An Assessment of the National Institute of Standards and Technology Measurement and Standards Laboratories: Fiscal Year 2003 (2003)

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11 Chemical Science and Technology Laboratory: Division Reviews BIOTECHNOLOGY DIVISION Technical Merit The purpose of the Biotechnology Division is to maintain a research laboratory as the primary resource for the biotechnology measurements, models, data, and reference standards required to produce biochemical products, enhance competitiveness in the world market, and allow the government to apply advances in biotechnology to the benefit of society. The Biotechnology Division has four groups: DNA Technologies, Bioprocess Engineering, Biomolecular Materials, and Structural Biology. The emerging Bioinformatics Group, mentioned in last year's assessment, remains as part of the Structural Biology Group. This year the division is under new leadership; the Bioprocess Engineering Group leader has been replaced and is now division chief. The DNA Technologies Group is pioneering a number of important methods. These include the development of SRMs for human identification and a critical database on short tandem repeats (STRs). The group also houses the NISTINational Cancer Institute (NCI) Biomarker Validation Laboratory (BVL), part of NCI's Early Detection Research Network (EDRN). Other programs include the geno- typing of single nucleotide polymorphisms and the establishment of methods for detecting and quanti- fying DNA damage and repair in cancer detection and treatment. This research is state of the art and continues to push the technology into new, productive, and high-impact areas. The Bioprocess Engineering Group focuses on developing measurement methods, databases, and generic technologies related to the biomolecular field in manufacturing. The group is active in bio- catalysts, biospectroscopy, biothermodynamics, and DNA separation and measurements. The group's work is of high quality and is clearly described in a well-designed Web site (www.CSTL.nist.gov/ NOTE: Chapter 4, "Chemical Science and Technology Laboratory," which presents the laboratory-level review, includes a chart showing the laboratory's organizational structure (Figure 4.1) and a table indicating its sources of funding (Table 4.1~. 143

44 AN ASSESSMENT OF THE NIST MEASUREMENT AND STANDARDS LABORATORIES: FY 2003 biotech/bioprocess/projects.html). The Biomolecular Materials Group focuses on studies of biological molecules and their potential uses in biotechnology. One emphasis is the study of thin films leading to determinations of the surface effects or character of biomolecules at surfaces. A closely related interest concerns the construction of biomolecular polymeric structures that act as scaffolds for tissue engineer- ing. A particularly promising project involves single-molecule measurement using pores of nanometer scale. Each of these studies is making fundamental advances in the understanding and control of biomolecular materials engineering. The Structural Biology Group participates in the Center for Advanced Research in Biotechnology (CARB), a joint NIST/University of Maryland research center located on the Shady Grove campus of the university about 4 miles from NIST. Scientists at CARE develop and apply measurement methods, databases, and state-of-the-art modeling methods to advance the understanding of protein structure/ function relationships. The individual programs are outstanding, and the group contributes a number of important resources such as the Protein Data Bank (PDB) to the world scientific community. Program Relevance and Effectiveness The Biotechnology Division faces unique challenges and vast opportunities resulting from the breadth of topics in the biological sciences, the rapidly changing nature of technology supporting new discoveries in life sciences, and the continuing emergence of new biotechnologies. To meet these challenges, it will be necessary to have a critical mass of personnel and equipment to address the appropriate issues in metrology and standards for each opportunity. A division 10 times the size of the current Biotechnology Division could not respond to all of the possibilities. Thus, the division must continually evaluate and reevaluate its portfolio of projects to ensure that they closely reflect and anticipate commercial needs. The recent adjustments in personnel within the division reflect this sense of reprioritization. In some cases, both critical mass and appropriate range of expertise can be obtained only by cross- divisional or cross-laboratory projects. Also, collaboration with external entities is clearly one method to leverage NIST resources; CARE is a good example. For CSTL, the challenge is to ensure that biology is incorporated appropriately into all divisions while fostering and enhancing within the Biotechnology Division a strong core of integrative biology (across molecular and physiologic scales) that is both current and quantitative in orientation. Overall, CSTL and the division have responded well to these challenges, although continuous reevaluation of the project portfolio remains a critical part of any strategy to respond to changing customer needs. The division can conduct three basic types of projects: (1) those responsive to current, identifiable needs; (2) those for the development of internal expertise in emerging areas in which evaluation and standardization of methodology are likely to be important; and (3) those for the develop- ment of new measurement technologies that, in themselves, will foster new biotechnologies. Examples of the first category are the Protein Data Bank, a real gem for NIST, and the effort to develop method- ology for the sampling and detection of genetically modified foods (a critical commercial need). Ex- amples of projects of the second category (for internal expertise) are those on proteomics and RNA- protein interactions. In particular with the Proteomics project, issues of standardization and validation are almost certain to emerge. An example of the third type of project is the cross-divisional effort, Single Molecule Manipulation and Measurement (SM3) initiative, which has a high probability of establishing new measurement methodology. The panel believes that all projects in the division's portfolio should be justified in one of these three categories. Within each category, the division must be willing to prioritize

CHEMICAL SCIENCE AND TECHNOLOGY LABORATORY: DIVISION REVIEWS 145 project value and eliminate less valuable although technically sound projects. To minimize the elimina- tion of technically sound projects, the division may need to seek out more extradivisiona1 partnerships to satisfy critical mass on some projects (e.g., partner with CSTL's Analytical Chemistry Division on analysis of genetically modified organism [GMO] foods). Overall, the division has made defensible choices in the project portfolio, adjustment of personnel, and partnering in cross-divisional or cross- laboratory projects and external collaborations. The division continues to maintain high external visibility and programmatic relevance. It functions with the fairly high level of external funding that it has received to sunnort its programs. Such funding 1 ·,. , · ·, · ,1 , · , · 1 · 1 1 r has positive aspects, since it requires the group to maintain a high degree ot customer responsiveness. The division has an ambitious portfolio of research projects that fall into the categories of health and medical products, forensics and homeland security, and food and nutritional products. Several projects serve as useful examples of responses to current, identifiable needs (category 1 projects) and highlight the breadth of program relevance. In the Human Identity/Forensic Science project, the division is developing new methods for DNA profiling, ranging from developing well-characterized DNA stan- dards for restriction fragment-length polymorphisms to performing research for rapid determination of DNA profiles by polymerase chain reaction (PCR) amplification and automated detection of fragments. These new methods have proven important for the identification of victims of the World Trade Center disaster of September 11, 2001, since the high degree of DNA fragmentation due to the severe environ- mental conditions meant that only about 50 percent of the specimens yielded results under standard DNA testing methods. An important project in the area of DNA diagnostics for the detection of human disease is the NIST component of the NCI Early Detection Research Network. This NIST project serves to refine recently discovered cancer biomarkers and to format new research tests for field trials in EDRN clinical laboratories. The rigorous validation of biomarkers for diagnostics is a critical issue that fits well with the development of measurement methodologies. These projects will offer high-impact improve- ments to human health. In 2002 the panel was concerned that the Proteomics Group might be spreading itself too thin and thereby limiting its ability to mount the kind of program needed in proteomics. However, the panel is now comfortable with the strategy of a small proteomics effort to develop the internal competency to assess developments in the field that will determine future NIST directions. A program that focuses development of new measurement technologies is the program on advanced mass spectrometry measurements of DNA damage. For example, the cellular accumulation of two major oxidative stress-induced DNA lesions in cells of Cocaine Syndrome patients after exposure to ionizing radiation has been identified. As a disease with implications for understanding the human aging process, these studies are undertaken as a collaborative effort with scientists at the National Institute of Aging. The program researchers and management should continue to carefully assess priorities and resource distribution to ensure that key programs are adequately supported. The group should also develop a plan that prioritizes its efforts in a way that is consistent with ongoing commitments and its current expertise base. The DNA separations and analysis projects are responsive to current, identifiable needs. These projects focus on GMO testing (a critical issue for agriculture and global trade), identification of pathogens (important for medicine and homeland security), and the development of DNA standards for use in industries involved in DNA vaccines and gene therapy. Much of the work in the biocatalysts and biothermodynamics projects has focused on understanding the chorismate biosynthetic pathway (en- zymes, thermodynamics, and so on). This pathway is important in agriculture and in the biomanu- facturing of aromatic amino acids and related compounds, and it has served as a model system for

146 AN ASSESSMENT OF THE NIST MEASUREMENT AND STANDARDS LABORATORIES: FY 2003 studying metabolism. The biospectroscopy projects address primarily categories 1 and 2. The develop- ment and production of fluorescent reference materials in the biospectroscopy project also address current, identifiable needs. Much of the other work in the division involves the development of internal expertise in emerging areas in which evaluation and standardization of methodology are likely to be important, such as broader application of fluorescence. Although it is appropriate for NIST to take the lead in GMO testing, this work is supported by only two people, who are also involved in several other projects. To increase the critical mass on this project, the Bioprocess Engineering Group should enhance its level of collabora- tions with both internal and external groups. The chorismate pathway project has been very successful; however, the panel recommends a reconsideration of this work and its contribution to the mission of the .. . . alvlslon. The issue of changing the group name to something other than Bioprocess Engineering came up several times during the panel review. The reason for concern seems to be that "Bioprocess Engineer- ing" does not accurately reflect the scope of the group and may be misleading to internal and external collaborators. One suggestion provided to the panel was "Biophysical Measurements," but this name seems too broad. Another, narrower suggestion was "Bioprocess Measurements," which may be too narrow. The panel recommends that the group continue to think about names that reflect its scope and purpose. Finally, the panel was encouraged by the efforts within the Bioprocess Engineering Group in the area of homeland security. These efforts include a substantial program funded by the Air Force. The group is also preparing a white paper on opportunities in this area for the Biotechnology Division as a whole. The Structural Biology Group continues to realize its potential as a high-quality program with international impact. The CARB center addresses projects in X-ray crystallography, biomolecular nuclear magnetic resonance (NMR) spectroscopy, protein folding, computational chemistry and model- ing, and mechanistic enzymology. This work can be characterized as being in categories 2 and 3; it is outstanding. A stimulating research environment exists within CARB, and it maintains the mission- oriented flavor critical to NIST programs. The value and uniqueness of CARB appear to be fully appreciated by NIST senior management, which views it as a paradigm for future NIST/academic _ _ ~ ~ ventures. Last year the panel expressed concern that NIST staffing levels at CARB were too low, and several decisions have been made in the past year to increase the NIST presence at CARB. The low staffing- level trend is being reversed by relocating the Protein Data Bank workforce to CARB, where natural scientific synergies exist. The NIST campus will continue to provide hardware support. The PDB, a category 1 program, is the premier world resource for data on protein structure and function and as such showcases NIST's role in biotechnology. The PDB Web site records approximately 6 million hits a month, providing an impressive metric of its value to the scientific community. As part of its move to increase the NIST presence at CARB, CSTL merged its Bioinformatics and Structural Biology Groups at CARB. Overall, the programs at CARB continue to be highly relevant, and the moves to bolster the NIST presence are important. However, the success of the CARB experiment should not obscure the need for a continued strategic plan. CSTL should develop a long-term plan that clearly describes what its future vision of NIST's role at CARB is and how it will respond to new growth initiatives for CARB from the University of Maryland. A clear plan of commitments will be an important component in attracting a first-rate director for CARB.

