Document QM2nxZ0XKw83x2LJwBaYr4Zx7

o i*/ /* +&* 'i & INTBRNATIONAL HAD ZINC RBSBARCH OROANIZATION, INC. >. i r< M MAO>tO *va*Ut, Nfw rO<W. N V BTB-AOBO l*M* OOOI 7 t* *y 3, 1966 Tot All Nabors of tbs UA-HiK> Usd Health sad Safety Ccsaitte* Art Prrllalnery Proposal froa Irotopaa, lac. Attached for your consideration Is s copy of "Sources of tend la Ancient sad Modern Enrlrooasnts" vrlttea for us st your rtnff'srt quart by Dr. Schutt of Xaotopes. Iae. X sa quits tnpreeeed vttb tbs out11ns ss presented la this proposal sad bops tbit yea srs also, Pleaee 1st ae hart your consents sad lapreeeloee so tbst additional lnforwd discussion can bs held vltb tbs contractor. The Aosrlesa Petrolmat Xnstltuts Is also sending tbls proposal out and asking for connints fra tbslr eoadlttees. When us bars received a ruff1clent expression of letsrsst. tbs ATX aad ourselves plan to request tbst s nastlng ba bald vltb 1 Xsotopss, Inc. for furtbar discussion# vblch, hopefully, vill lead to s concrete sad aors dataHad proposal. > Please 1st as bars your ecoawnts by >tey 17. X vould also lib# to bsar fre* say of our Berber# vbo vould Ilka to partlctfate la tbs proposed oreting sad j dlscurrtca vltb Xrotopar, Inc. Our present plana call for such s nesting to j ba bald as roco as pcsrlbls after Nry 17. If there Is s ruffle lent expression of latarast frxa our groups. Vary truly yours. 1 Ht 9 i Mfisv sUscbaast Don 0. fouler Project Nrnsgor I AN tN Tgs PrclUinary Proposal 50UKCCS Or ICAO IK ANCtCNT AKO K>OOtK CNVIK0XKCKT3 v'j . ; y, To bt Sobsittcd to tb* Lead Industries Association -A . Pr*pared By 0. r. Schuts April 2f IWTOPfl, IKCi 121 Woodland Avrrm# Wrstwood, X*v Jar soy I N 385.01 Isotopes, Inc. SOURCES OF LEAD IX AXCIEMT AMD MODOW EXVIRWOCHTS 11 COXTEXTS . Introduction Prlaltlve Ha Toxicological Standard a) Measureaeot of Lead lo Primitive Man b) Critique of th 1933 Study of Laad In "Primitive- Mexico e) Critique of Patterson's Indirect Estimates of Load la Vneontanlooted Man I Proposed InvestIgetIons Proposed Studtea of Lead In Fossil Environments a) Reservoirs and Long Island Sound b) rosall Soils c) Tree Rings Propoaed Identification of Sources Analytical Methods to be Employed Soapling Kathode Swans iy Proposed Work Schedule Personnel Cost References Psge 10 10 12 12 14 15 It It 1? II i; t. rv . v.*. t: if 11g.VJUMP'ij'W;UMffffflg1- r- Isotope*, Inc. i .f SOURCCS Or LEAD W AXCIDIT AXD HDDCRX CXVIXOtOCKTS < 1 Introduction A recent report by concluded from basic material bal ance and geochemical con1 drret Ion* that man a* an induatrlal animal hat aeveraly contaminated hla environment and la auffartng lead Insult on# hun dred time a greater than that preaent during hla biological evolution* The report further concluded that thta level of lnault, becauae It waa auatalned In a period too abort for evolutionary adjustment, la a danger to the well being of a large portion of our population. Such widespread environmental contamination vae regarded particularly eertoua b^cauar It la cumulative and cannot be eaally reduced ahould a critical level be reached. The above concluatona are in contradiction to a conalderabla array of aclantlflc opinion that ha* developed from extensive work In lead toxicology and pharmacology. In general, the moat prominent worker# have concludedi 1) that primitive man aufferrd lead lnault no leaf than one-half that preaently aiperlenced by Induatrlal man, 1) that there la a well-defined threahhold value of lead lnault below which man can exist Indefinitely without harm, and 3) that the preaant "normal" body burden (aa meaaured by the lead content of blood) of about one-third the threehhold value allow* an adequate margin of aafaty. The purpose of thi* propeeal 1# to review and evaluate the evidence pertinent to theaa contradictory concluatona and to outline a program of study neesaaary to resolve important points of conflict. It la concluded that tho use of haste geochemical and material balance considerations tp Indicate * rg LIA11747 yaw; { ;-r-'J^~.y-,-rf'ii*rr'i - -- -"tTf>-^im'>V-ArS:i;itf4 Iotope, Inc. TABLE 1 Parcentaga rr*<pjency Dlitrlbutlon of Lead 1* Urine of Croup* froa Varlou* Countrle* Lead In A/tl 0.00-0.099 0.01 0.03 0.03 0.04 0.08 0.04 Mexico (3) (19331 46 33 13 8 4 USA (3) (1*U_, -- 23 30 37 17 10 8 rranee (3) OW) -- 33 18 34 18 6 S Cermany (J) (1960 -- 38 31 11 1 -- Total Subjects 1 >0 33 13 Moon* 8-0.