m --K- I S* 'V/S U r * MI .1,-. ,r"* ^••^u.AW.t.n. *. 1 j./ •* 44 I y '» IS' V > -J- ^ *\*y* ARAB REPUBLIC OF EGYPT 1 /^/J' u ATOMIC ENERGY ESTABLISHMENT tic- S$\ t-. NEUTRON ;^0!H;^IQN^ALYSIS OP'URIflfc TAlCOETrun i We regret that some of the pages in the microfiche copy of this report may not be up to the proper legibility standards, even though the best possible copy was used for preparing the master fiche. A.n..l*.A.E.E./Rcp.-lC5 ARAB REPUBLIC OF EGYPT ATOMIC ENERGY ESTABLISHMENT NUCLEAR CHEMISTRY DEPARTMENT NEUTRON ACTIVATION ANALYSIS CF URINARY CALCULI By \\ SOUKA, S. SOUKA, M\ SANAU <ttid A.A. ABDEL-RASSOUL 1974 SCIENTIFIC INFORMATION DIVISION ATOMIC ENERGY POST OFFICE CAIRO, A.R.E. CONTENTS A B S T R A C T i INTRODUCTION , . 1 EXPERIMENTAL 2 RESULTS AND DISCUSSION 5 ACKNOM'IEDGEMTWT?? 10 APPENDIT 11 REFERENCES 14 NEUTKON ACTIVATION ANALYSIS Of U!UNAT>V CALCULI By N. SOUKA, S. SOUKA+, W. SANAD and A.A. ABT)EL-RASSOUL ABSTRACT Neutron activation analysis of u collection of urinary calculi has been undertaken,, Search for silver, selenium, zinc and cobalt -was carried out. Cobalt presented a measurable concentration in all the investigated calculi. The cobult content in oxalate stones (around 1200+93 ppn>)> was found to be approximately five times its value in phosphate stones (around 200+21 ppm). The cobalt content in the examined calcium oxalate- triple phosphate mixed calculi lies betireen both concentration levels. Clinical pathology Laboratory Sidnawy Health Ensurance Hospital, Cairo. IflEHODUCTlOfi Recently, several investigatore have shown that a defi­ nite relationship exists between the concentration level of several trace elements in human body and certain diseases. The determination of trace eiemenos is further considered as a helpful tool to clarify many physioiogical processes. In this connection, activation analysis offers considerable pote­ ntialities relevant to both reliability and high detection sensitivity of various elements. Trace analysis of urine, was one of the subjects treated by neutron activation analysis. Determination of Ha, G.l,' Al, Br, I, Au, Mn, Sr, as well as radioactive deposits and several toxic elements was made with, great precision^ K xuie^ * , has determined the detection limits for 72 elements in'urine, these limits were in some cases as low as 0,000^ ppm.• Urinary calculi resulting from disorders in the urinary system and formed in any part of the urinary tract, have been classified by biochemists into simple calculi and mixed cal­ culi^'* '. In general, these stones are mostly composed of substances normally excreted in the urine, together with a certain amount of protein material. On rare occasions, for­ eign bodies may be found and may form the nucleus of a stone. Substances found in calculi include : uric acid, urates, cal­ cium oxalate, alkaline earth phosphates (Ua and-MgJ, triple phosphate (.magnesium ammonium phosphate.), calcium carbonate, cystine, and xanthine^"''. It is unusual to find a stone com­ posed of only one urinary constituent-, though it is often that one of the substances present is- in marked preponderance. .Procedures for the determination of macro constituents in uri­ nary calculi have been well established^'"*"'. No attempts, apart from the study reported by herring et al. , have been undertaken'to determine trace elements in urinary stones. _ o „ In a radiological surveillance of inorganic urinary calculi Herring et al. , indicated "that urolithiasis patients con­ sume approximately three times the concentration of strontium jii the national diet data (.^r concentration was measured with reierence to Ga concentration;. The present v.ox'ii. is a uon-'Ue?aoruc't»ive neutron activation analysis of urinary calculi, ana it aims maimy at studying the variation in concentration of certain trace elements with the chemical form or the calculus«, EJCWSHIMia'AL Physical and_OhemicaI Analysis of Oaicuii: A collection of urinary calculi, surgically removed from urolithiasis patients, and amounting to about ii? stones, has been analyzed physically and chemically^°»"'(see Appendix I;. These calculi were characterised by certain differences in physical and chemical properties* Pending on these differen­ ces, the collection was divided into three groups, see Table (i;. uroup I s oxalate stones consisting mainly of calcium oxa­ latef Group II s phosphate stones containing either triple phos­ phate or calcium phosphate© Group .III i mixed stones of the two f orementioned types. Neutron Activation Analysis of Calculit JSrperxments were conducted along the same lines set forth for activation analysis^ \ The different calculi were weighed and encapsulated in thin aluminium foils. Known weights (. yug concentrations; of the following standards : silvert selenium, zine and cohalt, were separately encapsulated in the same man­ ner. Both the test samples and monitoring standards were.irr- - 3 - Table (l): physical and Chemical Analysis of Urinary Calculi. Group I Group II Group ITT Physical Analysis : Colour dark brown •white yellow LayerB numerous dense numerous white concenteric yellow brown concen- yellow concen­ layers frith white teric layers ter ic layers. nucleus und surface with vhite shows fine man*illa­ nucleus. tions . JJaulitative Chemical Analysis: Carbonate — trace truce Calcium moderate nil truce Magnesium nil triple phosphate triple phosphate Oxalate +++ nil + Phosphorus trace in +++++ +++ nucleus Uric acid ++ ++ Urates ++ ++ Ammonia trace + trace Fibrine + nil nil Cystine trace nil nil Xanthine nil nil nil .