CHEMICAL SCIENCE AND TECHNOLOGY LABORATORY: DIVISION REVIEWS Division Resources 147 With respect to division resources, the issues of critical mass and portfolio review merit attention, given the breadth and depth of current interest in biotechnology. The division cannot do everything. Considering the wealth of opportunities in this field, the panel believes that the division's staff should be growing and is concerned that in fact it seems to have decreased slightly. On the other hand, the panel is encouraged that some restructuring between groups was done to staff new projects more efficiently. The facilities and equipment in the division are excellent and adequate to fulfill its mission. The DNA Technologies Group lost two full-time employees, who were transferred to the Bioprocess Engineering Group in a move to align expertise (the restructuring mentioned above). The DNA Tech- nologies Group boasts a number of state-of-the-art resources. The high-speed matrix-assisted laser desorption ionization (MALDI) time-of-flight mass spectrometers with automated sample preparation, capillary electrophoresis (CE), and gas chromatography/mass spectrometry (GC/MS) facilities are ex- cellent. The Structural Biology Group has maintained constant staffing over the past year. The group is well outfitted for cutting-edge research, given that the X-ray diffraction and ultrahigh-field NMR facilities are outstanding. The PDB resources are impressive. The Biomolecular Materials Group lost one full-time employee in the past year. The group's relatively small size restricts its ability to take on new projects and continues a long-term trend in loss of faculty. The facilities and equipment available for the work of this group are excellent. PROCESS MEASUREMENTS DIVISION Technical Merit The Process Measurements Division of CSTL provides a central, national source for reference materials, calibration of measurement equipment, and data on materials properties. A core responsibility of the division is the improvement and dissemination of national measurement standards for tempera- ture, fluid flow, air speed, pressure and vacuum, humidity, liquid density, and volumetric measure- ments. To facilitate communicating the panel' s findings concerning the Process Measurements Division, a summary is first provided, followed by details of the visits to each of the division's groups. The technical quality and merit of the Process Measurements Division can be illustrated by the following achievements during FY 2003: · Achievement of the ability to concentrate an analyte ~10,000x in a microfluid environment. The panel is impressed with the clever use of thermal and electric-field gradients used to achieve this competence; · Involvement of the division with two NIST Competence projects, which in the panel's view speaks to the quest for excellence and for advancing the state of the art in measurement science; · Development of a new piston calibrator for jet fuel flow sensors and pioneering of a unique design for a diverter valve needed to reduce the uncertainty of large water flow calibrations; · Capturing the distinction of being first in the world to advocate the use of the backscattering configuration for Raman spectroscopy to eliminate polarization effects as sources of intensity differ- ences for samples measured by different laboratories, and development of an advanced mathematical model to simulate such scattering by ternary and quaternary III-V compounds;

148 AN ASSESSMENT OF THE NIST MEASUREMENT AND STANDARDS LABORATORIES: FY 2003 · Completion of a study of the intrinsic stability of sensors without their electronics, which indi- cated that the electronics may be limiting the uncertainty and therefore will require improvements to match the stability of MEMS pressure sensors; · Development of plans to explore standardization needs in the area of dynamic pressure measure- ment; and · Adoption of ISO/IEC 17025 standards for all calibration projects. The panel continues to be impressed by the concentration of measurement knowledge and expertise in this division and by the quality of its work. Delving more deeply, the panel was especially impressed with the ongoing projects discussed in the following subsections. Molecular Electronics Molecular Electronics a competence project funded at approximately $1.3 million per year for 5 years (it is in its third year) appears to be a model for its breadth, integration of talent at NIST (six groups in three divisions and two laboratories), and collaboration with Hewlett Packard and IBM. This project's alternative approach to electronics technology is based on single-electron devices having molecular-sized components, and it uses nonlinear processes that are analogous to silicon-based diodes and transistors. Because the processes originate from synthesized molecules, the dimensionality is much smaller and is more dense than that of traditional devices. The CSTL effort is focused on testing a variety of methods that will provide early input into the feasibility of this approach. One such method is two-photon photoemission, which accesses unoccupied electronic levels and tracks electron relaxation effects. In this impressive project, short pulses (~10 femtoseconds) of variable wavelength from titanium- sapphire lasers are used to analyze molecular structure using the two-photon photoemission technique. Fluid Science The division's determination and dissemination of fluid properties respond directly to industry needs for thermal-based mass flow measurement systems, which are limited in performance by the accuracy to which fluid properties are known. Technologies and competencies developed in the fluid science project have been applied by the division's thermometry researchers. Acoustic technology developed in the Fluid Science Group has been applied by the Thermometry Group to primary acoustic thermometry. Improvements to the ITS-90 temperature scale have resulted. This method has been applied up to 575 K, and the goal of 800 K appears obtainable. This fluid science project is also striving for development of a primary pressure standard based on measurements of the dielectric properties of helium. the goal is to achieve a 1() to 2() ppb uncertainty with the cross-capacitor He-dielectric measurement approach. So far, 100 ppb has been demonstrated. A novel, cross-capacitor made from a single edge-grown sapphire crystal has been developed and shows promise; however, a state-of-the-art capacitance bridge is required to meet the ultimate goal. Vendors are being sought to provide the needed tool. The panel raises a question that must be considered: If a key measurement tool needed for the primary standard is not currently available, does this introduce an extra limitation into the utility of a primary standard? The panel also questions how this approach compares to the resonant silicon pressure sensing approach being pursued by others. The project continues its ongoing effort to map the thermophysical properties of gases used in semiconductor processing, which is challenging because some of these gases are highly reactive or

CHEMICAL SCIENCE AND TECHNOLOGY LABORATORY: DIVISION REVIEWS 149 corrosive. This acoustic resonator R&D area seems well connected with the semiconductor industry and academia and might benefit from closer interactions with the Fluid Flow Group. Work accomplished by the fluid property measurements project includes the use of an oscillating gas column around a heated honeycomb in combination with an acoustic resonator to measure fluid properties with greater accuracy Art and k to 0.3 percent, p and cp to 0.1 percent, and c to 0.01 percent). The Raman Spectra Calibration Library has made significant advances in the calibration of Raman spectra by creating Raman intensity standards, promoting the use of backscattering and advanced modeling of the scattering from spatially inhomogeneous samples. Thermal and Reactive Processes Optical absorption measurements of synthetic soot produced from the controlled combustion of heptanes are being studied, with the goal of developing SRMs of known composition and with known characteristics. These SRMs will allow users (especially transportation, energy, and environmental industries) to calibrate their instruments, determine uncertainties in their measurements, and develop appropriate models. The Process Measurements Division has a unique technical competency in this area. It would be interesting to see a correlation between the absorption characteristics of soot in the air caused by air pollution and the synthetic soot standards developed as reference materials. The group developed an SRM for Raman spectroscopy. Raman spectroscopy is becoming widely used in a number of industries, so the need has increased for a simple, reliable calibration technique for this measurement method. The development of a standardized glass (SRM 2241) is a practical approach for providing an easily transferred, stable, intensity calibration source that can be activated by laser light at 785 nm, a common laser wavelength. SRMs used for Raman spectroscopy at other wavelengths will be developed and made available in the future. The panel is pleased with this activity. Fluid Flow The Process Measurements Division has continued to improve fluid flow rate measurement capa- bilities and to reduce uncertainties. The completion of the small PVTt (pressure, volume, temperature, time) system gas flow standard represents a significant milestone, replacing traditional proven piston and cylinder and bell technologies with a fully automated calibrator that had been documented to reduce uncertainty by a factor of 10. This represents a level of accuracy that is best in the world for gas flow rate. A larger PVTt system is under development and approaching completion. The division has also developed an improved liquid flow rate calibration technique that is expected to have a significant impact throughout the liquid flow rate calibration community. The division has pioneered a uniquely designed prototype diverter valve that provides for self-cancellation of an error source that has plagued gravimetric flow rate calibrator systems for decades. The panel views this accomplishment as a creative solution to reducing the uncertainty of this calibration. The Process Measurements Division continues to lead the international community through CIPM and Sistema Interamericano Metrology (SIM) working groups. The division is conducting projects for DOD aimed at improving flow rate measurement accuracies for both liquid and gas flow by an order of magnitude. A newly constructed liquid fuel piston calibrator with a flow range of 0.01 to 3 gal/min and accuracy of 0.025 percent is now being tested for a DOD customer. The division is pursuing development of a low-gas-flow measurement assurance program utilizing a new breed of highly stable commercial flow sensor nozzles and laminar flow elements (annular, Re < 500, L/D 2 ~2000~. Round-robin testing and participation with outside testing organizations are

150 AN ASSESSMENT OF THE NIST MEASUREMENT AND STANDARDS LABORATORIES: FY 2003 exemplary. The division also continued the effort to complete the Exhaust Gas Flow Laboratory, which cost between $3 million and $4 million to build. Once completed, this facility will allow the develop- ment of important collaborations with the automotive industry. Process Sensing With respect to work on microheater sensors, conductometric SnO2 or TiO2 film sensors of ~500 A in thickness and ~ 100 x 100 Em in size have been able to sense 20 to 200 ppb of satin and can also detect mustard gas and GA-tabun with a response time of ~50 s. A new, monolithic pre-concentrator may increase sensitivity by 10 times. In addition, carbon nanotube growth on MEMS micro-ho/plates has been demonstrated, clearing the way for the evaluation of their performance as gas sensors. Sensitivity, selectivity, speed, and stability issues must still be addressed to improve performance. As with other micro-ho/plate microsensors based on doped SnO2, TiO2, or differential calorimetry which promise the possibility of attractive performance parameters such as low power, low cost, and compactness- achieving stable operation over thousands of hours still represents a major challenge and should be considered carefully. This project is relevant to homeland security and chemical warfare agent defense technologies. Plasma Process Metrology In 2002 the Plasma Process Metrology project developed a method for two-dimensional mapping of the gas temperature of plasmas using the planar, laser-induced fluorescence method. Results have been shown for a CF4 plasma operating at several different pressures. This is a nice application for a high- level, advanced metrology method. This measurement method could potentially be used to explore the thermal effects of particles in plasmas which, along with heat transfer studies, will likely be of interest to the semiconductor industry. In response to last year's concerns of the panel, the Plasma Process Metrology team has developed a new, inductively coupled, 300-mm plasma process reactor. This system closely resembles the process tools used by chip manufacturers and is a significant advance beyond the tool previously used, which is referred to as the GEC tool. Microfluidics The Microfluidics project developed an ingenious approach to both concentrate (210,000:1) and separate analyte in liquid/ionic microfluidic streams. This procedure is based on achieving a unique balance of forces on ionic analyses (fluorescent dyes, amino acids, proteins, DNA, and colloidal par- ticles) in overlapping and opposed electric field and temperature gradients (temperature gradient focus- ing). Concentration of analyses at ratios greater than 10,000 to 1 were demonstrated and considered by the panel to be a significant achievement. Pressure and Vacuum The panel discussed with the group leader the merits of developing alternate approaches for support- ing calibration service customers. One approach discussed would be to replace such traditional calibra- tion services with "NIST traceable programs." Such a program might apply processes similar to those used for NIST-traceable reference materials, laboratory intercomparisons, and measurement assurance

CHEMICAL SCIENCE AND TECHNOLOGY LABORATORY: DIVISION REVIEWS 151 programs. Among its benefits would be the sort of traceability and proficiency test data required by the customer to meet the requirements of ISO/IEC 17025 standards. The program would benefit the cus- tomer by transferring the world-class accuracies of NIST to commercial and military primary calibration laboratories and by providing continuous assurance of accuracy. NIST would benefit by having flexibil- ity in the scheduling of workloads for better utilization of laboratory resources and a more stable income stream. The panel was told that the cultural change associated with the application of ISO/IEC 17025 standards throughout the Process Measurements Division has been beneficial, and that improvements in the quality of calibration services are expected. An objective evaluation of the impact, if any, of the new quality program on the technical merit of divisional programs would be appropriate after full implemen- tation at the end of 2004. The adoption of ISO/IEC 17025 standards is also applauded by the panel. Thermometry The panel noted that the Thermometry Group continues to exert technical influence on the interna- tional temperature measurement community, as demonstrated by its developing the program for and peer reviewing articles for the 8th International Temperature Symposium that took place in 2002 in Chicago. The Thermometry Group presented eight papers. The group also completed work on Key Comparison 3 (K3) of the international Consultative Committee on Temperature. NIST was the pilot laboratory for the most comprehensive intercomparisons ever conducted. A temperature range covering -189 °Cto+660°C was done. This past year, the Johnson Noise Thermometer prototype was completed, and a noise-to-power accuracy ratio of better than 0.1 percent was documented over the range considered. The ability to recalibrate such sensors in situ for example, for space station applications is viewed by the panel as very significant. Completion of construction of the acoustic thermometer was followed by validation testing, includ- ing the measurement of the temperature of the gallium melting point, which showed excellent agreement with earlier work. Excellent results at indium and tin freezing points give confidence that the division will finally be able to resolve problems in the temperature scale. Program Relevance and Effectiveness The Process Measurements Division continues to be responsive and forward thinking in supporting certain industries (e.g., semiconductor and automotive). It was not clear to the panel whether other important segments of U.S. industry (e.g., process, gas, biomedical) were getting the same attention or would perceive the division's programs as relevant to their needs. Overall, this panel was again im- pressed by the effectiveness and progress toward automation in many of the division's projects. A fair amount of effort at CSTL seems to be focused on the semiconductor industry. How does this compare to the effort it invests in the other 5 out of the 12 CSTL program areas that the division is supporting? The division has continued efforts to develop and maintain close contact with manufactur- ers and other customers, including integrated circuit manufacturers, in response to comments made in the FY 2002 assessment. The division's determined effort to bring all calibration programs into compliance with the ISO/IEC 17025 standards is expected to highlight the relevance of NIST programs, especially in the eyes of its calibration service customers. It would be especially beneficial for NIST to publish its ISO-compliant quality manual and other relevant quality documents on the Web. Commercial and government calibra-

