ANALYTICAL APPROACH
Analytical Chemistry in the Aftermath of the Gulf War D. L. Donohue and Rolf Zeisler International Atomic Energy Agency Wagramerstrasse 5 P.O. Box 100 A-1400 Seibersdorf Austria
The 1991 Gulf War came to a n end with t h e acceptance by Iraq of t h e cease-fire terms embodied in United Nations Security Council Resolution 687. T h i s r e s o l u t i o n s p e c i f i c a l l y called upon the International Atomic Energy Agency (IAEA), assisted by t h e U . N . S p e c i a l C o m m i s s i o n , to carry out inspections of all Iraqi nuclear installations a n d to develop a plan to destroy, remove, or r e n d e r harmless all items related to the development of nuclear weapons or nuclear-weapons-usable material. Within two weeks of t h a t resolut i o n , a n IAEA A c t i o n T e a m w a s formed. I t s first inspection, which took place w i t h i n six w e e k s , consisted of sorting through t h e rubble of t h e b u i l d i n g s i n T u w a i t h a , t h e m a i n r e s e a r c h c e n t e r of t h e I r a q 0003-2700/93/0365-359A/$04.00/0 © 1993 American Chemical Society
Atomic E n e r g y C o m m i s s i o n . T h e team took custody of all nuclear materials and visited the Tarmiya site. As time went on, other inspections by t h e IAEA in collaboration w i t h t h e U.N. Special C o m m i s s i o n e n a b l e d i n v e s t i g a t o r s to o b t a i n a clearer picture of w h a t h a d been a multibillion-dollar clandestine program to produce a nuclear weapon. The IAEA Action Team succeeded in implementing, on very short notice, a comprehensive program of inspection activities by calling upon an i m p r e s s i v e r a n g e of technical a n d administrative resources within t h e IAEA a n d i t s m e m b e r s t a t e s . T h e IAEA l a b o r a t o r i e s in Seibersdorf, Austria, played an important role in this effort by performing hundreds of analytical measurements on samples b r o u g h t back by inspectors. These analytical results were used to plan subsequent inspections and to verify the declarations made by the Iraqi authorities about their activities prior to the war. In this ANALYTICAL APPROACH we will describe some of the contributions made by the IAEA
laboratories to ensure the success of the Action Team's mission, a n d we will a t t e m p t to convey some of the c h a l l e n g e s w e faced d u r i n g t h i s project. Background
Two specific l a b o r a t o r i e s i n t h e IAEA's Department of Research and Isotopes were responsible for s u p porting the Action Team. The Chemical Analysis a n d Isotopic Analysis U n i t s of the Safeguards Analytical Laboratory (SAL) and the Chemistry Unit of the Physics, Chemistry, a n d I n s t r u m e n t a t i o n (PCI) Laboratory performed t h e majority of the measurements. Additional analytical support was provided by government laboratories in t h e member s t a t e s , t h e A u s t r i a n R e s e a r c h C e n t e r in Seibersdorf, t h e Atom I n s t i t u t e of the Austrian Universities in Vienna, and a commercial analytical laboratory. In the initial phases of the project, inspectors a n d analytical chemists were confronted with the need to define what, if any, undeclared nuclear
ANALYTICAL CHEMISTRY, VOL. 65, NO. 7, APRIL 1, 1993 · 359 A
ANALYTICAL APPROACH a c t i v i t i e s h a d t a k e n place; w h e r e a n d , if p o s s i b l e , w h e n t h e y took place; and by what means they were accomplished. To answer these ques tions, it was i m p o r t a n t to consider all a s p e c t s of t h e s u s p e c t process when the sample collection and anal ysis system was designed. Considering the degree of destruc tion of t h e I r a q i facilities a n d t h e Iraqis' efforts to conceal certain a s pects of their program, it was neces sary to collect a large number of en vironmental or construction material samples to search for unusual traces of n u c l e a r m a t e r i a l s . To facilitate this sampling, inspectors were sup plied with m a t e r i a l s such as filter papers for smear samples and plastic or glass bottles for bulk samples. At the laboratory, the samples were coded and split into three parts: one sample for assay in the IAEA labora tories, one for possible analysis in a laboratory outside the IAEA, and one for archival purposes. The initial goal of the