* .014 .01 .039 .003 .030 .003 .037 .003 an and atandard deviation *r Mown a* calculated by ICeho*, t l (*) (3) I'-i-'i, iam JPfPP - j; I $a3^3y**. #r -4# '.im*!W&gWii "W wi ni, a^-asaa "' tlA11748 I sotopea, Inc. If th aetabollm of lead 1* a function of concentration In the envlronsent, we any Hava, at praeent, a dletortad view of tHa natural lead dietrlbutlon In tha body. THa only baala for evaluating tba toxicological affact of land on aan la to aatabllaH aa a baaa llna tha blochcalcal bahavlor of load under condition* approximating tHo*a prevalent during tha long period of aen'e biological evolution. Although tba ultimate reaolution of tha problem trill require l study of prlaltlva Nn In a natural uncontaailnatad environment, valuable data concerning tha significance of lead In our present environment can be obtained by going back In tine to atea aura peat environmental lavala *fose Ulsed* In eedlmentary at rata and In tree ringa. - : - ` `-r ' ' A' * ~ *,* hr' \ - " * '"V* ~" fr^potH Investigation* The a**torrent of lesd In the environment of primitive mo My be accomplished Indirectly in two ways. Me con mi cure lead in contemporary environments that have been isolated from Industrial contamination by geoiraphical and cultural factor! (aa attempted by Xehoe, et al/3^) or we can meaaure lead In foaall environment! isolated by burial or enclosure. Al though It ia ultimately essential to study the distribution of lead la primitive contemporary Mn In isolated areas such as the upper Am too basin or Caster Island, to establish the natural metabolic behavior of lead In man, the Initial study proposed here la limited to an Investigation of a more accessible area to provide the preliminary data necessary to relate the lead levels of our present environment to environments of the past. Proposed Studies of lead in fossil environment J'i A number of environments representative of the past are readily access < ible to us. Tor essmple, the lead content of our drinking water and other surface waters should be recorded in the sedimentary strata at the bottom of our reservoirs and in bong Island Sound, seeds stored for long periods should be representative of soil contents provided contamination hat not taken place, and tree rings should record the atmospheric lead concent rations and provide a yearly record of particulate fallout. ` Aa each of theae environments la studied, at discussed below, samples esn be tsksn for Isotopic analysis which will help to "fingerprint* the leed and slucidstt Its origin when compered with the isotopic composition of leed from various known sources.  ) Reservoirs and Long Island Sound Each year the public water supply reservoirs undergo a cyclical addition of water and weterboma sediaent. In k w cates, th* lead content of the water in the reaervolr la a aatter of record, but where It la not, an eatlaate of paat concentration level* a*y be derived fro* the adaorbed Ion content of th* sediment layer* deposited each year. Coapcrlson of the laotoplc compo sition of reaervolr water with that of poaalble aourcea nay Identify Ita origin and may also serve to differentiate between the adsorbed Ion concentration and th* lead which la a norMl part of the slneral grains. On a larger scale, a study of the water, sedlaenta, and living . ,ii and foosll biota of bong Island Sound can serve to Indicate th* degree to which lead hat been Introduced over the past few hundred years. The study of bong Island Sound will serve as an exaaple of a rela tively enclosed water body close to a high level of industrial activity. It la of direct laportance only with respect to certain fish tnd shell fish which art used for huwn consumption. The study of public reservoirs, however, la of -j direct laportance because of the large number of people affected by the public j *. water supply. The proposed study will extend beyond the usual pibllc health surveys In that an stteapt will be Mde to Identify the source of lead and to evaluate the degree to which lead of Industrial origin It Involved/*- Ve propose to study at least four reservoirs and samples ftcm