A i `-i. O0 (i i s It t as a t o a y 1, >i ClSil-i
hiredI.
'Ci; \\V,i
lit.
a
e< b:
y ci la I): li icl O!
II-
ti b. h: tc u 1 'n
A\
oceanic plants ami chni.fcf s in animal livers and
. a I s -- ami lietolives Ihat Close new-formed en
a v ' mors c-
zyme break down many vi
:y Itvi cal pl:i..\l'vi, big- tal hormones, including; sex
ish small fish, and hormones. In laboratory ex
e a t 1; jer fish.
periments ilh plscons, us
j*i eyin'i oil Pa- ing a b i p h e n y l compound ea b ids have now vlr- c s'.lcd Aroclor 1202, made by v . n i s h e d Dr. Rise- Monsanto, Dr. Ris-ivoagh's .! : *!*. Rut .-nr.ult in- croup ms found lltal PCD Is c* * .. of C.iiiiV.rr.i i five times more p o w e r f u l
'./w'i \Kv\ mostly thriii DOT in its lion noneVC . ! rd:*;u:rbS, ^tt! *c-slroyir.g activity.
JO * . bo i o,r. i- i*.!cinj * The i ex hormones, accord
. And what of the effect of tlto biphenyl compounds in humans? The c o m p o u n d s have a l r e a d y been found, ominously. In -the milk of inolhers analyzed by Dr. J. II. Endjrooa and Dr. F. A. Roland at Colorado College, and Dr. Risebrougli is now hoping to tost for their pres ence among nursing molhors hero.
As Dr. R i s e b r o u g h has written: "They arc Hgiily
wrong."
llow the PCB cnntpouiv.h may affect human food sup plies and human lives ate q u e s t i o n s for future re search. The oae certainty now Is that they can bo mui:'.l everywhere, that they have invaded the feod-prodwir.g levels of the oc.-.vis, a*. I '.nt their presence is rising s r ir'.ly.
Officials of the Xlosiiiir.'o cottipar..' in St. lands v ere
hi* a* M fu
sl
:
!. !'
ing to Dr. Risebrough, play
, oi a.u!y.*v5 of an intpcrbnl to b in calcium
metabolism, and as a iesu'1j
* ls
1cf the pilhitio; by PCP and!
: A only ; bont a *DDT the eggs of birds like
in '? PCH rs DDl' i lide.ms are nov far thinner!
U ic 1-.tr. oly: usd more fragile than they
toxic to matt v.'y.-n Inhaled as vapors, and Ike more heavily chlorinated components have greater toxleily. No toler ance limits have boon set for human food su p p i l o t and litclr canccr-cauitn.'i proper-
tasked lor comment on Dr. K i s c b r o u g l t 's report last {week. After three day.: of i queries a company tp'jkcs| man would only say tlr.d top Monsanto scientists and sr.bs I executives were studying U.
o ti r-
at:.;, a fiis.
a;-.*d to l i.
!l T.'V i \ K\ !v
;,n : s*rcj HUMANS
i- 'lv.tc;i a fisii i'd| T!ie ci.lcium-dcficiont
eggs
lb s r e m a i n to m ined."
FOOD
bo
deter
Dr. RisebrcugVs f e l l o w researchers attacking t It o PCD pollution problem In clude Dr. D. B. I'caknll cf
for c\*- \\ ti ! #Vf.
j hrc.*i!: prematurely ar-d fail Dr. Riscbiough and his col- Ccrncll; Staveil G. ITc-irii-n,
|;r 'r.t
) bi:V . as.d their
to produc i hr tchl!::;^;. Titus-leags-es have found evidence a zoologist a t Dm.' ;; Dr.
f |;oy. in- |.ot*. Sjh lVani-i.-.^o tic dr dine of Ihc dcon --I dial tits biphenyls, like DDT, Mottle K. Kirvea at the S;m
cod on Is. V.h;
-- is
the end cf its evolutionary! era carried widely across lit Diego N a t u r a l llislu-y
r. :;orons -- th:rc 1j ': rord. U lied adapted over' oceans by winds and water Museum, and Paul ReVh: in
n IC .-IV re .". ll. i:i P b r. ! millions of years to its nadir | c u m u li. A r g i t m e n t s that llio otarine rcsouaM J:' r l
nppar-
i Itiseln'cngh mvi i.'s col-, m l cnvis'onnic it but it could \ they can be used safely be- Rerkotay.
L