analytical chemists was to quickly answer the following questions: • Is there radioactive material in the sample? What radionuclides are present? • Are uranium or other actinide ele ments present in the sample? • Are isotopically disturbed uranium or compounds of u r a n i u m t h a t are indicative of a particular enrichment process present? • What are the quantities of radio nuclides, fission products, or actinide elements in the samples? It was imperative t h a t the inspec tors and chemists closely coordinate their efforts in determining the best method of sample treatment, priori ties for analysis, and where to send the subsamples for outside measure m e n t s . The inspectors r e q u e s t e d a variety of m e a s u r e m e n t s to aid in t h e i n v e s t i g a t i o n of both declared and undeclared nuclear activities in I r a q . T h e r a n g e of s a m p l e t y p e s shown in Table I includes environ mental samples from nuclear facili ties, construction materials used in U enrichment or Pu production, and nuclear-grade process materials. Analytical capabilities
SAL. The analysis of nuclear materi als for U and Pu content as well as isotopic composition was and still is the main work performed by the SAL in support of IAEA safeguards under the nonproliferation treaty and other agreements. In this article, however, we will focus on the types of samples (including some listed in Table I)
t h a t were unique to the inspections in Iraq or those that required the ap plication or development of new ana lytical methods and protocols. The techniques selected for analy sis by the SAL (2) require high preci sion a n d accuracy, high selectivity for U or Pu and, in some cases, high sensitivity (because of the problems associated with shipping large sam ples). Table II lists t h e a n a l y t i c a l t e c h n i q u e s applied a t t h e SAL for analysis of the samples obtained by the Action Team. Certain techniques
such as high-resolution gamma ray spectrometry and X-ray fluorescence (XRF) spectrometry can be used to measure a large number of isotopes or elements. For this reason, these m e t h o d s were used extensively in screening the non-nuclear material s a m p l e s , w h e r e a s t h e more t r a d i tional Safeguards Analytical tech niques were used for the nuclear ma terial samples. PCI Laboratory. The PCI Labo r a t o r y p e r f o r m s a b r o a d r a n g e of m e a s u r e m e n t s in s u p p o r t of IAEA
Table 1. Analytical measurements requested for samples obtained by the IAEA Action Team Sample category Non-nuclear materials Environmental
Construction materials
Nuclear materials
Sample type
Information requested Presence and amount of U and Pu Presence of other radionuclides Presence and amount of F, CI, U, and Pu isotopes Presence of high explosives Purity, type, or identity
Smears Vegetation Son Debris Rocks, ores Water Graphite Steel Beryllium Unknown metals U metal U compounds Pu compounds Po U, Pu waste and scrap
Amount of U and Pu Amount of U and Pu isotopes Amount of Po Compounds of U and Pu Trace elements in U compounds
Table II. Analytical techniques used at the SAL Analytical technique
Component measured
High-resolution gamma ray spectrometry
Pu isotopic abundances Amount of 241 Am, 237Np Presence of radionuclides
Alpha particle spectrometry
238
X-ray fluorescence spectrometry
Major, minor, trace elemental analysis
Κ-edge densitometry
Amount of U, Pu, Th, Np in solutions
McDonald/Savage potentiometric titration
Amount of Pu in pure nuclear materials
NBL modified Davies/Gray potentiometric titration
Amount of U in pure nuclear materials
Optical emission spectrometry
Trace elements in U compounds
Pu abundance Presence of 210Po
Thermal ionization MS
U, Pu isotopic abundances
Isotope dilution MS
Amount of U, Pu in small samples
