Patrick G. Grant

Elemental compositions of comet 81P/Wild 2 samples collected by Stardust

We measured the elemental compositions of material from 23 particles in aerogel and from residue in seven craters in aluminum foil that was collected during passage of the Stardust spacecraft through the coma of comet 81P/Wild 2. These particles are chemically heterogeneous at the largest size scale analyzed (∼180 ng). The mean elemental composition of this Wild 2 material is consistent with the CI meteorite composition, which is thought to represent the bulk composition of the solar system, for the elements Mg, Si, Mn, Fe, and Ni to 35%, and for Ca and Ti to 60%. The elements Cu, Zn, and Ga appear enriched in this Wild 2 material, which suggests that the CI meteorites may not represent the solar system composition for these moderately volatile minor elements.

The Use of STIM and PESA to Measure Profiles of Aerosol Mass and Hydrogen Content, Respectively, across Mylar Rotating Drums Impactor Samples

A method has been developed for measuring profiles of aerosol mass on thin (480 w g/cm 2 ) Apiezon-L coated Mylar films employed in rotating drum aerosol impactor samplers using the ion beam analysis technique scanning transmission ion microscopy (STIM). The greased Mylar films are excellent impaction substrates and possess excellent uniformity in projected density, making them an ideal substrate for STIM analysis. The uniformity in projected density of a film enables STIM with a 3 MeV proton beam to produce profiles of aerosol mass with an accuracy of better than 90% and a mass sensitivity approaching 10 w g/cm 2 . Further, we have extended proton elastic scattering analysis (PESA) to the same films, achieving measurement of an organic surrogate. Although the films contain ∼ 20 w g/cm 2 hydrogen, the spatial uniformity in film hydrogen content enables PESA with a 3 MeV proton beam to produce profiles of hydrogen arising solely from the aerosols with an accuracy to within - 1 w g/cm 2 and a mass sensitivity of ∼ 1 w g/cm 2 . These measurements when combined with synchrotron-x-ray fluorescence (S-XRF) measurements on the same film allow mass closure, sum of species versus measured mass, a key quality assurance protocol, to be approached. All 3 techniques were applied to very fine and ultra-fine particles collected in Fresno, CA, November, 2000 by slotted DRUM samplers. Temporal resolution in the resulting profiles was h 6 h. The dramatic changes in composition versus size and time, and new types of elemental correlations unseen in PM 2.5 filters, will be major assets in correlating aerosols and health impacts, visibility degradation, and the effects of aerosols on climate.

Analysis of aerosols from the World Trade Center collapse site, New York, October 2 to October 30, 2001

The collapse of the World Trade Center (WTC) buildings #2 (South Tower), #1 (North Tower), and #7 created an enormous collapse pile which emitted intense plumes of acrid smoke and dust until roughly mid-December, when the last spontaneous surface fire occurred. We collected particles by size (8 modes, ≈12 to 0.09 micrometers diameter) and time (typical resolution of 1 to 3 h) from October 2 until late December at the EML 201 Varick Street site roughly 1.8 km NNE of the collapse site and 50 m above ground level. Here we show some of the 70,000 mass and elemental data from the time period October 2 through October 30. Identification of a WTC collapse pile source for aerosols seen at the receptor site were based upon the simultaneous presence of finely powdered concrete, gypsum, and glass with intense very fine combustion mode mass episodes concurrent with winds from the southwest quadrant. The results, derived from seven independent beam-based analytical techniques, showed that while PM10 and PM2.5 24 h values rarely, if ever, violated federal air quality standards, WTC-derived plumes swept over lower Manhattan Island, resulting in intense aerosol impacts of duration a few hours at any one site. The WTC plume resembled in many ways those seen from municipal waste incinerators and high temperatures processes in coal-fired power plants. The size fractions above 1 micrometer contained finely powdered concrete, gypsum, and glass, with sootlike coatings and anthropogenic metals, but little asbestos. Composition in the very fine size range (0.26 > Dp > 0.09 μm) was dominated by sulfuric acid and organic matter, including polycyclic aromatic hydrocarbons (PAHs) and their derivatives, and glasslike silicon-containing aerosols. Many metals were seen in this mode, most, but not all, at low concentrations. The concentrations of very fine silicon, sulfur, and many metals, as well as coarse anthropogenic metals, decreased markedly during October, probably in association with the cooling of the collapse piles. Values of very fine elements seen in May, 2002 at the WTC site were only a few percent of October values.

