Focus
The Susquehanna
River swirls around
In the early morning hours of Wednesday, April 11, 1979, a 3-mL water sample was flown into McGheeTyson Air Force Base in Tennessee. A team of health physicists, drivers, and riggers met the plane and delivered the tiny sample to Oak Ridge National Laboratory's (ORNL) Analytical Chemistry Division. T h e sample was primary coolant water from the nuclear reactor at Three Mile Island, Middletown, Pa. A nuclear accident had occurred and, just as in many similar situations in the past, analytical chemists were among the first to be called upon to provide vital information. By the afternoon of the next day, preliminary analytical results were phoned in to representatives of the Department of Energy and the Nuclear Regulatory Commission in Harrisburg, Pa. " T h e r e had been an accident,'" explains Wilbur D. Shults, Director of the Analytical Chemistry Division at ORNL, "and any analytical informa lion they could obtain at that time would help them understand how severe the accident had been." In response to this need, ORNL chemists analyzed the 3-mL sample for the concentration levels of uranium, boron, plutonium, sodium, and lithium; the isotopic distributions of uranium, plutonium, and lithium; the pH and gross radioactivity; and the activity levels of 20 radioisotopes. In addition, semiquantitative analyses were performed on 23 other elements and isotopes by spark-source mass spectrometry, and a study was done to determine possible losses of radioéléments to the glass sample vial via adsorption. " T h e most
Three Mile Island nuclear generating
ORNL Analyzes Three Mile Island Reactor Water important thing was that we were able to get so much data on such a small sample, and in a very short time," Dr. Shults continues. "We phoned up preliminary results by Thursday afternoon, on virtually everything in the sample. We were able to do 90% of the work they asked for in a period of a day and a half." " T h a t is a real reflection of what can be done in analytical chemistry by today's technology, when you're able to bring lots of tools to bear on a given problem." T h e analytical tools utilized at ORNL on the TMI sample included micro-titrimetry, γ-ray spec trometry, neutron activation analysis, and spark-source, thermal emission and ion microprobe mass spectrome try. "Certainly there are laboratories around that could do a good job at the mass spectrometry, and others t h a t could do a good job at the 7-ray spec trometry, and so on. But the nice thing about the national laboratories is t h a t they have such a wide variety of techniques at their disposal," Shults explains. The ORNL team found the boron concentration to he approximately 3200 ppm, by isotope dilution sparksource mass spectrometry and microtitrimetry. "This was a most impor t a n t number at the time,'" Shults says. "Boron was being added to the
station
water as a neutron poison to help control the accident. It's important to have enough boron there so you can be assured of controlling the reactor, but too much boron could change the chemistry of the radioéléments in the water itself and cause complications." Other important numbers were the uranium (110 ppb) and plutonium (0,24 ppb) values, the isotopic activities ( 131 I was highest with a reading of 8200 microcuries per milliliter), and the uranium isotopic distribution. Calculations predicted a 2:, °U concentration in the fuel of 2.26 atom %. ORNL found a 2:ir, U value of 2.22 atom %, which Shults calls "a very impressive and comforting finding." " T h e news here is what was done, not what was found," Shults continues. " T h e really notable aspect is just how much information can be obtained on such a small amount of sample." ORNL is now considering devoting a session of the Conference on Analytical Chemistry in Energy Technology, to be held in Gatlinburg, Tenn., October 9-11, 1979, to analytical aspects of the T M I incident. "In times of crisis like this," Shults says, "often it's the analytical people who get involved at the very earliest stage. But they usually stay involved. There are three stages to an incident like T M I . In phase 1 there was an emergency to be controlled. In phase 2 an assessment had to be made of the situation for the long term. Phase 3 is the cleanup and recovery operation. Analytical chemistry is involved intimately in all of these phases. And I think that's part of the excitement of being in analytical chemistry."