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ANALYTICAL APPROACH programs. The activities of the PCI Laboratory range from the measure ment of radionuclides in the environ ment (e.g., the international Cherno byl project) to the provision of quality control standards under the Analyti cal Q u a l i t y Control Services p r o gram. Techniques for the screening and analysis of inspection samples from Iraq, which are divided between destructive and nondestructive anal ysis methods, are shown in Table III. To d e t e r m i n e F a n d CI, n e u t r o n activation analysis (NAA) with auto mated equipment can be used for the rapid evaluation of a large number of samples (2). Gamma ray spectrome t r y was used extensively to screen samples for radioactivity and to de tect t h e presence of u r a n i u m above the background level of - 1 μg/g of sample. Also m e a s u r e d by g a m m a ray spectrometry were fission prod uct elements t h a t r e m a i n e d in t h e s a m p l e s after r e p r o c e s s i n g of t h e spent reactor fuel. The advantage of this method is t h a t results are pro vided quickly, w i t h o u t e l a b o r a t e sample preparation. Another advan tage is the broad range for detecting radionuclides without requiring prior knowledge of sample composi tion. XRF analysis, whether with exci t a t i o n by a n X - r a y t u b e or by a radioisotopic source such as 109 Cd, is also a r a p i d s c r e e n i n g t e c h n i q u e with a detection limit for uranium of ~ 1 μg/cm 2 . Most other elements of interest (except for the lightest ones) were also measured by this method, and it was ideal for determining the composition of metals, powders, or solutions. Quantitative information can be obtained if appropriate stan dards are available. Among the destructive analytical techniques used, laser fluorometry offers the highest sensitivity and ac curacy for u r a n i u m d e t e r m i n a t i o n (3). This method relies on the optical fluorescence of uranium compounds following illumination by UV laser light. T h e s a m p l e p r e p a r a t i o n for such measurements involves ashing the specimen in air at 500 °C to r e move all organic components, fol lowed by dissolution in h o t n i t r i c acid. In some cases, it is necessary to use a solvent extraction procedure to chemically separate the U from in terfering elements. The final m e a s u r e m e n t by l a s e r f l u o r o m e t r y is performed in a phosphate medium to achieve a high luminescence yield. Information about the concentra tion of uranium and many other ele ments in dissolved samples was ob-
t a i n e d with inductively coupled plasma optical emission spectrome try (ICP-OES). This method was es pecially useful for m e a s u r i n g t h e t r a c e e l e m e n t s in w a t e r s a m p l e s from the pool of the Soviet IRT-5000 reactor and from the spent-fuel stor age p o n d s . T h e p r e s e n c e i n s u c h samples of e l e m e n t s from t h e fuel cladding or core would be indicative of corrosion or d a m a g e to t h e fuel and would have h a d serious conse quences. T h e I C P - O E S r e s u l t s , in conjunction with the pH and conduc tivity measurements, gave a consis t e n t picture of t h e i n t e g r i t y of t h e fuel rods in these locations. Finally, certain m e a s u r e m e n t s of Pu in Iraqi samples were performed with alpha particle spectrometry. The sensitivity and selectivity of this method for Pu is quite high; it has a detection limit of < 1 ng (4). Quanti t a t i o n of t h e amount of P u present was accomplished by the addition of a 2 3 6 Pu tracer of known quantity. In terference by U in this measurement is minimal because it has lower spe cific activity and emits lower alpha particle energies. S a m p l e - h a n d l i n g protocol
The a n a l y t i c a l schemes applied to t h e n o n - n u c l e a r m a t e r i a l samples were specially developed to allow the inspectors to make rapid and selec tive measurements without demand ing optimum performance in t e r m s of precision. Another important ob jective was to obtain as much infor mation as possible from a sample be fore i t w a s d e s t r o y e d by f u r t h e r chemical processing. Usually, a preliminary m e a s u r e ment was performed to screen sam ples for t h e presence of i m p o r t a n t components such as uranium, pluto nium, or other radionuclides. Initial s c r e e n i n g for u r a n i u m w a s p e r formed by workers at the Austrian