a pro file along long Island Sound. Sediment cores and water samples will be taken t tnd analysed with the ms s spectrometer, emission spectrograph tnd atomic 3 "i absorption spectrometer. In this way the Isotopic composition ctn be determined and the emission spectrograph and atomic absorption spectrophotometer methods ri can be calibrated by u m of primary isotope dilution dot*. Thia calibration data can than ba uaad In othar quantitative atudjee to affact reduction In analyt ical coat* whara isotopic ratio Information la not retired. b) roaall- Soli* bead to noil* la of direct Importance to man'a diet bacauae of it* uptake by plant* and subsequently by anlamla. A number of well-defined foaail interglacial aotla are available for atudy in the northeaatem 1 United State*. If thaae aolla have not been contaminated by ground voter or lead aeroeol depot It loo, they thou Id be good indicator* of the level of lead in the diet of uneont taint ted man. The laotople compotlt Ion of the lead la 4 eoch toll* might ba a uteful indication of the extant of contamination pretent. Study of atored teed* may alto provide e tource of information on the degree of plant uptake at a function of time over the last S0-100 year*. Sampling mi analytical methodology ttoiler to that deacrlbed In a) above vill be uted. c) Tree king* The distribution of C** In tree ring* demonstrate* the Halted rx- cherge between the living outtide tiaaue* of the tree and the Inactive interior. Although lead eight be expected to be aomewhat more mobile than ctrboo, be cause carbon it a major structure! component of the tree cell*, there la atill a good poasibility that tree ring* will record hi*torlc*l changeidn the led level of the *ir *nd toil environment. The amount measured would be * sum of lead taken up from the toil and through the letve* and bark. The uptake of lead in plant* ha* been used M a geochemical protr pecting tool ahowing that the environment i* reflected in biological proceste*. However, only one etudy haa been made of tree ring* which *howm the dittributlon of lead with tlme^. The result* of thla atudy are shown In Table I. jUttH J*-; 1 XaOtOpaS, IBC. 11 That* rasulta ara not eonclualva because wa do not know tha natural distribution of laad In traaa In uncontaalnated environments, but they do auggest tha potential value of traa rings aa Indicators of traca element eoneentrst Ions In paleoenvironments. Borne Idas of tha natural metabolic distribution of laad aa a function of tint can ba gained by coopering similar apacias which hava grown In environments of high natural laad and low artificial contamination with traaa grown In anvlromanta of low or avaraga natural laad but high lav*la of artificial eontaalnatlon. i TABLE 2 i Laad Content of an Ela Traa (Varmont) (4) Tima Ynri 1B4S-1I70 1900-1910 1940-194? 1914-1959 Bark and cambium Cd Content pro 0 0 0.01 0.04 0.01 Pb Contant ppm 0.14 0.12 0.M 0.74 2.9 / J ' ': O Materials suitable for study art svalLsbls and cover on* to two thousand year* of environmental history. Study of tr* rings in different ar*ss could reveal th* historical pattern of the spread of lead contamination. Ve propose to study th* lead content of trees grown In contaminated envlronsents and in environments of high natural soil lead. Where cooteminent* are of different isotopic composition from th* soil lead th* degree of contamination can be established unequivocally and the source of contamination can be Iden tified. The number of trees studied will depend on the avellablllty of older samples and th* degree of difficulty experienced In obtaining meaningful samples from llvlr^ trees. Aa described In a) above,mult 1 pi# analytical methods will be used to provide intercallbratloo data for various sample matrices. Proposed Identification of Sources Paint dust, coal fly-ash, lead alkyl decomposition product* and various natural amttrlal* such as volcanic aah, silicate dust, and sea aeroaola have all been Identified as possible sourcea of lead rain out and fallout. Cadi of these Mterlala will contribute more or less to th* atmospheric lead concen tration and each may have lte own characterlatlct Isotopic composition, goth the relative contribution and Isotopic ccssposltlon will be different