ANALYTICAL CHEMISTRY, VOL. 51, NO. 9, AUGUST 1979 • 951 A
Focus
Marijuana : How Much THC? Investigators at the University of Illinois at Chicago Circle and Southern Illinois University have collaborated in the development of an analytical technique which is capable of identifying marijuana and determining the concentration of its psychoactive component. Juei Liu and Mary Fitzgerald at Chicago Circle and Gerard Smith at Southern Illinois presented their findings at the Great Lakes Regional Meeting of the American Chemical Society in June. T h e analytical method is based on the identification of four cannabinoids by mass spectrometry. One of these is A^tetrahydrocannabinol, the psychoactive component of Cannabis sativa. Tests to identify the plant are still among the most common performed in forensic laboratories, according to Dr. Liu. " T h e Duquenois-Levine color test in combination with microscopic identification of the physical characteristics of cannabis is very effective in most cases," explained Liu. "However, the Duquenois-Levine test alone does not identify the presence of specific cannabinoids." An extraction/GCMS method does provide such information, but it requires a laborious extraction and a large quantity of sample, which in many cases is not available.
Liu's procedure involves the introduction of approximately 0.2 mg of sample into the ion source of a mass spectrometer with a direct insertion probe. A direct insertion probe facilitates the analysis of low volatility samples. T h e probe is inserted through a vacuum lock into the ion source, and the probe tip is heated to volatilize the sample. Mass spectra obtained on cannabinoid standards are compared with sample spectra in order to make the
identification. If the sample is cannabis, the correlation between the sample spectrum and that of the pure cannabinoids gives favorable correlation parameters. With the capability to look at the individual cannabinoids without a time-consuming extraction, investigators will not only be able to identify the presence of marijuana and cannabis derivatives (like hashish) more quickly, but also they'll be able to tell if it's good stuff or bad.
Regional Instrumentation Facilities Established by NSF " T h e instrumentation has all been ordered to my knowledge, and some of the centers are actually in operation right now." Fred Findeis, head of the Chemical Synthesis and Analysis Section of the National Science Foundation (NSF), was describing the Regional Instrumentation Facilities program, which is funded by NSF. "Contrast the situation in the world today with the late 40's," Dr. Findeis continued, "when a university might have had a UV-visible spectrometer; they might have had a single beam infrared; they would have a Polarograph; they would have an electron diffraction apparatus, often homemade. T h e situation is just dramatically different today. This is an instrumentation-oriented society, because instrumentation leads to the creation of new knowledge. And there has to be a concept of sharing of instrumentation in order for us to serve the needs of U.S. science in an optimum way." T h e concept of sharing is what NSF's Regional Instrumentation Facilities program is all about. The program was established to make expensive state-of-the-art instrumentation widely available to qualified scientists, including those at smaller academic institutions and industrial labs. In fiscal year 1978, the NSF funded the establishment of Regional Instrumentation Facilities at six institutions: University of Arizona, carbon-14 dating and trace analysis by accelerator techniques; Colorado State University, nuclear magnetic resonance (NMR); Johns Hopkins University, mass spectrometry; University of Nebraska— Lincoln, mass spectrometry; University of Pennsylvania, laser facility; and University of South Carolina, NMR. "It's a very serious enterprise that the Foundation believes is in the best interests of U.S. science," Findeis con-
9 5 2 A • ANALYTICAL CHEMISTRY, VOL. 5 1 , NO. 9, AUGUST
1979
tinued. "How else is a university to develop resources to buy instrumentation in the half-million dollar range? In some aspects it's going to be a cross-cultural enterprise. It's going to expand the horizons of U.S. science. Certainly the contact at the facilities by scientists of diverse disciplines is going to be a healthy one—it's inescapable. T h e proof of the pudding is going to be the reaction of the scientific community, as to what extent they view these as resources that are their resources. And I think that good scientists are always aggressive and will approach these facilities with a wide variety of problems." Facilities can be used only for research for which prompt publication of results in recognized journals is intended, but a sample that is essential to an investigator's research protocol may still be classified as "routine" by the instrumentation facility. Governmental, industrial, and academic researchers may all participate in the program. "Not only universities, but the small college community can take great advantage of these if they are aggressive and propose research that is appropriate to the center. It's a grand opportunity," explained Findeis. T h e six regional facilities are described below. Johns Hopkins University T h e Middle Atlantic Mass Spectrometry Laboratory (MAMS) at the Johns Hopkins University opened on May 29, 1979, with a symposium on the analysis of "middle molecules," which are larger than molecules normally handled by mass spectrometry, but smaller than DNA and the larger biomolecules. The symposium was attended by approximately 70 scientists from local colleges, universities, and industrial laboratories.