Research Center in Seibersdorf. They used alpha particle counting in an ionization chamber for the high est sensitivity. In both the SAL and the PCI laboratory, additional screening was carried out with highresolution gamma ray spectrometry a n d e n e r g y - d i s p e r s i v e XRF spec trometry. Gamma ray spectrometry has a high sensitivity (nanogram to microgram levels) for radionuclides with relatively short half-lives, as in the case for m a n y fission products and certain isotopes of Pu. The XRF method w a s used to screen for t h e presence of u r a n i u m , with a detec tion l i m i t of - 1 μ g / c m 2 . B e c a u s e uranium is a naturally occurring ele ment that is present in soil at a con c e n t r a t i o n of - 1 lig/g, t h e r e were certain analytical problems associ ated with the "blank" levels, prima rily in the environmental samples. Following initial screening m e a surements, samples that showed ele vated levels of U or P u were m e a s u r e d by o t h e r n o n d e s t r u c t i v e methods, such as NAA (for F and CI content), before being submitted for chemical dissolution and further de structive analysis. Care was taken in the chemical t r e a t m e n t of the sam ples to minimize the danger of con tamination. The primary methods used for the determination of U con tent—laser fluorometry and isotope dilution MS along w i t h other com plementary methods—were espe cially valuable in the analysis of ura n i u m o r e s f r o m Al Q a i m , a s discussed below. The chemical treatment of samples containing U or Pu depended on the matrix. Filter paper smears were di gested in nitric acid; soils, ores, and rocks were dissolved in n i t r i c / h y d r o f l u o r i c a c i d ; a n d g r a p h i t e or metal pieces with suspected surface contamination were leached with ni tric or hydrochloric acid. Certain an-
Table III. Analytical techniques used at the PCI Laboratory Analytical technique Nondestructive analysis Neutron activation analysis Gamma ray spectrometry X-ray fluorescence spectrometry Conductivity and pH Destructive analysis Laser fluorometry Inductively coupled plasma optical emission spectrometry Alpha particle spectrometry
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Component measured F, CI, U U and radionuclides (fission products) U and elemental composition Ionic concentration of solutions U U and trace elements U and Pu
alytical techniques such as isotope dilution MS required t h a t the samples undergo further chemical processing steps. T h u s the analysis of one sample could involve a significant amount of effort and measurements with several analytical techniques. More t h a n 500 environmental or smear samples and nearly 600 n u clear material samples from the 15 Action Team inspections in 1991 and 1992 were analyzed at Seibersdorf. External analytical support In a d d i t i o n to t h e m e a s u r e m e n t s performed at Seibersdorf, selected samples were distributed to laboratories outside of the IAEA that could offer special analytical services or a rapid response for screening m e a surements. The A u s t r i a n Research Center in Seibersdorf supplied alpha p a r t i c l e m e a s u r e m e n t s for t h e screening of n o n - n u c l e a r m a t e r i a l samples for the presence of U and, in collaboration with the Atom I n s t i tute of the Austrian Universities in Vienna, carried out NAA. Samples of steel were sent to a commercial metallurgical laboratory to d e t e r m i n e their type and, therefore, their usefulness for building gas centrifuge components (used for u r a n i u m enrichment). Government laboratories in several member s t a t e s accepted samples on which t h e y performed highly sensitive a n d precise m e a surements. Results of analytical measurements: selected examples Several cases will be described in which analytical measurements were performed on non-nuclear material s a m p l e s s u p p l i e d by t h e A c t i o n T e a m . T h e s e cases exemplify t h e r a n g e of m e a s u r e m e n t t e c h n i q u e s applied and d e m o n s t r a t e how t h e results of such analyses can be combined with the inspectors' observat i o n s for a more complete u n d e r s t a n d i n g of t h e n u c l e a r a c t i v i t i e s under investigation. E v i d e n c e of e l e c t r o m a g n e t i c s e p a r a t i o n of u r a n i u m i s o t o p e s . The revelation t h a t Iraq h a d been u s i n g t h e electromagnetic isotope s e p a r a t i o n (EMIS) process for enriching 235TJ came as a surprise to many people in the scientific community. It was not until the third inspection t h a t the Iraqi a u t h o r i t i e s admitted to the existence of this program and described their activities in detail. This declaration by the Iraqis contained information about the