for differ ent trees snd mey even change aa a function of tin* but for anyone are* it may be possible to Identify the sources of lead Input to a close approximation. Tor example, coal fly-ash should have a very different Isotopic composition from lesd alkyls because the lead la from geologically different sources* Where quantitative anelyela ia corroborated by emUsion spectrograph a ns lysis other elemental ratio* will also be determined to help Identify the origin of complex mixtures on air filter pepera. iKto^tit Inc. U [ " Analytic*! Methods to be teployed A previous section discussed the Inadequacy of the analytical methods used vi In the 19)9 study of lead In primitive nan. Although substantial Improvements hav* been aada ainca then, the entire framework of lew-level lead analyala haa recently been placed tn quest loo by Tatsumoto and Patterson* values fcr *? tea water which war* tan to fifty times lower than prevloua datarnlnattona. Than# values vara obtained by Isotope dilution. Although Isotope dilution analysis represents one of th* most accurate j and sensitive analytical techniques available. It Is expensive and cannot be justified except for the lowest levels of detection or for aeasureaents of characteristic Isotope ratios. A variety of other orthods for lead determtna- tloo exist such as colorlaetry, mission spectrogrsphy, atonic absorption spectrophotometry, stripping polsrography etc. tadh of these net hods Is appropriate for certain concentration levels and saeple matrices. Regardless of the method chosen for routine A- analysis. Isotope dilution analysis can be used to established standard values of high accuracy which can be used for Instrument calibration, rurther checks on analytical accuracy can be nsde by use of fb110 as a radiochemical tracer to *; essure the yield of various loo exchsngeor solvent extraction purification pro II cedures. As mentioned above considerable attention will be glveain this pilot study to supply multiple quantitative analyses calibrated by primary Isotope dilu I. tion determinations. The information so gstned esn be used to advantage later < where It My be desirable to perfora s large number of analyses at reduced eost i < without lost of occurocy. r- :.r 1: & .: ' Sailing HatSoda Correct choice of aaoplea, veil proper preparation end storage, are Important for valid results. Careful attention will be paid to calibration of flltera where air aawplea were taken and to changes In concentration doe to adiorptlon loaaea or contaotnat ion of water aaoplea. The world-wide experience of leotopee, Inc. In taking blolog leal and envlronoental aaoplea will play an loportent part In the aucceaa of the propoaed project. "3 f^ - V* **i*kt' Si--iry i A single study by Kehoe, #t serves as our only empirical bod* for comparing th# degree of artificial lead Intuit to modern man with th* level of environmental load experienced by primitive Mn. It ha* been ahown that -i any of the data presented In thla atudy war* probably ' iraccurate, that all avanuaa of access to lnduatrlal load war* not Investigated, and that tha coneluaIona baaed on th* data were untound atatlatlcally and were apparently aade without aufflcient appreciation of the tla* teal* of huaan evolution and tha capability of men to adapt biologically to environmental change*. la view of th* Inadequacy of th* only empirical atudy available, an Indirect method baaed on biochemical and geochemical relattonahlp* waa de vised by Patteraon^^ for estimating the amount of lead In uncontamlnated mao and led to conclusion* very different from those of th* previous atudy. Al though the method underlying Patterson'* Indirect approach la not above question, * the conclusions still appear to warrant a review of th* earlier empirical atudy upon which th# prevailing eoocept of th# "normal" bedy burden of lead In an la baaed. Because the Inferred natural levels of lead ara to widely different from modern observed level*, and becaua# accurate knowledge of thesa level* la eaaential to an understanding of lead metabolism and toxicology, it I# proposed that a modern empirical evaluation of uncontaminated anvfrwment* b* undertaken utilising the moat careful sampling technique* and tha moat accurate and aenaittva analytical method* available. This Investigation would Include an attempt to identify th# source* of environmental lead by establishing the characteristic Isotope composition Saiv-.