Focus
Phil Lyon and Michael Gross (left to right) with the Kratos MS-50 at the University of Nebraska—Lincoln. MCMS mascot, Claudius the alligator, is perched in upper right-hand corner of photo MAMS will provide mass spectral measurements in support of organic structure elucidation, structure confirmation, and stable isotope analysis. T h e instrumentation will also be available for fundamental studies. It is expected t h a t the facility will serve the life science related disciplines, including chemistry, biochemistry, pharmacology, environmental sciences, and medicine. Instrumental capabilities include high mass analyses with high sensitivity, high resolution mass measurements, positive and negative chemical ionization, and field desorption. T h e high sensitivity region will be the area accessible at 8-kV accelerating energy; i.e., 1-3000 amu. But the center's Kratos MS-50 high resolution spectrometer, fitted with a 23-kG magnet, a DS-50 data system, and a PerkinElmer Sigma III gas chromatograph, has already measured masses well above 6000 daltons, with no indication it will quit there. Robert Cotter, facility manager of MAMS, explains: " T h e special high field magnet on our facility mass spectrometer allows us to identify ions t h a t weigh up to 10 000 daltons. We expect to develop the new methodologies and expertise required to extend mass spectrometry into this new territory." Chemical facilities and assistance are available for final preparation and derivitization of samples. Investigators are encouraged to visit M A M S to participate in designing and executing their mass spectral measurements. Interested scientists may contact Dr. Robert Cotter, MAMS, D e p a r t m e n t of Pharmacology, T h e Johns Hopkins University School of Medicine, 725 N o r t h Wolfe Street, Baltimore, Md. 21205.
University of Nebraska—Lincoln T h e Midwest Center for Mass Spectrometry (MCMS) was established at the University of Nebraska—Lincoln in late 1978. MCMS, like all the regional instrumentation centers, is both service-oriented and researchoriented. Demanding problems requiring state-of-the-art instrumentation and detailed experimental planning and analysis will be assigned high priority. However, routine service such as acquisition of low resolution spectra or low resolution gas chromatography/ mass spectrometry will be provided at a lower priority for smaller universities and industrial laboratories that have no mass spectrometric equipment. Five mass spectrometers, acquired by faculty at the University of Nebraska—Lincoln over a number of years and incorporated into the center, are currently accessible: • Kratos-AEI MS-50, interfaced to a Perkin-Elmer Sigma II gas chromatograph and equipped with a computer system. Both electron impact and chemical ionization sources are available, as well as the capability for metastable ion studies. T h e static mass resolving power of the instrument is 180 000, the highest available with any commercial mass spectrometer. It is being used to get elemental compositions by peak matching or by full high resolution scans, to do trace analysis (as low as ppt) and to conduct fundamental studies on fragmentation processes. (M. L. Gross) • Hitachi RMU-6D Mass Analyzed Ion Kinetic Energy Spectrometer ( M I K E S ) , used primarily to elucidate fragmentation mechanisms. (Professor M. L. Gross)