large facilities at Tarmiya and Ash Sharquat, the number of isotope separators (calutrons) that were operating at T u w a i t h a and Tarmiya, and the amount of 2 3 5 U that was successfully s e p a r a t e d . The Action T e a m was shown parts of the isotope separators that had been dismantled, destroyed, and buried in an attempt to conceal t h i s p r o g r a m . A few p a r t s from the ion sources and collectors of the calutrons were brought back for analysis. In addition, samples were t a k e n from t h e d e c l a r e d p r o d u c t batches, covering a range of 2 3 5 U enrichment from depleted (< 0.1 wt%) to ~ 6 wt%. Figures 1 and 2 show photos of an ion source and collector pieces from a 1200-mm calutron declared to have been in operation at Tarmiya. These graphite pieces were scraped with a razor blade to remove - 1 g of powder from t h e surface t h a t w a s t h e n
leached in nitric acid to dissolve the uranium. This was followed by isotopic m e a s u r e m e n t s using a t h e r m a l ionization mass spectrometer (Finnigan MAT-261). Results are shown in Table IV. The ion sources t h a t were sampled for analysis contained only natural uranium. The data from the sampled collector pieces showed enrichments not exceeding 6%. The Iraqi authorities declared five batches of u r a n i u m n i t r a t e product solution from the EMIS process work at Tarmiya. These were said to contain several h u n d r e d g r a m s of enriched uranium with a 235TJ content of between 3 and 6 wt%, as well as other recovered m a t e r i a l w i t h depleted or n e a r - n a t u r a l 2 3 5 U a b u n dance. The product solutions h a d b e e n r e m o v e d f r o m five t a n k s a t T a r m i y a a n d b u r i e d in p l a s t i c bottles. Each bottle was sampled by t h e IAEA i n s p e c t o r s ; t h e samples
Table IV. Results of isotopic measurements for calutron pieces Sample I.D. Ion source 1 Ion source 2 Collector 1-1 Collector 1 -2 Collector 1 -3 Collector 1 -4 Collector 1-5 Collector 2-1 Collector 2-2 Collector 2-3 Collector 2-4
235
U abundance (wt %) 0.71 0.71 0.76 5.82 4.76 0.39 6.84 0.06 5.94 4.22 0.79
Remarks Natural U Natural U Slightly enriched Enriched Enriched Slightly depleted Enriched Highly depleted Enriched Enriched Slightly enriched
Figure 1. Ion source from electromagnetic isotope separator. ANALYTICAL CHEMISTRY, VOL. 65, NO. 7, APRIL 1, 1993 · 365 A
ANALYTICAL APPROACH were analyzed at the SAL with thermal ionization MS to determine the isotopic composition and with isotope dilution MS to d e t e r m i n e the u r a nium content (Table V). The measured isotope information closely matches the declared information. Investigators combined the concentration data with the measured volumes of solution in the bottles to determine the total amount of material present. E v i d e n c e of p l u t o n i u m product i o n . In 1991 Iraq declared t h a t it had established a program for reprocessing spent fuel to recover Pu. This was c a r r i e d out by dissolving one "exempted" spent-fuel assembly from the 10% enriched fuel for the Soviet I R T - 5 0 0 0 reactor, yielding
- 2.26 g of Pu. It was subsequently discovered t h a t the Iraqis also i r r a d i a t e d n a t u r a l U fuel p i n s in t h e IRT-5000 reactor. This resulted in production of an additional 2.7 g of Pu. IAEA i n s p e c t o r s s a m p l e d all of these p l u t o n i u m - b e a r i n g materials and sent them to Seibersdorf for immediate analysis. By using the most rapid analytical method, high-resolution g a m m a ray spectrometry, a m e a s u r e m e n t of t h e P u i s o t o p i c a b u n d a n c e s (except for 2 4 2 P u ) a n d the 241Am content was obtained. From these data, it was possible to infer the most recent date of chemical processing of the samples, which gave a n approximate timetable for the undeclared activities. Table VI
Figure 2. Graphite collector pieces from electromagnetic isotope separator.
Table V. Results of measuring uranium nitrate solutions Sample Tank Tank Tank Tank Tank Tank Tank Tank Tank Tank Tank Tank Tank
1-1 1-2 2-1 2-2 3-1 3-2 4-1 4-2 5-1 5-2 5-3 5-4 5-5
Declared 235U (wt %)
Measured 235U (wt %)
Measured U concentration (mg/g)