152 AN ASSESSMENT OF THE NIST MEASUREMENT AND STANDARDS LABORATORIES: FY 2003 tion and testing laboratories could use such documents for a variety of purposes, not the least of which would be as guides and templates for their own documents. The division provides considerable consultative and advisory services for its calibration customers and researchers. The availability of NIST experts for telephone consultations is a valuable service to U.S. industry and the U.S. government. Providing such assistance is said to consume as much as 25 percent of division researchers' time. NIST seminars and workshops provide another valuable dissemi- nation vehicle for technologists and researchers to interact with NIST experts in their field. The results of NIST programs and technical information were made available to the public during the past year through a variety of means, including free, Web-based processes, computer media, publi- cations, talks, participation in committees, and workshops. The division's output included 93 publica- tions, 90 presentations, 1 CRADA, 9 patents or patent applications, 1 SRM, 187 calibrations or tests, participation in 96 committees, 1 editorship, and 5 workshops/meetings. Division Resources Division facilities continue to show improvement. Construction of the new metrology building is progressing, and the panel looks forward to the day when many divisional areas are able to take advantage of this environment that will be among the best in the world. Calibration charges to customers currently cover only about 70 percent of CSTL' s costs. The panel encourages CSTL to recover its full costs through a combination of cost reduction and price increases. This may result in performing fewer calibrations and transferring more calibration work to secondary standard laboratories, such as CCESI, Flow Dynamics, and Aldan, but would leave more time for research on measurement and calibration automation. The resources of the division are adequate, espe- cially in view of the impending readiness of the new metrology building. Responsiveness to Panel Recommendations The division's response to the panel's suggestions in the FY 2002 report to boost Web-based data dissemination was that "data for gases used in semiconductor manufacturing are freely disseminated." This response is not viewed as being especially proactive. There was no mention of adding one property column (viscosity), nor of attempts to relate the division's Web site to other CSTL Web activities. The panel did not see that resources and structure for increasing the rate of Web-based data dissemi- nation were implemented as recommended. Additional Comments The Process Measurements Division has developed and demonstrated the capabilities of micro- hotplate and microcalorimetry sensors in terms of their high sensitivity, and it could earn high regard in the sensors community if it were able to clarify the fundamental expectations and limitations of the stability of nanoscale and thin-film sensor technology. The panel also suggests that rather than abandon- ing the established custom of charging for the use of NIST's property data, some minimum access in terms of downloaded megabytes or computer milliseconds over a subscription period could be allotted to each new e-mail address in order to familiarize potential customers and researchers with the hidden wealth of information.

CHEMICAL SCIENCE AND TECHNOLOGY LABORATORY: DIVISION REVIEWS SURFACE AND MICROANALYSIS SCIENCE DIVISION Technical Merit The Surface and Microanalysis Science Division performs research to accomplish the following: 153 · Determine the chemistry and physics of surfaces, interfaces, particles, and bulk materials and determine their interactions with a broad spectrum of analytical probes, including electrons, photons, ions, atoms, and molecules; · Determine the chemical and isotopic compositions, morphology, crystallography, and electronic structure at scales ranging from millimeters to nanometers; · Determine the energetics, kinetics, mechanisms, and effects of processes occurring on solid surfaces and interfaces as well as within materials and devices; · Study the total chemical measurement process as well as source apportionment in atmospheric chemistry using advanced isotope metrology and chemometrics; and · Develop and certify key Standard Reference Materials and Standard Reference Data. The overall quality and dedication of the division's staff are extremely high. Since last year's review, the Surface and Microanalysis Science Division has further modified its organizational structure in order to focus its projects on its primary mission. It has reduced the number of groups from four to three, having redistributed the staff assigned to the Atmospheric Chemistry Group to other groups. This change is an excellent example of the division's responsiveness to recommendations of the review panel in the FY 2002 report. The reorganization appears to be an effective step toward concentrating the staff talents on core competencies. The transition is proceeding as important legacy projects are brought to a proper conclusion, and assimilation into the new group structure should be completed this year. The three remaining groups are the Microanalysis Research Group, the Surface and Interface Research Group, and the Analytical Microscopy Group. The division's technical programs continue to be world-class, with many clearly being at the leading edge of research. During the past year, the division organized six major workshops on a national level and organized a number of sessions at other types of conferences as well. The division has participated in important site visits to approximately a dozen major companies and is involved with a number of important CRADAs. Furthermore, it has active collaborations with several external companies, both domestic and international. Multiple collaborations with other NIST laboratories and external support- ing organizations attest to the high value of its scientific work. The division has also presented numerous important technical papers and talks at both domestic and international technical conferences. This output attests to the intent of the division to share appropriate results with the professional community in order to further the general aims of the scientific community. All of this speaks very well for the division and its current activities. The research work performed by the Microanalysis Research Group has long been noted as being world-class and leading edge. Many of the standard techniques used worldwide in microanalysis are almost fully based on this valuable NIST program. Recently, this group has shown its determination to retain its research leadership by continually developing new approaches to what has been standard methodology. An example is the use of the NIST microcalorimeter in Boulder to obtain high-resolution X-ray spectroscopic data and apply them to the problems of electron probe microanalysis. This major development in instrumentation is currently being commercialized in the United States and Europe by two instrument manufacturers. Although it is unfortunate that intellectual property issues in NIST kept this technology from being widely distributed for some time, that problem has apparently been solved,

154 AN ASSESSMENT OF THE NIST MEASUREMENT AND STANDARDS LABORATORIES: FY 2003 and commercial instruments are in the early stages of beta site installations. The impact of this instru- ment will be significant owing to its rapid throughput and its high-energy resolution. The group contin- ues to maintain its world leadership by having early access to the tool, which is now in Gaithersburg, and by demonstrating its practical applicability. It is expected, on the basis of this work, that this instrument will eventually change the complexion of manufactured electron probe microanalysis sys- tems. A further example of the Microanalysis Research Group's intent to retain leading-edge capability is its current exploration of the silicon drift detector, also for X-ray spectroscopy. Although the resolution of this tool is comparable to that of the older semiconductor detectors, the speed of data access will most likely lead to its widespread industrial application, since the speed of data acquisition is essential for the control of complex manufacturing processes. Data collection speeds are expected to improve by as much as two orders of magnitude with the use of this technique in some circumstances. The development of an XML data format for spectroscopic hyperdata in the Transmission Electron Microscope Laboratory is extremely important, and the division is to be commended for supporting this work. This general data format allows for very impressive methods of spectral data storage and analysis and is destined to become a standard, nationally accepted format. This is, of course, completely consis- tent with the mission statement of CSTL. This hyperspectral data storage tool applies to more than the X-ray spectra demonstrated to the panel, and widespread utilization is to be expected. Program Relevance and Effectiveness The opening remarks from late year's summary of the Surface and Microanalysis Science Division remain valid and are simply repeated here for reference: The Surface and Microanalysis Science Division uses a variety of methods to ensure the relevance and effectiveness of its programs. It is mapping key activities to the NIST Strategic Focus Areas. For exam- ple, nanotechnology is supported by the division's project on cluster-ion SIMS for high-resolution depth profiling, the Competence program on molecular electronics, and overall general chemical imaging. Support of homeland defense has been an integral part of the division for many years, with projects in forensic particle analysis, quality assurance and control methods for the U.S. Atomic Energy Detection System (USAEDS), gas mask standards, and analysis of explosives particles. The division has new activities in support of health care, including monitoring boron neutron capture chemotherapy using SIMS analysis of tissue samples, drug delivery using nonlinear optical spectroscopy, nanoscale analysis of compounds of pharmaceutical interest using near-field scanning optical microscopy.] it remains unclear, however, how carefully these programs are coordinated with other projects in CSTL, the larger NIST, other national laboratories, and external university and industrial research. The large number of industrial visits this year is laudable but, as mentioned in last year's report, more extensive utilization of the NIST Industrial Fellows Program is encouraged. Such longer-term interactions with industrial and university laboratories would assure CSTL that the work that it is doing in the area of standards development is, in fact, the work that is required by these external researchers to facilitate their R&D efforts. Although these in-depth interactions are possibly limited by funding and heavy staff responsibilities, it is critically important that they be fostered, even if internal programs might be temporarily delayed in the process. 1National Research Council, An Assessment of the National Institute of Standards and Technology Measurement and Standards Laboratories: Fiscal Year 2002, National Academies Press, Washington, D.C., 2002, p. 106.

CHEMICAL SCIENCE AND TECHNOLOGY LABORATORY: DIVISION REVIEWS 155 The decision-making process used in defining individual projects in the division is also not particu- larly clear. Although most of the work that the panel has seen is of outstanding quality and relevance, some projects seem to have been based on individual researchers' interests rather than a clear connec- tion to the mission of the division. It is very important that these connections be made and justified. It is clear to the panel that the visibility of the Surface and Microanalysis Science Division in the technical community is quite high, from the number of presentations made at professional society meetings or meetings organized by the division's staff. The division organized five workshops of critical importance and also organized sessions at other meetings as well. This activity is commendable and indicates that the division takes a leadership role in many aspects of surface and microanalysis science. The panel is quite pleased to note that some highly relevant standards have been developed and applauds the division's efforts in this regard. The work on the provision of intermediate "golden standards" is also a critical response to industrial needs that cannot be satisfied by a true SRM, which would take much longer to provide to the nation's researchers. This work has clearly been very effective in supporting industrial needs. It did not appear clear to this panel that division projects are carefully controlled for duration and results. Some projects that have been continuing for some time do not seem to be much closer to their targets. Decisions should be made on the basis of realistic project goals as well as the importance and viability of the individual efforts. Consideration of standard project management and tracking method- ologies with milestones should be made by the division and utilized where appropriate. The continuing program to characterize single crystals of silicon-germanium will have a profound impact on the semiconductor industry, but it must be emphasized that the window for completion of this work is a small one. Clearly recognizing this problem, researchers working on this problem have defined a class of "Interactive Materials" which, although not SRMs, will allow industry to have a reasonably well characterized material upon which to base analyses, with the expectation that other laboratories utilizing these materials will come reasonably close to the same results under similar operating conditions. The panel commends the development of such Interactive Materials and suggests that the approach be spread more widely throughout NIST. The work to reduce the relative error in electron-probe microanalysis is obviously very important, and it appears that progress is being made. However, the panel is concerned that although this program has been in existence for a while, no executive-level summary has been offered from which the progress can be gauged. Expected project milestones for such long projects should be made available to review panels, and some method of tracking progress must be available. This comment also applies to other, relatively long-term projects in this and other divisions. fine Surface and Interlace xesearcn Croup continues to do very important and leading-cage work. This group is investigating infrared near-field scanning optical microscopy in a way that is intended to advance the capability for obtaining high-resolution surface information. The technique will produce a 50-fold increase in lateral resolution while maintaining the spectroscopic capability of Fourier transform infrared spectroscopy (FTIR). The group is also developing confocal Raman microscopy as a tool for surface and interface characterization. Increasing the chemical information content of surface and interface analysis techniques is a very important goal. The combinational instrument approach, the inclusion of a range of techniques in a single instrument, is clearly pushing instrumental capabilities and developing techniques that will have great industrial applicability. The panel commends these efforts as being clearly in line with the division's mission. The exploration of tools to characterize molecular electronics is therefore being carefully balanced in such a way that the measurement techniques will have widespread applicability in other technical areas as well. The group is exploring the basis of ~~ ~ r ~ T . r ~ ~ ~ i.