• Fourier Transform ICR Mass Spectrometer, a research instrument which has many of the capabilities of conventional ion cyclotron resonance and is now under development for analytical purposes. (Professors C. L. Wilkins and M. L. Gross) • Threshold Photoelectron-Coincid e n t Photoion Mass Spectrometer, used to determine ionization potentials and to study the chemistry of ions in very precisely defined energy states. (Professor G. G. Meisels) • T i m e Resolved Chemical Ionization Mass Spectrometer, which can be used to study kinetics and equilibria of gas-phase ions and to develop analytical chemical ionization methodology. (Professor G. G. Meisels) In addition, three other instruments will become available in the future. T h e first is another Kratos MS-50, which should be ready in November 1979. Equipped with three analyzers, it has the capability of separating at high resolution an ion beam representing a single component in a mixture and collisionally activating it to produce structurally informative fragments, which can then be analyzed using the third sector. Gerhard Meisels, Chairman of the Department of Chemistry at Nebraska—Lincoln, will supervise construction of a Californium-252 Plasma Desorption Mass Spectrometer for the center by late 1980. Finally, the present F T mass spectrometer will be rebuilt and equipped with a larger magnet and improved sample-handling capabilities by December 1979. Michael Gross, Director of MCMS, says that the two MS-50's will perform a majority of the service analyses for the scientific community. Both instruments will be fully automated with their own dedicated computers, separate and complete for each instrument. "They can be used in a variety of experiments: normal structure proofs or identification of new compounds from synthetic chemists," Dr. Gross points out. "They can produce complete high resolution mass spectra, where all the peaks have an exact mass determined. They're capable of highly specific trace analysis, down to the parts-per-trillion level in some cases. Both will be useful for fundamental studies in mass spectrometry and for understanding fragmentation patterns of compounds. These two instruments will really be the heart of our center. T h e other instruments are less service oriented but are available for collaborative projects by contacting the principal investigator." Application forms and further information about M C M S can be ob-
A N A L Y T I C A L CHEMISTRY, VOL. 5 1 , NO. 9, AUGUST
1979 • 953 A
Benjamin Greene and Leslie Hallidy make adjustments on the mode-locked Nd-glass laser in the Ultrashort Pulse Laser Laboratory at the University of Pennsylvania. This laser generates ultrashort pulses for picosecond transient absorption spectroscopy tained by writing to: Director, MCMS, Department of Chemistry, University of Nebraska, Lincoln, Neb. 68588. University of Pennsylvania T h e Regional Laser Laboratories (RLL) at the University of Pennsylvania will provide state-of-the-art laser instrumentation for research, along with technical laser and spectroscopic expertise. T h e facility will be user-oriented and investigators will be aided in the planning of their laser-related research by a support staff of experts in optical electronics and laser chemistry. On February 13, 1979, a widely-attended RLL workshop on lasers in biology, chemistry, and physics was held at the university. Robin Hochstrasser says of the workshop, " M a n y people were extremely interested in using the labs, and the workshop gave us a clearer picture of regional needs in the laser area." T h e RLL will consist of 4 main laboratories for research, and a laboratory for crystal growth and for the preparation and purification of materials: • Infrared (IR) Laser Laboratory. Tunable infrared radiation will be developed in the laboratory by using the Raman effect in gases as a means of spectrally shifting the o u t p u t of a high power pulsed tunable visible dye laser. This laser source will be useful in investigating IR spectroscopy, enhanced reactions, energy transfer, and energy redistribution in both gases and condensed phases. A primary goal of the lab will be the development of more versatile IR sources, drawing on emerging IR laser technologies. In addition to IR lasers, optical components to control laser beams, monitor laser emission, and measure weak IR emission will be available.