„ 4 - 13 2 adiated in the UA-KR-1 at a mean neutron flux of 10 yn/cm sec. for 25 hours. After a suitable cooling period (about 6 weeks.), each of the activated calculi was transferred to a fx^esh plastic vial and set for gamma pulse height analysis. The first step in the analysis, is to identify the com­ ponents in the gamma ray spectra o± the different calculi. This has been undertaken by tracing the gamma spectra of each calculus using a true coaxial Ge(Li) detector, 30 cnr intre- nsic volume^ "•', connected to a multichannel (512 channels) counting assembly, model E.D* 120o Standard gamma sources of Am241 (59.568 KeV), Co^7 (122.05 KeV and 136.406 KeV) and Gs *' (661o59 KeV) were used to calibrate the energy scale. The counting period was 10 minutes in all cases. The second step in the analysis, is to determine the amounts of the elements of interest in the different calculi. This is carried out by a comparison of the photopeak areas in the compound spectra of the calculi with those of the res­ pective irradiated monitoring standards, accounting for any differences in experimental conditions (cooling time and coun­ ting geometries). - 5 - HBSUI/TS AND DISCUSSION Tracing the gamma spectra of the irradiated calculi, in­ dicated that the neutron induced nuclides Ag (£•, = 260 d9 main X-energies 0.45, 0.68, 0.88 and 1.39 MeV), Se75 (T-^ 120 d, main X -energies 0.12, 0.14, 0.28 and 0.4C MeV;, and Zn65 (Ti/ = 24-5 dp /6 -enrgy 0.31 annih., 1.11 MeV) could not be qualitatively detected in the complex measurements carried, oirtr • On the other hand, Go proved to be pre­ sent in all calculi, as characterised by peak energies 1.17 fin Me? and 1.32 MeV. '-d© identity of Co was further evidenced. by giving an almost constant GE/ 1.17 J CE^ 1.33 ratio in. the spectral measurements of the different samples analyzed and that of the monitoring Co-standard (where: G,represents the net integral counts under respective photoelectric pealc)* An example of the produced spectra is given in. Fig. (1J>. From the fore-lined considerations, it is clear that no accurate estimates for Ag, Se and Zn, could be given. This is probably due to their absence or presence in concentrations beyond the detection limits under used experimental conditions. For the quantitative estimation of cobalt, the half area under the higher side of the photoelctric peak of the 1.^3 MeV line has been accurately measured, and compared with that of the irradiated cobalt standard. This eliminates the pos­ sible interference of contaminants that might exist at lower energies. Fig,(2), represents an enlarged scale of this peak, for three different calculi,, each belongs to one of the investi­ gated, groups, i'he integrated, counts, have been normalized to one gram of the investigated, samples, and the analytical results are represented in. , Table (.2). Prom the tabulated data, it is obvious that the cobalt content changes with the chemical form, of the s-cone. Gobalt is more concentrated in calcium ... 6 _. 1.17 MeV 1.33 MeV - • ^ , n 13 -2 j3f ~ 10 n,,CB) „sec t. irr ^± 25 hours, 'cooling 6 weeks. In minutes, counting Ge(Li) 30 car I ± 40 80 120 160 200 240 280 320 Channel Number Fig. (l)s An example of Produced Gamma Spectra. - 7 - 270 275 280 Channel Nuiuber Fig. (2): The 1.33 MeV $ -peak for Representative Samples of the Different Calculi. -- 8 - oxalate calculi (giving an average cobalt content of 1200 +, y> ppiii), ana is less concentrated in the triple phosphate calculi (having a mean value of 200 ± 'dl ppnO. Calculi of xiiixed calcium oxalate and triple phosphate (group III), con­ tain cobalt in concentrations that lie between the two fore- mentioned concentration levels, Tabic (2)., Hue ooserved llu- uvuai-iona in me cobalt contents for this type of calculi, could be attributed to differences in the relative proportions of the oxalate and phosphate components. Generally speaking,, oxalate stones are formed in acidic urine, while phosphate stones are formed in alkaline urine„ The acidity of urine, however, could not explain the observed inarmed variation in cobalt concentration* On the other hand, the etiology of urinary calculi is by no means clear9 possible factors may bei the high concentration of urinary salts, var­ ious infections, deficiency in vitamin A, para thyroid tumor ana nephrocalcinosis* Unfortunately, no clinical interpreta­ tion could be set in the light of the available data, and further work is necessary to clarify this point.