156 AN ASSESSMENT OF THE NIST MEASUREMENT AND STANDARDS LABORATORIES: FY 2003 enhancing imaging phenomena so that measurement protocols will be scientifically based. The group thereby established that contrast is not an absorbance phenomenon. The materials distributed to the panel by this group also demonstrated that very specific industrial companies were to be the beneficia- ries of this work, again in keeping with NIST's overarching mission statement. The Analytical Microscopy Group works on a number of highly varied projects. The critical nature of this work does not require elaboration, and the division is quite up to the task of providing critical information in this area of national need. An important project was the development of methods for the trace detection of explosives, a program clearly related to the needs of homeland security. This work involves the characterization of particles that come off clothing via air bursts, swipes of luggage, and so on. The detection and identification of such particles should probably involve wider cooperation within and outside of CSTL, because many pockets of expertise throughout NIST are relevant to this work. The determination of the scientific underpinnings for such work is critical and appears to be receiving appropriate attention in this group. An important focus of the work with the chemical characterization of particulate matter relates to homeland security, with work concentrating on explosives with the Trans- portation Security Administration, dirty bomb characterization, and gas mask calibration. The development of secondary ion mass spectroscopy (SIMS) SRMs for implant standards seems to be leading to successful SRM introductions, but the panel believes that these materials should have been developed and distributed much sooner. The "Interactive Materials" mentioned above clearly have an important place in this program because of the complexity of SRM development and its obvious conflict with industrial timescales. Nevertheless, the development of these standards is commended and is recognized as an extremely valuable contribution. The understanding of degradation mechanisms for such standards is clearly being addressed. It is useful to emphasize how important and useful this work has been to the semiconductor industry. The work on particle and isotope methodology seems to be a collection of legacy projects as the staff explores next steps, with the division reorienting the original Atmospheric Chemistry Group along its primary competencies. Several of these projects for example, the enhanced sensitivity of the cobalt- 60 autoradiography over gamma spectroscopy and the collaboration with the University of Maryland- have provided particularly practical information. One example of a legacy project involves the charac- terization of asbestos particles, which does not appear to be particularly innovative. The work reported on Auger and Electron Spectroscopy for Chemical Analysis databases is ex- tremely important internationally and is recognized for its quality and usability. The panel was told that the database receives "thousands of hits" by professionals in any one month and is thus a very important tool for the surface science community. The panel believes that funding for this work is not adequate. A number of the technical presentations to the review panel did not consistently convey the objec- tive, the significance of the accomplishment, or how the results would be used by U.S. industry. The panel recommends that more careful attention be paid to the quality and uniformity of presentations. The foregoing critique should be recognized as being in the spirit of fine-tuning; the panel strongly believes that the work of the division is highly relevant to the goals of CSTL and of the nation. The effectiveness of these programs is clearly indicated by the high regard that most external organizations, educational and industrial, have for the work of the division. A picture of high quality and effectiveness is characteristic of the division, and this should remain in focus as these remarks are interpreted. Division Resources The Surface and Microanalysis Science Division has 39 full-time permanent employees as of January 2003, substantially the same as in the previous year. The panel is concerned, however, that the

CHEMICAL SCIENCE AND TECHNOLOGY LABORATORY: DIVISION REVIEWS 157 ratio of technical support to professional employees is far from optimal. NIST professionals still find themselves doing a great deal of work that does not really fully utilize their capabilities. Instrumentation upkeep appears to be adequately covered by service contracts. Most industrial organizations have found that the expense of technical support personnel usually translates into more effective and productive utilization of its professional staff. Thus, the panel suggests that as opportunities arise to replace professional staff, a plan should be put in place that would, over some reasonable period of time, evolve the staffing levels into a more appropriate ratio of professional to support staff. The panel expects that this issue will be addressed. The previous panel suggested changes in the Atmospheric Chemistry Group. The division re- sponded by eliminating the group and redistributing the staff to other groups. The logic for this move was made clear, but the current panel is not sure that the older projects have not continued, albeit in a different area of supervision. Some of these projects are clearly important, but project deadlines for the completion of this work should be made clear. A careful plan to absorb all of these staff members into their new group environments should also be created. The division' s numerous postdoctoral employees add greatly to the vitality of the organization and might benefit from opportunities for closer mentoring. Their lack of understanding of the reward system utilized by NIST should be corrected. There is a perceived lack of direct interaction and communication between staff management and staff members. Drop-in laboratory visits are encouraged. The division seems to be well equipped with modern instrumentation, but some of it, although fully functional, is quite old and in need of updating. For example, the electron microprobe has been updated with new spectrometer fixtures and software and electronics, but the purchase of more modern instru- mentation would probably have been more cost-effective. Last year the panel took note of the fact that the Microanalysis Research Group did not have access to an in-house focused ion beam (FIB) system. The FIB has become the standard method for preparing samples for transmission microscopy as well as for scanning electron microscope observation and analysis. Clearly there is much to understand in the artifacts presented by such samples prepared by FIB tools, and NIST is clearly the appropriate place for this work to be done. FIB was, in fact, to be made available to CSTL, but funding reversals caused this item to be temporarily dropped. This panel very strongly recommends that this instrument be procured as quickly as possible, so that the Microanalysis Research Group can maintain its world-class leadership in this analytical regime. The panel views this issue as crucial and needing immediate attention. The recent purchase of a SIMS instrument seems to be meeting specifications and proving to be of great value. Unfortunately, the new Auger system has, after quite a few years, failed to meet its specifications. Future equipment purchases should better protect NIST from failure of suppliers to appropriately meet required instrument specifications, and financial sanctions should be included in purchase agreements. From the perspective of meeting its primary goals, the instrumentation suite is nevertheless world- class, and in the area of microanalysis the division is clearly a world leader. PHYSICAL AND CHEMICAL PROPERTIES DIVISION Technical Merit The Physical and Chemical Properties Division serves as the nation's reference laboratory for measurements, standards, data, and models in the areas of thermophysics, thermochemistry, and chemi- cal kinetics. The panel commends the division for its excellent balance between experimental and theoretical expertise in all areas of the program, and particularly notes the continued emphasis on

158 AN ASSESSMENT OF THE NIST MEASUREMENT AND STANDARDS LABORATORIES: FY 2003 maintaining its unique experimental capabilities. This emphasis is important, as experimental work continues to be Reemphasized throughout the thermodynamics community. Loss of expertise in com- bustion calorimetry with the recent retirement of the project's principal investigator was noted by the panel. The division conducts work of unsurpassed quality in making fundamental measurements of thermo- physical and thermochemical properties. Division research is organized around eight focus areas that cut across group project boundaries: basic reference data; computational chemistry; fundamental studies of fluids; tools for chemical analysis; cryogenic technologies; measurements for the environment; data for process and product design; and properties of energy-related fluids. Selected highlights of these pro- grams are presented below as a means of illustrating the high technical merit of the work that is performed. The division consists of six groups, three at Gaithersburg (Computational Chemistry, Experimental Kinetics and Thermodynamics, and Chemical Reference Data and Modeling) and three at Boulder (Experimental Properties of Fluids, Theory and Modeling of Fluids, and Cryogenic Tech- nologies). Additionally, three independent projects are also located at Boulder (the Thermodynamics Research Center, the Membrane Science and Technology project, and the Properties for Process Sepa- rations project). Computational Chemistry An example of outstanding theoretical work within the Computational Chemistry Group is the recent study of transferability of hybrid functionals highlighted in Science magazine in October 2002. Significant increases have occurred in the external use of the Computational Chemistry Comparison and Benchmark Database developed by the group since the database became available to the public 3 years ago. Additionally, the group has been active in the organization of conferences related to computational chemistry; examples include the First Industrial Fluid Simulation Challenge, in collaboration with the Boulder-based Theory and Modeling of Fluids Group, and the first of a new conference series on computational biophysics, which was organized and co-chaired by the group leader. Experimental Kinetics and Thermodynamics The Experimental Kinetics and Thermodynamics Group provides reliable kinetic and thermody- namic data and standards pertaining to industrial processes, environmental chemistry, energy efficiency, and fire suppression. Its products include evaluated kinetic and thermodynamic data, evaluated chemi- cal models, computational tools, data compilations, and thermodynamic standards. The group has continued to increase Web-based access to its data. Particular achievements this past year were completion of a project to put the NDRL (Notre Dame Radiation Laboratory~lNIST Solution Kinetics Database on the Web and initiation of a project to make thermodynamic data evaluations Web- accessible. The group has also made use of the Web to make spectroscopic data obtained from a variety of sources widely available. These data include vacuum ultraviolet spectra critical to the development of new lithographic tools for semiconductor production and infrared spectra on a wide range of halocar- bons to aid in the calculation of global warming potentials. The recent development of an indium thermal analysis standard in collaboration with the German standards organization Physikalisch-Technische Bundesanstalt was a successful operation in which the capabilities of the two organizations were combined to produce a new differential scanning calorimeter standard for industry. These collaborative efforts are critical to leveraging the world-class thermody- namic capabilities of NIST.

CHEMICAL SCIENCE AND TECHNOLOGY LABORATORY: DIVISION REVIEWS 159 The panel is pleased to learn that the problems associated with the kinetics database are being addressed by assigning the abstracting tasks to members of the group. This solution has the additional advantage of providing more expert commentary on the data. The panel applauds the effort to make information from both kinetics databases accessible from the WebBook (http://webbook.nist.gov) and recommends that these efforts to integrate the data activities across the division be continued. Chemical Reference Data and Modeling The Chemical Reference Data and Modeling Group recently released a major update of the NIST Mass Spectral Database. The new release features major improvements in both coverage and quality. Spectra for more than 54~000 compounds were added. bringing the total to 147~198 compounds. Spectra for 1,735 commercial compounds ot special Interest were measured by Ammo at Nip ~ . Store than - ~ ~ - ---r - -A -- -- - -- ~ - - ---o---o --- - - - - --- - - - - - ~ - - - - - ---r - ---- -- - - ~ r - - - 1 ~ ()()() spectra formeriv in the main library were replaced hv hi~her-~ualitv spectra All Chemical - ~ ~ ~ ~ ~ -r ~ ~ ~- ~~ - ~ - ---~ - -a -~~ ~~~ ~ ---~~-~~ --- - I ~ ~ - ~ - ~ r -~~~ ~ ~~ - ~ ~~-~~~ ~ - -1 ~~~~-- i -r ~ ~ ~- ~~~ ~ --- Abstracts Service registry numbers were verified, and more than 4(),()()() new registry numbers were added. Annual sales continue at 2,500 units, representing one-half of the GC/MS instruments sold worldwide. The NIST Chemistry WebBook has been continuously available for the past 5 years and is now being used at a rate of 500,000 users per year (as defined by distinct Internet Protocol addresses), with 50 percent being return users. Review work on WebBook sources for ion chemistry is ongoing with partners at the University of Tennessee and in New Zealand. Future addition of information on the safety of reactive chemicals is under discussion with the Synthetic Organic Chemical Manufacturers Association, the American Association for Clinical Chemistry, and the Chemical Safety Board. The NIST automated mass spectral deconvolution and identification software (ADMIS), originally developed to facilitate the detection of chemical weapons in support of the international Chemical Weapons Treaty, is finding more applications in other large-scale analysis projects. Examples include the detection of pollution in waterways and the determination of effects on genetic changes in food, as well as anticipated additional uses in homeland security. Experimental Properties of Fluids The Experimental Properties of Fluids Group collaborates closely with the Theory and Modeling of Fluids Group to enhance the value of basic data used by industries involved in refrigeration, air condi- tioning, solvents, and natural gas technology. The group's significant accomplishments during FY 2003 include the completion and commissioning of the worlds most accurate instrument for measuring P-p-T properties, the double-sinker densimeter; measurements of additional thermophysical properties of several of the new refrigerants; and progress on the development of a physical properties database for ~ , 1 ~ 1 1 ~ 1 1 . . .. . . me. . . . . . . . . . . .. . . . . 1omc llqulds. l he panel was particularly Impressed by the group s ongoing contrlbubon to the develop- ment and dissemination of thermophysical data for refrigerants being used to displace ozone-depleting chemicals. Theory and Modeling of Fluids The Theory and Modeling of Fluids Group performs theoretical and simulation studies of the thermophysical properties of fluids and their mixtures. The group has made important advances in obtaining properties of aqueous mixtures by ah initio calculations combined with molecular simulations. The second virial coefficients of a number of gas/water systems were obtained over large temperature