-, ;-r. of tha lead from each source. In this way If action to reduce th* level af y* V -V. ^ *<-. /v> v-r_ ii 'i-iift'-nii , ,**2u*r*rJS&: ji Isotopes, Inc. 16 contfalrttt Ion is Indicated the quantitatively most significant sources csn be altered first and needless hsressaent end wests of resources csn be avoided* Proposed Worfc Schedule Ve propose to carry out the foregoing prograe within 13 Booths from the ties an agreement is reached* Characterisation of various source Materials will proceed first; followed by the environmental studies, (hiring the entire tle, study of the pertinent literature will be undertaken to provide a study which i 'i is up to date and cognisant of the latest development* In the field* Blaoothly progress reports will be submitted and it is hoped that close liaison can be Maintained to provide a stlaulatlng cross fertilisation of ideas and dlrection of the project. We anticipate that the result* of the work will be of a calibre suitable for publication, but recognise that such publication will be ss at the discretion of the Usd Industries Association. tengsal The (investigation will be directed by l>r. D.T* Schutt who la currently Manager of field project* devoted to the applicetion of envlromental sampling to the detection of underground nucleaf teat*. Dr. Schuts*# e* per tenet include# geochenical prospecting for lead, line,1 apji copper deposits In the states of Heine and Artiom. He did his doctoral dissertation at Tata University where he developed Methods for ultra-tcroen*lyl* of tree# element# In sea water by neutron activations analysla^^. The Method* developed were applied to samples Dr. Schuts collected in the Antarctic wMls aboard th# bins r.ltsritn in 190~'s4. Subsequent to that study he completed a survey of silver in Connecticut streams and the Long Island Sound ustr^ eolation spectrograph/ end neutron activation analysts. Other atudiee have included the developoent af a Method for *-r#y MJJMJf! ,JU 1JMy! .5 v> ie / >"1? -i flooreacenc* determlnat too of atrontlun In h * water and th application of that method to a voxId vid# collection of aamplea. Dr. Schuts will b aaaleted by Dr. E.V. Willie currently aanajar of the Scientific Service* Departvent of Iaotopea, Inc. Dr. Wlllla haa directed the development of analytical nethod* at Iaotopea, Inc. alnea leaving Cambridge la 1964. While at Cambridge he waa a foremoat authority oa carbon-14 dating and la that context la eminently qualified to carry out a atody of recent geological proceaaea. The high profeaalonal atatua of Dr. Wlllla 1* atteated by hi* recent a*lection aa President of the International Comalaaloo on Aboolute Age of Pleistocene Depoait* of the IKJUA Conference held la Boulder Colorado la Sept enter 1963. Technical and analytical aaalaUnca will be provided by tha welltrained and experienced ataff of the Scientific Servleea Department of Isotopes, lac. Cojl Tha coot of the above atody and analytical prograa la aattaated to be approxImtely 153,000. umww jjpy ncmcxca -*s V (1) Pattrraon, C. C., (196$) Cortaalnatad and Natural Lead Environment* of K*n. Archive* of Environmental Health, U, 344. (2) Kehoe, R. A., Thamann, P., and Cholak, J., (1933) On the Noraal Abaorptlon and Excretion of Lead. I. hoed Abeorptlon and Excretloa la Primitive Life} J of Ind. Hygiene tS^ 25 7-272. (3) Echo*, R. A., (1961) The Hetaboltam of Lead In Man In Health and Dlaeaae) The Kerbcn Lecture*, 1960, J. Royal lnat. Public Health 24, 31-97, 101-20, 129-43, 177-203. i- (4) Schroeder, H. A. and Balaeaa, J. J., (1961) Abnormal Trace Metal* la Mans Leadi J. Chronic Dlaeaae*, 14, 401-425. (5) Tataumoto, M. and Pattrraon, C. C., (1963) Th# Concentration of Common Lead In Sea Waters Earth Science and Hetoorltlc* Ed. J. Cela* and E. D Goldberg, Worth Holland t\jb. Co., Amaterdam. (6) Schutt, D. r. and Tureklan, K. K., (1965) Th* InveatigatIon of th* Geographical and Verttcal Dtatrtbutlon of Several Trace Element* la Sr* Water Uling Meutron Activation Arjlytlas Ceochla. et. CboemochLa. Acta J9j, 259-313. * .A...'H1 aa.;jByyjaf;-aR a '7.