• Nanosecond Flash Photolysis Laboratory. This laboratory will provide state-of-the-art laser instrumentation designed for transient spectroscopy using excitation wavelengths from 175 nm to about 900 nm, and with a time resolution of ca. 1 0 - 8 second. This part of the facility is designed for research in kinetic spectroscopy and transient analysis. Excimer, YAG, and nitrogen-pumped laser systems can be used in experiments. • Ultrashort Pulse Laser Laboratory. This laboratory will specialize in systems operating in the time regime from 10~ 8 to 1 0 _ l s second. Two faculty research laboratories at the University of Pennsylvania are already conducting picosecond research in the molecular dynamics of solids, solutions, and gases. T h e lasers they use are specially developed for carrying out spectral studies of transients created by light in the condensed phase, and are capable of coherence dynamics studies and quantitative studies of laser-induced processes. One of the facility's argon lasers will be used to simultaneously p u m p 2 dye lasers, producing 2 tunable synchronized picosecond sources. One special application of this system is time-resolved coherent anti-Stokes Raman scattering, useful in studies of coherence dynamics and in time-resolved vibrational (Raman) spectroscopy. A system is being developed which will allow time resolution and spectral characterization of low q u a n t u m yield fluorescence from short-lived states. A streak camera is available for measurements of fluorescence lifetimes from 2 ps to 10 ns and coherently generated pulse profiles. T h e ultrashort pulse facility will be useful for investigations in relaxation processes, reaction kinetics in solution, molecular re-
954 A • ANALYTICAL CHEMISTRY, VOL. 5 1 , NO. 9, AUGUST 1979
orientation in liquids, coherence dynamics, photodissociation, luminescence lifetimes, photochemical reaction intermediates, conformation changes in biomolecules, solid-state research, and low temperature processes. • Laser Spectroscopy Laboratory. T h i s laboratory will specialize in high resolution laser spectroscopy and coherence effects in gases and low temperature solids. Possible research areas include nuclear-electron spin interactions in molecules, Zeeman effects, Stark shifts and splittings, fine and hyperfine structure of atomic transitions, rotational transitions in Doppler-congested molecular spectra, and other areas where extremely narrow-band lasers and Doppler-free spectroscopies can substantially augm e n t current research programs. • Materials Preparation and Purification Center. This laboratory will undertake the ultrapurification of solvents, reagents, and dyes for facility experiments and a research program in laser materials. A crystal growth laboratory and a synthetic lab can be used for the preparation of new materials in forms suitable for laser experiments. For further information about RLL, contact Professor R. M. Hochstrasser, R L L Director, Chemistry Department, University of Pennsylvania, Philadelphia, Pa. 19104. University of South Carolina T h e principal instrument at the South Carolina Magnetic Resonance Laboratory is a Bruker WH-400 Fourier transform N M R spectrometer. T h e instrument at present has fixed frequency probes for *H at 400 MHz, 19 F at 376.3 MHz and 13 C at 100.6 MHz. Broad-banded probes to cover the range from 10 to 162 MHz (4lK to :!I P) are also available. In addition to normal 'H-decoupling capability, the spectrometer has the ability to generate a decoupling frequency between 1 and 162 MHz. Four other N M R spectrometers are on site, and two of these are multinuclear instruments: the WP-200 and the XL-100. T h e former has a wide bore (90 mm) magnet and has the necessary hardware to perform cross-polarization and/or magic angle spinning experiments on l 3 C and 11;, Cd. In the near future these cross-polarization experiments will be completely multinuclear. Investigators at the facility have had some success with the developm e n t of "other nuclei" probes. Paul Ellis, facility director and associate professor of chemistry at South Carolina, is working on a new probe design
Focus
Rheodyne simplifies LC sample injection again. We made the best injector even better. Rheodyne's Model 7120 Syringe Loading Sample Injector has carved out an outstanding reputation in the LC field. Last year sales more than doubled. People seem to think it's the best around —and we modestly agree. Now we've made it even better —with new features that make sample injection simpler and more reliable than ever before. Flushing now unnecessary. With the improved valve, Model 7125, the entire contents of the microsyringe is injected into the sample loop and flows to the column. No sample is left behind' in the valve. Consequently, you don't have to flush the valve between injections unless you're doing trace analysis. Longer valve life. Less wear. Both rotor and stator are made from new materials to minimize wear as they slide over one another. This extends valve life considerably. Our new Model 7125 replaces the popular 7120 in all applications. Does all the 7120 does and more. Has the same mounting dimensions. Price is $540. New automatic model. Our automatic Model 7126 combines the new 7125 with pneumatic actuators and time-ofinjection switch so you can use it in automatic LC systems. Compact. Sturdy. Reliable. May be used in the manual injection mode anytime you wish. Price is $780. Get the details now. Contact Rheodyne Inc., 2809Tenth St., Berkeley, Calif., 94710. Phone (415) 548-5374.