160 AN ASSESSMENT OF THE NIST MEASUREMENT AND STANDARDS LABORATORIES: FY 2003 ranges with uncertainties smaller than those in the experimental data. This work is an example of the synergies possible between the unique experimental measurement capabilities and theoretical work within the division. In the past year, in collaboration with other researchers in the division, this group also obtained diffusion coefficients of salts in supercritical steam and released Version 7 of the REFPROP database. Cryogenic Technologies A recent advance is the scale-up of pulse-tube refrigerators (developed in the Cryogenic Technolo- gies Group) to large capacity that is, 500 W at 30 K from the smaller-scale 5- to 20-W applications that continue to be used across a wide spectrum of applications from radio astronomy to superconduct- ina electronics and superconducting motors. Design of this scale-up required that extensive instrumen- ~7 1 ~7 ~7 1 1 · ~ . . . . . . . . . . tahon for a test-regenerator and pulse-tube apparatus be constructed In order to conduct laboratory studies of the refrigeration losses that begin to dominate as capacity is scaled up. Loss sources noted and quantified include flow misdistribution, increased axial conduction, and gravity-induced convection, among others. This past year also saw the completion of the 11 L/h two-stage pulse-tube Neon liquefier and transfer of the system to Praxair; technology transfer with this industrial partner is ongoing. The Neon liquefier is a good example of the types of associations with the more than 29 cryogenic compa- nies that have been industrial partners of the group through consultations and CRADAs. Thermodynamics Research Center - .. . alvlslon. Significant and rapid progress has been made since the transfer of the Thermodynamics Research Center (TRC) to NIST Boulder in mid-2000. The TRC Data Entry Facility is up and running in high- quality space. An important development in the past year has been the adoption of the thermal data format standards, developed by TRC and collaborators, by a number of major journals in which primary thermodynamic data for fluids are published. The thermal data format is based on XML and greatly facilitates error-free exchange and storage of thermophysical data. These data will be used to support relevant NIST and CSTL missions. In addition to the primary data collection effort, significant re- sources have been allocated for data quality assurance for new and existing data in the TRC databases. The panel is impressed with this rapid and efficient transition and now looks forward to efforts to integrate the TRC's staff and projects with the other data collection and evaluation activities of the Membrane Science and Technology As part of a NIST Advanced Technology Program (ATP), new apparatus has been developed to continue the high-throughput study of membrane transport. This enhanced apparatus, which uses sensi- tive in-line fluorescence detectors and a fiber-optic multiplexer to provide in situ analysis of eight cells, is in the final testing and demonstration stage. The high-throughput work is relevant for efforts to measure fundamental diffusion and solubility data and to elucidate transport mechanisms. In addition, further work has been done on data measurement systems for pressure-driven membrane separations. With the completion of the ATP work the major source of funding for the Membrane Science and Technology project in recent years the panel recommends that division management carefully review whether resources remain to carry forward this project at a level above the critical mass.

CHEMICAL SCIENCE AND TECHNOLOGY LABORATORY: DIVISION REVIEWS Properties for Process Separations 161 The Properties for Process Separations project recently used its unique experimental capabilities to study the stability of high-temperature organic heat-transfer fluids at the request of the National Renew- able Energy Laboratory. These organic heat-transfer fluids, which are used in solar panel electric power generation, must be stable at temperatures to 315 °C and pressure to 4 MPa. Results to date indicate that most of the common hydrocarbon fluids examined are not stable as heat-transfer fluids in solar trough applications: other candidate fluids must be developed. A detailed study that improves the ASTM copper strip corrosion test for sulfur-based impurities in wet liquid petroleum gas (ASTM D-1838) was published and communicated to the appropriate ASTM technical committee. The project's initiative to use in-situ FTIR spectroscopy to collect vapor-liquid equilibria data, particularly on mixtures that are reactive, corrosive, or toxic, has been demonstrated this year by measurements on the test system carbon dioxide + e-butane. Program Relevance and Effectiveness The Physical and Chemical Properties Division has continued its excellent efforts to ensure that its technical programs are relevant to the needs of its customers. A variety of mechanisms are used to gather input on current and planned division activities, and suggestions and requests from external organiza- tions are particularly encouraged. Examples of events during which division personnel interact with people from other institutions include standards committee meetings, technical conferences, bench- marking and roadmapping activities, professional society meetings and committees, and trade organiza- tion events. Staff take lead roles in organizing these gatherings and often hold them at NIST, as in the case of the 15th Symposium on Thermophysical Properties (discussed below), the International Asso- ciation for the Properties of Water and Steam Annual Meeting, the Industrial Molecular Simulation Challenge, and the TRCINIST consortium. Division researchers have informative relationships with a variety of individuals (e.g., guest researchers and collaborators from industry and universities). The panel notes in particular that the balance between work with short- and long-range goals indicates that input from these mechanisms has been and will continue to be effective in helping to set priorities in project selection and continuation. The panel notes continuing cross-divisional efforts (with the Analytical Chemistry Division) to provide support for the NIST homeland security initiative through the ongoing development of mass spectral methods for the detection of biological weapons. The degree of support for this and other homeland security-related initiatives is unknown until the new Department of Homeland Security is fully organized. The relevance of division programs is constantly being renewed and refocused through the mecha- nism of base fund reprogramming, both at the division level and at the CSTL level. Examples of new program directions that were derived from this process in recent years include the creation of the Computational Chemistry Group and the addition of the Thermodynamics Research Center. As mentioned above, the division maintains excellent balance between shorter-term service-ori- ented programs and longer-term research programs. Examples of this balance include the following: research to create a mass spectrometry/mass spectroscopy and ion trap library while maintaining and releasing updates to the existing NIST mass spectral library; research on properties and equation-of- state surfaces of fluid mixtures near the critical point while updating property databases such as Version 7.0 of the NIST REFPROP database; and kinetics research on model reactions in ionic liquids while converting the NDRLINIST kinetics database for free radical reactions in solution to a Web-based and XML-oriented database.

162 AN ASSESSMENT OF THE NIST MEASUREMENT AND STANDARDS LABORATORIES: FY 2003 The programs of the Physical and Chemical Properties Division have an impact on a wide array of industries and research communities, in part by bridging the gap between research directed at the often- short-range goals of industry and the long-range, open-ended inquiries commonly pursued in universi- ties. Examples of the value and recognition of division efforts include the receipt by a staff member of the Federal Laboratory Consortium Technology Transfer Award and the notification that the NIST Chemistry WebBook was voted as the winner in the Portals and Information Hubs category of the Best Chemical Sites in a Web contest sponsored by, among others, the U.K Royal Society of Chemistry. Important products of the division are databases that scientists use to develop computational models and analytical techniques for industrial, environmental, and fundamental chemistry applications. The division is to be commended not only for gathering, evaluating, and maintaining the information neces- sarY to produce these databases but also for performing critical experiments and computations in areas . . . . . . . , ~ ~ _ O ~ ~ such as gas- and liquid-phase kinetics, thermodynamics, mass spectrometry, and fluid properties in order to provide the data and the underlying understanding that allow the division to make high-quality information readily available to technical communities. Another area in which the division's work has significant impact is international standards activi- ties, such as the efforts on research related to alternative refrigerants. Division staff are active in a number of organizations on this issue, including the International Energy Agency, International Union for Pure and Applied Chemistry, and ISO. Also, in addition to database products and committee activi- ties, the division provides unique standards and services for fluid flow under cryogenic conditions and SRMs as international standards for calorimetry and thermodynamics. The division makes strong and well-directed efforts to convey NIST results to the relevant scientific and engineering communities. It effectively utilizes basic tools such as publications and presentations; in FY 2002, 127 papers were published, primarily in peer reviewed journals; 125 presentations (53 invited) were made at scientific meetings; and staff served on 69 national and international scientific committees. The number of citations to research papers, technical reports, and books originating within the division is a potentially useful performance metric. The breadth of the Physical and Chemical Properties Division's reach into relevant communities can be seen in several other statistics. The Chemistry WebBook was visited from more than 500,000 unique Internet addresses last year (an increase of 43 percent in a year). Roughly one-half of all gas chromatography/mass spectrometry instruments sold worldwide include the Mass Spectral Database. The impact of division research is felt in a variety of ways by different research disciplines, but overall NIST plays a major role in the cross-fertilization of many fields and in integrating the results for the benefit of industrial users throughout the world. The division has been the primary organizer for the highly successful and visible Symposium on Thermophysical Properties held every 3 years in Boulder. The 15th conference in the series was held June 22-27, 2003. The symposium exemplifies the pivotal role that the division can play in bringing together researchers interested in various aspects of thermophysical properties of fluids. Division Resources As of January 2003, staffing for the Physical and Chemical Properties Division included 55 full- time permanent positions, of which 46 were for technical professionals. There were also 16 nonperma- nent or supplemental personnel, such as postdoctoral research associates and temporary or part-time workers. The congressionally allocated resources (STRS) made available to the division remain constant or are shrinking. This situation requires division management to obtain additional resources from outside

CHEMICAL SCIENCE AND TECHNOLOGY LABORATORY: DIVISION REVIEWS 163 NIST or from other internal sources or to reallocate existing resources so as to maximize the impact of the remaining programs. Either approach has the potential to affect the quality of the division's work negatively. The percentage of the division's funding received from other government agencies was 21 percent in FY 2002, a slight decrease from FY 2001. The current level is high enough to ensure that NIST work is relevant to external parties. A significant fraction (15 percent) of the current funding arises from sales of the Mass Spectral Database. About 90 percent of the revenue from these sales is returned to the division to maintain this important database. However, other divisional products are currently provided to customers free of charge over the Web these include the Chemistry WebBook and the chemical kinetics database. The panel continues to recommend that, because the information in these databases is critical to many scientists, NIST should consider imposing a user fee for access, especially since the resources to support the project are limited. Users would likely accept paying a fee in order to guarantee that the databases are current and that they provide increasingly useful features. The panel also notes that more than 95 percent of the income from sales of Standard Reference Data- bases by NIST is generated by the Physical and Chemical Properties Division. Although the division continues to sustain excellence in existing experimental and theoretical areas and because of the interest in expanding into emerging computational areas, the panel is concerned that the flat budget does not allow for sufficient new hires to renew and maintain the valuable expertise, thus precluding the division. Continuation of this flat-budget trend will result, in the not-too-distant future, in the loss of sufficient critical mass of expertise, thus precluding meaningful output of the division. The significant and continuing challenge of flat or declining overall resources has been noted at the labora- tory level in previous CSTL assessments. The panel is also concerned about the age distribution of researchers within the division; there have been relatively few recent additions of permanent staff at the entry (junior) level. The staff in Gaithersburg and Boulder are a key asset of the division. The many examples of significant individual accomplishments by staff attest to the high quality of the team of scientists gathered in support of the NIST mission. This quality was demonstrated during the past year by the election of three researchers as fellows of the International Union of Pure and Applied Chemistry. A Department of Commerce Silver Medal was also conferred on a division member. Division personnel are lead editors of two major journals (International Journal of Chemical Kinetics and International Journal of Thermophysics), editors of the Thermodynamics Research Center Thermodynamic Tables, and associate editors of 18 other publications. These awards and positions of responsibility demonstrate the high regard in which division staff are held by the scientific and industrial communities. With the recent installation of ventilation hoods and special exhaust systems, satisfactory progress has been made on facilities issues in Building 24 in Boulder. This upgrade is an excellent example of the responsiveness of division and laboratory management to panel feedback and suggestions. However, the panel believes that installation of an elevator must remain a high priority in order to meet current access standards in Building 24; division plans describe this improvement as being of the highest priority. The panel looks forward to progress on the issue in the coming year. Although adequate to support routine experimental conditions, the exhaust and ventilation systems at the Gaithersburg facilities are still an ongoing concern because of the generally poor air quality in the laboratory and office modules in all of the general-purpose laboratory facilities. The Physical and Chemical Properties Division's laboratories are not among those that will be moved to the nearly completed Advanced Measurement Laboratory, so this issue will not be resolved with the opening of the AML. In terms of capital equipment, no funding issues appear to limit the initiatives undertaken by division scientists in Gaithersburg or Boulder. In fact, generally, most of the division's range of labora- tory equipment exceeds that available in nearly all industrial and academic laboratories.

164 AN ASSESSMENT OF THE NIST MEASUREMENT AND STANDARDS LABORATORIES: FY 2003 The panel continues to look for improvement in Web access to the products produced by the division. Coordinated access to the data in the Chemistry WebBook and the TRC database, and indeed a single Web point of entry for access to all chemical data at NIST, are goals acknowledged by the division. With the growing trend away from hard-copy distribution to Web-based distribution of data, there is a need to ensure permanent accessibility by the user community. Because the Physical and Chemical Properties Division generates more than 95 percent of the sales of Standard Reference Data- bases, the division should take the lead in developing and implementing a strategic plan for NIST to ensure archiving and permanence of the Web-based data distribution systems. Because of ongoing resource pressures, the panel strongly recommends that the division address the issue of cost recovery for databases in general, possibly through a subscription mode for full access to the data via the Web or through a workable per-retrieval charging mechanism. Current division plans are to develop a proposal by the end of FY 2003 to provide access to the TRC tables via the Web on a fee basis. Finally, the panel encourages increased use of remote interaction and collaboration tools, such as Web-based audio- and videoconferencing and application sharing. These tools are now available at relatively low cost and have the potential to enhance interactions among researchers in different groups. Some additional investments in hardware and software infrastructure may be necessary for taking full advantage of these tools. Although this is a broader NIST issue, the Physical and Chemical Properties Division is the only NIST division divided between Gaithersburg and Boulder, and it thus stands to gain significant benefits from such tools. ANALYTICAL CHEMISTRY DIVISION Technical Merit The Analytical Chemistry Division (ACD) carries out the following activities: · Research concerning the qualitative and quantitative determination of chemical composition; · Development and maintenance of state-of-the-art chemical analysis capabilities; · Dissemination of tools for measurement traceability and quality assurance (such as reference materials, reference data, and other services); and · Demonstration of the international comparability of U.S. standards for chemical measurement. The division serves as the nation's reference laboratory for chemical measurements and standards to enhance U.S. industry's productivity and competitiveness, ensure equity in trade, and provide quality assurance for chemical measurements used for assessing and improving public health, safety, and the environment. The division maintains world-class metrology based on core competencies in analytical mass spectrometry, analytical separation science, atomic and molecular spectroscopy, chemical sensing technology, classical and electroanalytical methods, gas metrology, nuclear analytical methods, and microanalytical technologies. These core competencies reside in five groups: Spectrochemical Methods, Organic Analytical Meth- ods, Gas Metrology and Classical Methods, Molecular Spectroscopy and Microfluidic Methods, and Nuclear Methods. The skills and knowledge derived from laboratory-based research concerning the phenomena that underpin the measurement of chemical species in a broad spectrum of matrices are continuously applied to the development and critical evaluation of measurement methods of known accuracy and uncertainty. The five primary research groups collaborate in a number of high-priority

CHEMICAL SCIENCE AND TECHNOLOGY LABORATORY: DIVISION REVIEWS 165 program areas, including reference methods and standards for clinical diagnostics; measurement stan- dards for forensics and homeland security; measurement methods and standards for nutrients, contami- nants, and adulterants in foods; environmental measurements and standards; methods and standards for advanced materials characterization; methods and standards for commodities characterization; and mi- croanalytical technologies (lab-on-a-chip). The technical merit of the work within ACD has been acknowledged in a number of ways. During this past year, research in the division resulted in 147 peer-reviewed publications, up from an average of 123 per year over the previous 4 years. In addition, two members of the division staff maintained an editorial board membership and an editorship, respectively, with prestigious international journals. The Department of Commerce Bronze Medal for work in visualization methodologies for the communica- tion of complex statistical information was awarded to a division scientist. Finally, the position of the division within the national and international metrology communities is demonstrated by staff participa- tion in 136 scientific committee assignments an increase from an average of 116 per year over the previous 4 years. Discussions of current division work illustrating technical merit are presented by group in the following sections. Spectrochemical Methods Research activities of the Spectrochemical Methods Group continue to set an extremely high stan- dard, and the panel compliments this group for its diligent performance in accordance with the mission of NIST. The various programs associated with mass spectrometry, X-ray fluorescence, optical spec- trometry, and sample preparation are proceeding well, and they underscore the productive role that this group plays in creating, developing, and maintaining the SRMs that constitute 71 percent of such products produced by the division. The group has also adapted well to the demands created by new projects aligned to homeland security and the World Trade Center investigation. Furthermore, it contin- ues to show its leadership, relative to other worldwide activities, in all its areas of involvement. The Spectrochemical Methods Group has a long history of providing research and standards to support environmental measurements regulated by the Clean Water Act of 1972, the Safe Drinking Water Act of 1974, and the Clean Air Act of 1970. A new inductively coupled plasma mass spectrom- etry method for high-precision comparisons of multielement standards was designed and applied this year to support the quality assurance and proficiency testing programs conducted for the Department of Energy and the Environmental Protection Agency (EPA). This method is capable of yielding 0.2 percent uncertainty for multielement solution standards, and it was applied in the determination of five elements in 13 different mixtures analyzed in support of the EPA-proficiency testing program. Projects associated with the existence of mercury in the environment continue to deal with one of the most important regulatory concerns, and the group made measurements and certified standards across a range of projects using the recently developed method based on cold-vapor isotope-dilution inductively coupled plasma mass spectrometry. Mercury was determined in a wide variety of SRMs: urine, inorganic sediment, crude oils, pine needles, bovine blood, mussel tissue, fish tissue, and coal. In the area of air quality, the Spectrochemical Methods Group has been working with the National Institute of Occupational Safety and Health to develop a new series of SRMs: Silica on Filters. Respi- rable crystalline silica is an occupational hazard whose presence in the workplace is strictly regulated by the Occupational Safety and Health Administration. It is poorly measured by standard industrial tech- niques (X-ray diffraction, infrared, ultraviolet/visible). Thus, both the demonstration of a safe work- place and effective enforcement of regulations have been frustrated. The new SRMs have been prepared by depositing SRM 1878a, which is certified 100.00 percent + 0.21 percent crystalline alpha-quartz, on polyvinyl chloride filters.

166 Organic Analytical Methods AN ASSESSMENT OF THE NIST MEASUREMENT AND STANDARDS LABORATORIES: FY 2003 The Organic Analytical Methods Group is responsible for the publication of 44 papers in peer- reviewed journals, 5 NIST special publications, and 62 presentations at national or international scien- tific meetings, and it issued 10 SRMs. These accomplishments represent an impressive annual record, all the while maintaining high technical quality. This group is quite effective in providing advanced metrology work in its key activity areas and is highly regarded, as attested to by awards received and publications. Major group activities included measurements and standards in these areas: clinical/health, the environment, food and nutrition, forensics and homeland security, and international comparison studies. STRS activities included development in the five main areas of support based on the major group activity categories. SRM development was completed in each of the major areas: the environment, clinical/health, food and nutrition, and forensics. The clinical/health activity placed an emphasis on in vitro diagnostics with its completion of several SRMs. Recent research activities in organic mass spectrometry have focused on the development and critical evaluation of new approaches to the quantitative determination of biomolecules (e.g., proteins) in biological matrices. The recent acquisition of a liquid chromatography capability with tandem mass spectrometry (LC/MS/MS) system and a matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometer has significantly increased the group's capacity for the determination of trace-level analyses of health, nutritional, forensic, and environmental importance, as well as for structural studies of natural products. Recent efforts have been directed toward the development and critical evaluation of reference methods for trooping I (a new marker of myocardial infarction), thyroxin and triiodothreonine (thyroid function), cortisol (a marker for endocrine function), speciated iron (ane- mia and hemochromatosis), homocysteine (a risk factor for myocardial infarction), folio acid (an essen- tial nutrient that reduces the risks of heart disease and neural tube defects), and prostate-specific antigen for prostate cancer. A particularly timely project currently under way is the development of an ephedrine SRM for both tablet and drink-additive matrices. The group currently maintains the National Biomonitoring Specimen Bank at two locations, the NIST Gaithersburg campus and the Hollings Marine Laboratory in Charleston, South Carolina. At present, the primary specimen banking activities involve tissues collected from marine mammals throughout the United States, including Alaska, and seabird eggs collected from seabird colonies in Alaska. There are now 2,087 marine mammal tissue specimens banked in the National Biomonitoring Specimen Bank, representing 737 individual animals and 34 species, and 188 seabird eggs from 3 species. These banked specimens represent a resource that has the potential for addressing future issues of marine environmental quality and ecosystem changes through retrospective analyses. . .. . . Gas Metrology and Classical Methods The Gas Metrology and Classical Methods Group is composed of a staff of 17. During the past year, 12 gas mixture standards, 7 conductivity solution standards, 1 anion solution standard, 3 pH materials, and a sodium oxalate reductometric standard were completed. In addition, 42 gas mixture standards were recertified for various clients. The group also worked with five specialty gas companies to develop 35 batches of NIST-Traceable Reference Materials. The more than 1,000 individual gas cylinders comprised by these 35 NTRM batches will be used to produce approximately 100,000 NIST-traceable gas standards for end users worldwide. This work, completed over the preceding calendar year, repre- sents excellent productivity and quality for a technical group of this size.