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t h a t will speed up the analysis of bio logical molecules by a factor of ap proximately 80. "Something that would have been a 12-hour experiment will be a 10-minute experiment. This is for any biological samples that have moderate line widths, i.e., line widths in excess of 25 Hz, on any nucleus." More detailed information about the facility may be obtained by writ ing to: South Carolina Magnetic Reso nance Laboratory, Department of Chemistry, University of South Caro lina, Columbia, S.C. 29208. University of Arizona
A regional facility for radiocarbon dating and particle induced X-ray analysis has been established at the University of Arizona. A tandem electrostatic accelerator and associated instruments, now under construction at General Ionex Corporation, will be used for carbon14 dating. The instrument will be able to obtain H C dates from samples which are small compared to those needed for conventional methods—a few milligrams instead of grams. It will be used to measure the ! 4 C con tent of tree rings of a known age, and to date archaeological and hydrological samples, precious artifacts, works of art, and much more. Although per formance characteristics are yet to be established, it is expected that the in strument will measure recent 14 Cdates to about ±80 years and will have an age limit of about 60 000 years. The accelerator system should be ready for use in about 15 months. A recent de scription of the accelerator dating technique is given by H. E. Gove et al.,
IEEE Transactions, NS-26, 1414 (1979). Trace element determinations will be carried out at the center by mea surement of the energies as well as the intensities of Κ and L X-rays emitted by samples which are undergoing bombardment by charged particles. This technique, known as P I X E (Par ticle Induced X-ray Emission) is de scribed in detail by S. A. E. Johansson and T. B. Johansson in Nuclear In struments and Methods, 137, 473-516 (1976). P I X E instrumentation avail able at the center includes 2- and 5.5MeV Van de Graaff accelerators, vari ous target chambers, Si(Li) detectors with 200-eV resolution, a bent crystal spectrometer with 1-eV resolution, a Nuclear Data 6610 data acquisition system, and various plotting and printing devices to provide hard cop ies of results. T h e P I X E system is capable of de tecting most elements with Ζ > 10 at the 1-ppb level. The expected preci sion is 10% or better at concentrations of a few ppm for most elements. Inquiries about the facilities at the center may be addressed to: N S F Re gional Instrumentation Facility, De partment of Physics, University of Ar izona, Tucson, Ariz. 85721. Colorado State University
A regional NMR facility has also been established at Colorado State University in Fort Collins, Colo. This center will be based on four NMR in struments. Three of these are new su perconducting NMR spectrometers funded by the NSF grant. They are a Nicolet wide-bore NT-150 spectrome-
Stephen Kirchner, Quintus Fernando, and Steven Schubert PIXE apparatus at the University of Arizona at Tucson
(left to right)
with
Focus ter, a Nicolet wide-bore NT-200 spec trometer, and a Nicolet NT-400 spec trometer. In addition, the Colorado State University Chemistry Depart ment's J E O L FX-100 spectrometer has been incorporated into the center. T h e "wide-bore" designation of the first two instruments refers to the physical space available for the sam ple probe. A wide-bore spectrometer enables the investigator to analyze a large amount of sample, which is ad vantageous when working with dilute solutions, and to carry out specialized probe modifications requiring extra space. T h e NT-150 at Colorado State University is capable of detecting nuc lides with resonance frequencies rang ing between those of l 5 N and Ή , and will be used mainly for liquid samples. T h e NT-200, on the other hand, will he used mainly for obtaining spectra on solid samples by magic-angle spin ning and cross polarization. It will be used initially for 1:i C, but later for other spin-'/a nuclides as well. T h e Nicolet NT-400 will see a lot of use for protons, but will also be used for low frequency nuclei resonating up to about 1 5 N, including r,v Fe, 1 0 i Rh, and 1