CHEMICAL SCIENCE AND TECHNOLOGY LABORATORY: DIVISION REVIEWS 167 In work of the Classical Methods team, pH is being ascertained with an uncertainty of 0.0015 to 0.002 pH units using a NIST Harned Cell. This current work has improved NIST primary pH metrology and seeks to relate pH measurement across national laboratories worldwide. Other work includes the development of an absolute conductivity cell for pure water. Improved analytical tools for real-time measurement of trace-level vapors in the atmosphere are critical for the evaluation of new technologies for reducing hazardous industrial emissions. Toward this end, the group is critically evaluating the capabilities of Fourier Transform microwave spectroscopy for real-time sensing applications. The high spectral resolution and high sensitivity of Fourier transform microwave spectroscopy suggest that the technique can provide unambiguous identification of vapor- phase analyses. The original goal of this project was to address the needs of the automobile industry to identify and quantify trace levels of oxygenates in exhaust emissions. Success in this work will also affect many other critical applications, including the detection of chemical warfare agents. Molecular Spectroscopy and Microfluidic Methods The Molecular Spectroscopy and Microfluidic Methods Group conducts research on the metrology of molecular spectroscopy; develops standards for the calibration, validation, and performance of instru- ments for measuring molecular spectra; and conducts research on microfluidic devices, methods, and applications for chemical analysis, including studies of materials and material properties affecting the flow of liquids in microchannels and the use of microchannel and other electrophoretic methods for forensic and toxicological applications and standards. The group is also responsible for the development and certification of optical transmittance and wavelength standards in the ultraviolet (UV), visible (VIS), and near-infrared (JR) spectral regions; Raman intensity correction standards; and fluorescence wavelength and intensity standards. Finally, the group works with users and manufacturers of analytical instruments to assess and measure the performance of analytical methods and to determine and address existing and future needs for analytical instrument standards ranging from device calibration and instru- ment performance through specifications for remote device control and data interchange. This group continues to demonstrate energy, innovation, and exceptional collaborative efforts with other sections and groups at NIST and with institutions and agencies outside NIST. The microfluidics team is particularly active in collaborative efforts and continues to recruit young, promising talent. The program relevance associated with this group's work is exemplified by its certification or recertification of nearly 70 solid absorbance filter SRMs and 202 optical filter sets. Continuing measurements were made on a number of other filter sets. In addition, nearly 250 units of SRM 2034 (holmium oxide UV-VIS wavelength standard) were certified and delivered to the Standard Reference Materials Program. These products are used across a wide spectrum of industry and fulfill an essential requirement. This year the microfluidics projects resulted in 11 publications, 4 patent applications, and 10 talks and posters. Funding for this area has come from the microscale analytical laboratory's competence award, an ATP intramural grant, a Single Molecule Manipulation and Measurement competence award, and STRS. This program area maintains collaborations with the Process Measurements Division, the Biotechnology Division, the Optical Technology Division, and the Semiconductor Electronics Division. The group continues to attract National Research Council postdoctoral research associates, adding one more this year to bring the group total to four. In the new competence area of Single Molecule Manipulation and Measurement, several solid accomplishments were achieved. Microchips were developed for the handling of water in fluorocarbon emulsions using optical tweezers; also, protocols were developed for wet chemical bonding of PDMS (polydimethylsiloxane) to PDMS and PDMS to glass. Other protocols developed included those for the

168 AN ASSESSMENT OF THE NIST MEASUREMENT AND STANDARDS LABORATORIES: FY 2003 production of ultrathin laminated chips with integral capillary ports for high-pressure, low-dead-volume applications, and for a filled loop injector for two-phase fluid systems. The group continued to study the parameters that affect flow in plastic microchannel devices. This past year, major progress was made in applying UV-laser ablation for fabricating microdevices, for studying parameters important to the postmachining properties of microdevices, and for carrying out both physical and chemical modifica- tions to the surfaces of microdevices. There seems little doubt that these studies will have a profound impact on the understanding of microfluidic design in micromachined systems in the future. Nuclear Methods Research in the Nuclear Methods Group focuses on the science that supports the identification and quantification of chemical species by nuclear analytical techniques. Current laboratory research activi- ties involve a range of nuclear analytical techniques, including instrumental and radiochemical neutron activation analysis (INAA and RNAA), prompt gamma activation analysis (PGAA), and neutron depth profiling (NDP). In addition, the group is developing further analytical applications of neutron focusing technology. The measurement capabilities within this group provide an excellent complement to those in the Spectrochemical Methods Group, as nuclear analytical methods depend on characteristics of the nucleus of the atom rather than on those of the electron shells, and therefore are insensitive to the chemical state of the analyte (i.e., matrix effects). In addition, the nuclear methods are generally nonde- structive and do not require sample dissolution, thus providing an independent assay. NDP and focused beam PGAA provide unique capabilities for the NIST facility in terms of location, sensitive analysis, and elemental mapping. To develop SRMs for microanalysis, the group has applied new INAA procedures to study the homogeneity of SRMs at small sample sizes. Many analytical techniques used in industry and academia rely on the analysis of very small samples (e.g., 1 log), typically in the solid (undissolved) form. Unfortunately, most SRMs are certified with minimum sample sizes of 100 to 500 ma, and they are therefore unsuitable for use as control materials for these techniques unless additional information is made available. Taking advantage of the sensitivity and nondestructive properties of INAA, the use of this technique for homogeneity studies of small samples has been evaluated and implemented for the determination of sampling characteristics for a number of environmental SRMs. The small analytical uncertainty associated with the INAA measurements allows extraction of the variability due to material inhomogeneity from the observed total variability within a given set of measurements. A good deal of this past year's effort has coincidentally involved materials of interest in advanced energy systems. A method has been developed and an apparatus built to produce titanium (and other metal) SRMs of known hydrogen concentration on the scale of a few kilograms. After preparation, the hydrogen concentration is verified by cold-neutron PGAA and gravimetry. This apparatus has also been used to prepare standards for the neutron-tomographic nondestructive analysis of turbine blades at McClellan Air Force Base. Current experiments of interest at the NDP instrument include the measurement of lithium concen- tration and distribution in thin films being studied for battery applications, studies of boron mobility in tungsten with the Army Research Laboratory, studies of shallow-doped boron content in silicon in conjunction with Advanced Micro Devices, the study of lithium distribution in lithium niobate, and the measurement of nitrogen in layers such as TiN and GaN. As a recent example, NDP has been used to measure nitrogen distributions in GaN/GaAs bilayers with Corning. This material is a base material for the construction of devices such as blue, light-emitting lasers. The nitrogen concentration is a crucial parameter for establishing the device characteristics. Nitrogen concentrations of MnN/ScN have been

CHEMICAL SCIENCE AND TECHNOLOGY LABORATORY: DIVISION REVIEWS 169 determined in conjunction with scientists from the NIST Center for Neutron Research and Ohio Univer- sity. MnN is a metallic antiferromagnetic material that can be used with ferromagnetic semiconductors to make spintronic devices for data storage systems. In addition to the collaborations highlighted above, staff in the Nuclear Methods Group have also worked on a number of high-priority projects with more than 20 other "outside clients" as part of their responsibility for supporting the NIST Center for Neutron Research National Users' Facility. Many of the current PGAA collaborations involve determining hydrogen in a wide variety of materials for different applications. For example, the group is currently collaborating with Jefferson Laboratory to monitor the hydrogen content of niobium that was used in the construction of the accelerator for the Spallation Neutron Source at Oak Ridge National Laboratory. PGAA has also been used to determine the hydrogen content of carbon nanotubes (a potential hydrogen storage material) and to study hydrogen uptake by solid proton conductors of formula BaPr~_xYxO3 for fuel cell applications. Other measure- ments made at the PGAA facility this year include H. S. Ca, and K in Nations, which have potential use as membranes in electrochemical separations and in fuel cells. Program Relevance and Effectiveness The issue of identity and differentiation is an important one for the Analytical Chemistry Division. Among the ever-expanding number and complexity of sensors and measurement devices throughout the nation, one unique capability of this division is not duplicated anywhere in the United States. This is the critical function of developing SRMs and concurrent technologies that provide exacting performance for highly repeatable, accurate, and reproducible measurements. The objective of the division is not preeminence in research to develop new measurement technologies, but rather the perfection of these technologies using specialized analytical metrology expertise. The expertise of the division should be applied to improve newer technologies into accurate, traceable, and reproducible measurements. These functions clearly differentiate the essential value of the Analytical Chemistry Division over other national laboratories, industrial research, and university skill sets. Increased requirements for quality of systems documentation for trade and effective decision mak- ing regarding the health and safety of the U.S. population have increased the need for demonstrating traceability to NIST measurements and standards and establishing a more formal means for document- ing measurement comparability with standards laboratories of other nations and/or regions. SRMs are certified reference materials issued under the National Institute of Standards and Technology trademark that are well characterized using state-of-the-art measurement methods and/or technologies for chemical composition and/or physical properties. Traditionally, SRMs have been the primary tools that NIST provides to the user community for achieving chemical measurement quality assurance and traceability to national standards. The division provides traceability of chemical measurements used in programs of national and international importance through SRMs, NIST-Traceable Reference Materials (NTRMs), measurement quality assurance programs in critical areas, and comparisons of NIST chemical measurement capabili- ties and standards with those of other National Metrology Institutes. Examples demonstrating program relevance and effectiveness follow. The NTRM program was created to partially address the problem of increasing requirements for reference materials with a well-defined linkage to national standards. An NTRM is a commercially produced reference material with a well-defined traceability linkage to existing NIST standards for chemical measurements. This traceability linkage is established via criteria and protocols defined by NIST and tailored to meet the needs of the metrology community to be served. The NTRM concept was

170 AN ASSESSMENT OF THE NIST MEASUREMENT AND STANDARDS LABORATORIES: FY 2003 implemented initially in the gas standards area to allow NIST to respond to increasing demands for high- quality reference materials needed to implement the emissions-trading provisions of the Clean Air Act of 1970 (while facing the fact that human and financial resources have not been increasing at NIST). The program has been highly successful. Since its inception, 12 specialty gas companies have worked with NIST to certify more than 9,000 NTRM cylinders of gas mixtures that have been used to produce more than 500,000 NIST-traceable gas standards. A recent study conducted by RTI International estimates that the net benefits of the NTRM program projected through 2007 will be between $50 million and $63 million, with a social rate of return of about 225 percent. International agreements and decisions concerning trade and our social well-being are increasingly calling upon mutual recognition of measurements and tests between nations. The absence of such mutual recognition is considered to be a technical barrier to trade, environmental, and health-related decision making. In recent years, mutual recognition agreements have been established related to testing and calibration services and with respect to the bodies accrediting such activities. The Analytical Chemistry Division has taken a leadership role on the International Committee of Weights and Measures- Consultative Committee on the Quantity of Material (CCQM) and the Chemical Metrology Working Group of the Inter-American System for Metrology (SIM) in order to ensure the effective, fair, and metrologically sound implementation of this mutual recognition agreement. Division staff members are leading various activities within CCQM and chairing the Organic Analysis Working Group. During the past 5 years, 53 comparison studies have been conducted under the auspices of the CCQM. The Analytical Chemistry Division has participated in 46 of these, serving as pilot laboratory in 18. An additional 36 studies are planned to be conducted over the next 3 years, and NIST has committed to pilot 9 of them. Providing chemical measurement quality assurance services in support of other federal and state government agency programs (on a cost-reimbursable basis) continues to be an important part of the division's measurement service delivery portfolio. During the past year, the Analytical Chemistry Division was involved in 25 projects with 11 federal and state government agencies. The division also had technical interactions that involved laboratory research and measurement activities with more than 20 professional organizations and societies, including the American Industry/Government Emissions Research (AIGER) consortium, American Association for Clinical Chemistry, American Society for Testing and Materials, Certified Reference Materials Manufacturers Association, National Food Proces- sors Association, National Council on Clinical Chemistry, and the National Environmental Laboratory Accreditation Council. Specific details concerning many of these interactions are provided below. Other high-priority efforts are directed at the detection of various poison agents in food, water, or air that might be used less for mass destruction and more for mass terror. Thus, the ongoing efforts to benchmark the detection of trace elements and the characterization of "natural" levels of elements in the environment, body fluids, and in our foods take on increased relevance. The division has added new certified values for Cd and Hg in the blood SRM 966 at concentrations of a few tens of parts per trillion and has completed analyses for a suite of toxic elements in the urine SRM 2670a at levels as low as 5 parts per trillion. NIST works with other government agencies, professional organizations, the private sector, and the international community through the recently formed Joint Committee on Traceability in Laboratory Medicine to prioritize measurement and standards needs. In addition to the clinical measurement reliability and cost issues that have driven measurement and standards for the clinical diagnostic markers project over the past 20 years, a very significant commerce and competitiveness issue has recently emerged the European Directive 98/79/EC on in vitro diagnos- tic (IVD) medical devices. By December 2003, manufacturers must declare that any new IVD product to

CHEMICAL SCIENCE AND TECHNOLOGY LABORATORY: DIVISION REVIEWS 171 be sold within the European Union complies with all the "essential requirements" of this directive. One of these requirements is that IVD products be traceable to "standards of the highest order" for ex- ample, nationally and/or internationally recognized reference methods and/or certified reference materi- als. At present, IVD devices are used in clinical laboratories to measure more than 300 different chemical or biochemical species. Reference methods and/or materials exist for about 30 of these. Approximately 60 percent of the IVD products currently on the European market are imported from the United States. Excluding home diagnostics, the overall worldwide IVD market is an approximately $20 billion market. Over the next decade, driven by the availability of new sensor-based measurement technologies, more and more clinical testing will be done outside the traditional clinical laboratory. The annual U.S. market alone for this new form of clinical measurements, called point-of-care testing (POCT), is cur- rently a billion-dollar market, growing at an annual rate of 10 percent. POCT is expected to be used extensively in the home as part of a self-care trend, which is currently experiencing a 70 percent growth rate. Published studies have concluded that POCT provides at least the same level of diagnostic value as centralized testing, but at half the cost. The standards infrastructure that has supported clinical chemistry for the past two decades must adapt to support POCT. Collaborative efforts need to be established among national standards laboratories, IVD manufacturers, and others in the medical professional community to develop appropriate technologies and nonbiohazardous standards to facilitate the provi- sion of data for medical decision making that are accurate and traceable to national/international stan- dards. NIST leadership in developing traceable POCT standards will help ensure continued U.S. domi- nance of the worldwide IVD market and foster more affordable health care both at home and abroad. The main directive to the Gas Metrology team is to produce universally available large-volume traceable mixtures. The primary standards are actually prepared at the NIST facilities in Gaithersburg. The requirements for new standards are determined based on inputs from the U.S. EPA, automobile manufacturers, specialty gas manufacturers, the AIGER consortium, and others. The team seeks to respond to regulatory and industry needs while maintaining world-class excellence in gas metrology. In response to AIGER's request, low-level NO (nitrogen monoxide) in nitrogen mixtures was provided. Specialized techniques were developed to condition aluminum cylinders to make them capable of holding such a mixture at stable conditions for extended periods. The team continues to interact with industry and regulatory groups, such as the California Air Resource Board and the EPA, in efforts to provide accurate standards for stack gas and automobile emissions measurements. The team is looking for industrial partners to work with in producing low-volume standards, which do not require SRM status. It seeks to be responsive to customer needs while managing the effort with limited resources. The Gas Metrology and Classical Methods Group has continued its collaboration with the EPA and the remote-sensing community in the development of a quantitative database of IR spectra for the calibration of IR-based technology used for real-time monitoring of airborne chemical contaminants along plant boundaries and within plant facilities. The spectra are being prepared using NIST primary gas standards. These standards have been critically evaluated at NIST and intercompared internation- ally. The use of SRD-79 to establish the traceability of open-path IR measurements will be required in the update of EPA method TO-16. SRD-79 currently has data for 40 compounds. The group also continues to support U.S. industry through the development and dissemination of high-priority reference materials on the basis of input from organizations such as the AIGER consortium and ASTM. Over the past 2 years, two new low-concentration nitric oxide gas SRMs have been developed. These SRMs are needed by the automotive industry in the development of new cars and to meet new regulations in California. These standards are also required by industry to meet new regula- tions covering stack gas emissions. These gas SRMs, one at 0.5 ppm (SRM 2737) and one at 1.0 ppm

72 AN ASSESSMENT OF THE NIST MEASUREMENT AND STANDARDS LABORATORIES: FY 2003 (SRM 2738), will be available for sale late in FY 2003. They are the result of an active collaboration between NIST and the AIGER consortium, which donated the candidate gas mixtures for the SRM. This work also involved collaboration with the Scott Specialty Gases Company to develop the technology used in passivating the cylinders. Interactive activities of the Molecular Spectrometry and Microfluidic Methods Group during the past year included measurements for the SIM intercomparison of holmium oxide solutions for the completed UVIVIS wavelength standards. Report preparation is under way. The report of the similar North American Metrology Organization study was published in Analytical Chemistry, and the results were used to establish new uncertainty values for the wavelength assignments of SRM 2034, Holmium Oxide Solution. To this end, it has been proposed that the spectrum of holmium oxide may be useful as an "intrinsic" standard a standard whose purity can be assessed inherently and whose wavelength "peak" values at given spectral slit widths can be certified independently and published as standard reference data. Therefore, a given artifact, independent of source, can be accurately assessed and, if found suitable, can be utilized as a standard. To substantiate this concept, it is necessary to assess the extent of the international agreement on the wavelength assignments for holmium oxide solutions. Accordingly, this group has begun a holmium oxide wavelength intercomparison with several NMIs around the world. If this concept proves correct, the wavelength values as a function of spectral slit width will be published as a Standard Reference Database. The Molecular Spectroscopy and Microfluidic Methods Group continues to provide statistics and data representation studies for the FBI, the NIST Office of Law Enforcement Standards, and other agencies investigating the use of DNA methods of forensic analysis. In close collaboration with the CSTL Biotechnology Division, significant progress has been made on three projects: the Armed Forces DNA Identification Laboratory-sponsored study of DNA extractability from archival media was com- pleted and the final report published; data entry and validation for the OLES-sponsored Mixed Stain Study #3 interlaboratory challenge exercise has been completed; and database and quality assurance procedures have been (and are being) developed for the Biotechnology Division's Y-STR databank, sponsored by the National Institute of Justice. Division Resources The Analytical Chemistry Division had approximately 90 scientists, technicians, and administra- tive/clerical support staff as of January 2003. The division has an annual budget of about $15 million, of which about $6 million supports programs for other federal and state government agencies and/or U.S. industry on a cost-reimbursable basis. Most of the funding sources have been relatively constant over the FY 1998-2003 period, with the STRS base funding increasing at a reasonable rate. The greatest variability over the past few years has been in the working capital fund derived from the SRM program. Over the past 4 years, there has been a steady decrease in personnel, specifically in the permanent and term professional categories. Unlike in previous years, a formal reduction in force (RIP) was undertaken this year based on budgetary concerns; the positions of four permanent professionals and one technician were eliminated. RIFs in scientific personnel have a particularly profound effect in this division, which has a very high service load with regard to the SRM program and international activities. It should be stated that part of the budget pressure experienced by this division is a direct conse- quence of needing to place priorities on the purchases of modern instrumentation that had long been delayed. For example, as pointed out in last year's assessment report, the lack of an inductively coupled plasma mass spectrometry system having collision cell capabilities was a glaring shortcoming. This and

CHEMICAL SCIENCE AND TECHNOLOGY LABORATORY: DIVISION REVIEWS 173 other purchases were made this year, at the partial expense of personnel. While these purchases are key to the performance of the division, the situation of having to choose between personnel and the tools necessary to carry out the mission of the division is disturbing. The successful operation of the division should be of concern at all levels of NIST, as the potential impact on U.S. industry is enormous. Given the financial difficulties of the past year, and particularly considering the RIF, the mood of the staff present at the skip-session (with no management present) was better than expected. Clearly there was a feeling of having to continue to do more with less. The staff members are extremely positive as suggested in their comments regarding the opportunities and the working environment at NIST, but they do express concern about the growing difficulty in replacing equipment or maintaining the scien- tific leadership position that they have come to expect. International cooperation was felt by staff to be beneficial; however, some commented that competition with other NMIs is not all positive: "Our interaction has been more of form or politically oriented than scientific results-oriented." It was felt by staff members that the division, while highly touted in CSTL and NIST reports, did not receive in-kind recognition internally through financial support of the programs. In short, they felt that the division as a whole was not valued, as exhibited through underrepresentation in exploratory research funding and from its being the sole division experiencing a RIF during the year. Interestingly, they did understand that division-level decisions regarding personnel and instrumentation purchases were not independent of one another. There was also concern expressed about a shortage of staff to maintain the SRM programs that generate significant revenue for NIST. Many comments were made relative to the leader- ship and communication skills of group leaders. As in previous years, communication relative to the budgeting process was noted as a shortcoming. On the other hand, the methods of setting priorities did seem to be well elucidated by the division leadership. In general, though, the vast majority of the staff in attendance at the skip-level session indicated that NIST and the Analytical Chemistry Division are very good places to work. The panel is concerned over the potential loss of expertise in some technical areas: in glass mixing, cutting, and polishing with the high precision required for SRMs and in precision machining for SRM quality fixtures. It is the panel's understanding that glasswork is contracted to former NIST employees, now retired, with some 70-plus combined years of NIST glasswork experience relative to SRMs. There is not a sufficient effort to replace this expertise with younger trainees. Secondly, the precise machine shops must operate in a nonsubsidized manner, placing pressure on the future existence of this function and expertise within NIST. With the world-class skill levels required in the manufacturing of quality SRMs, neglect of these functions could seriously jeopardize future SRM quality or costs of production. These important support services are considered to be of vital interest to CSTL as a whole. Recommendations Given the critical positioning of the Analytical Chemistry Division as the primary laboratory for the development and certification of an appreciable fraction of the NIST SRM portfolio, it is imperative that the division maintain the highest quality of personnel and instrumentation available in the United States. As demonstrated through the division's international activities, its participation and capabilities are crucial to the competitiveness of U.S. industries. The program directed at in vitro diagnostics is an excellent example. The RIF this year reflects strains on the organization in terms of making decisions between keeping highly skilled employees and maintaining state-of-the-art capabilities in supporting instrumentation. Clearly, given the charter of the division, this either/or situation cannot be tolerated, as both productivity and quality will suffer. The laboratory is encouraged to evaluate the real costs of SRM development and recertification, keeping in mind that both of these activities are de facto more expen-

74 AN ASSESSMENT OF THE NIST MEASUREMENT AND STANDARDS LABORATORIES: FY 2003 sive in terms of personnel and instrumentation costs than is reflected in the current SRM pricing and cost reimbursement. As an example of pricing disparities, a comparison of the cost of a NIST aluminum alloy SRM and a commercial aluminum Certified Reference Material (CRM) product reveals that the SRM costs approximately one-half the price of the commercial CRM. Clearly, this does not reflect the quality of SRMs and the supporting infrastructure required to maintain world leadership in standard materials. It is further suggested that unlike the situation with the current structure of the working fund, such projects have a nominal surcharge that is assessed specifically for instrument purchases that can in fact be accessed at the front end of projects (if needed). The division should begin to plan for major personnel changes in the Nuclear Methods Group. While there is no apparent immediate need in this area, it is clear from the demographics of that group that the vast majority of its scientists might take retirement over a limited time frame. Plans should be made for training potential replacement scientists as well as for developing new leadership within the group. Given the highly specialized nature of this group, there is not expected to be a large, young, talent pool, so the challenge will be great. The direction of standards development and basic research naturally evolves over time. In many respects, the success of the microfluidics effort in the Molecular Spectroscopy and Microfluidic Meth- ods Group has resulted in the creation of a very strong subgroup that is reasonably distinct from the remainder of the program. In fact, this subgroup addresses a long-standing shortcoming in the area of microanalytics. Clearly, the impact of micro-total analysis systems as its own subdiscipline within analytical chemistry is felt in many industrial sectors and is worthy of more serious attention by NIST in general, and not only through aspects of microfluidics. Perhaps a realignment of the groups in terms of elemental/inorganic analysis, organic analysis, molecular spectrometry, gas metrology and classical methods, and a new microanalytics group, may make sense. A microanalytics group would in many respects contain aspects of the other groups, but such a change would allow a focus specifically on analytical systems (i.e., a systems approach) and reference materials as they pertain to the ever-broaden- ing scope of micro-total analysis systems. The participation of division staff in international comparison activities is seen as a vital function. At present, staff limitations could eventually begin to place limits on the necessary activities. In addition to the time required to perform comparisons, report generation and travel also place demands on time and other resources. Finally, efforts are also required in the mentoring of staff of other NMIs not having the skill sets of the division scientists. To recoup these costs requires some specific mechanism other than the standard operating budget, which does not account for these activities in terms of personnel time and other direct costs. The activities related to homeland security are progressing well. Other opportunities may exist, in collaboration with the Transportation and Security Administration (TSA) possibly in the areas of methodology standardization, performance assessment, and reference material development. It may be that TSA is performing such services in-house, but these activities would certainly be appropriate for and well performed by the Analytical Chemistry Division. Such opportunities should be investigated.