Analysis of lichen thin sections by PIXE and STIM using a proton microprobe

Abstract In order to better understand the distribution pattern of mineral elements in lichen tissues, thin sections (15 μm) of the foliose, vagrant soil lichen Xanthoparmelia chlorochroa were examined using proton microprobe Particle induced X-ray emission (PIXE). This technique was used to make two-dimensional scans, with 5 μm resolution, across tissue cross sections of the test species. Element maps for Si, P, S, Cl, K, Ca, Ti, Mn, Fe, Cu, Zn, and As have been prepared. Several elements are strongly localized in the element maps. PIXE data are complimented with STIM, light micrographs, and SEM images. Preliminary data suggest that nuclear microprobe techniques may be useful in elucidating element absorption and transport mechanisms in lichens.

Characterization of mycobiont adaptations in the foliose lichen Xanthoparmelia chlorochroa (Parmeliaceae).

A cross section of the vagrant soil lichen Xanthoparmelia chlorochroa was analyzed using proton microprobe PIXE. Data were used to generate quantitative, two-dimensional element distribution maps for Al, Si, P, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, As, and Sr. Element maps show differential element partitioning between the stratified layers of the thallus. These data document transfer of inorganic nutrients across the thallus to the algal layer. Inorganic particle entrapment was also evident in the element maps. Dense accumulations of calcium oxalate at the junction of the medulla and the algal layer on the order of 10% by dry mass were discovered. Scanning electron microscopy and thermogravimetric analyses were used to characterize the calcium oxalate region. These data provide evidence for possible functional roles of the calcium oxalate layer, including regulation of water and light. Data also provide support for a mutualistic interpretation of the lichen association.

Elemental composition of human semen is associated with motility and genomic sperm defects among older men

BACKGROUND Older men tend to have poorer semen quality and are generally at higher risks for infertility and abnormal reproductive outcomes. METHODS We employed proton-induced X-ray emission (PIXE, 3 MeV proton beam) to investigate the concentrations of zinc, copper, calcium, sulfur, chlorine, potassium, titanium, iron and nickel in washed sperm and seminal plasma from non-smoking groups of 10 older men (65-80 years old) and 10 younger men (22-28 years old) who were concurrently assayed for sperm function and genomicly defective sperm. RESULTS The older group showed elevated zinc, copper and calcium in sperm and elevated sulfur in seminal plasma compared with the younger men. The older group also showed reduced motility as well as increased sperm DNA fragmentation, achondroplasia mutations, DNA strand breaks and chromosomal aberrations. Sperm calcium and copper were positively associated with sperm DNA fragmentation (P < 0.03). Seminal sulfur was positively associated with sperm DNA fragmentation and chromosomal aberrations (P < 0.04), and negatively associated with sperm motility (P < 0.05). Sperm calcium was negatively associated with sperm motility, independent of male age (P = 0.01). CONCLUSIONS We identified major differences in elemental concentrations between sperm and seminal plasma and that higher sperm copper, sulfur and calcium are quantitatively associated with poorer semen quality and increased frequencies of genomic sperm defects.

Attomole quantitation of protein separations with accelerator mass spectrometry.

Quantification of specific proteins depends on separation by chromatography or electrophoresis followed by chemical detection schemes such as staining and fluorophore adhesion. Chemical exchange of short‐lived isotopes, particularly sulfur, is also prevalent despite the inconveniences of counting radioactivity. Physical methods based on isotopic and elemental analyses offer highly sensitive protein quantitation that has linear response over wide dynamic ranges and is independent of protein conformation. Accelerator mass spectrometry quantifies long‐lived isotopes such as 14C to sub‐attomole sensitivity. We quantified protein interactions with small molecules such as toxins, vitamins, and natural biochemicals at precisions of 1–5%. Micro‐proton‐induced X‐ray emission quantifies elemental abundances in separated metalloprotein samples to nanogram amounts and is capable of quantifying phopsphorylated loci in gels. Accelerator‐based quantitation is a possible tool for quantifying the genome translation into proteome.

The stand-alone microprobe at Livermore

Lawrence Livermore National Laboratory (LLNL) and Sandia National Laboratories/California have jointly constructed a new stand-alone microprobe facility. Although the facility was built to develop a method to rapidly locate and determine elemental concentrations of micron scale particulates on various media using PIXE, the facility has found numerous applications in biology and materials science. The facility is located at LLNL and uses a General Ionex Corporation Model 358 duoplasmatron negative ion source, a National Electrostatics Corporation 5SDH-2 tandem accelerator, and an Oxford triplet lens. Features of the system include complete computer control of the beam transport using LabVIEW TM for Macintosh, computer controlled beam collimating and divergence limiting slits, automated sample positioning to micron resolution, and video optics for beam positioning and sample observation. Data collection is accomplished with the simultaneous use of as many as four EG&G Ortec IGLET-X TM X-Ray detectors, digital amplifiers made by X-Ray Instruments and Associates (XIA), and LabVIEW TM for Macintosh acquisition software.

Non-DNA Methods for Biological Signatures

Publisher Summary This chapter focuses on the methods that can determine chemical or structural features of biological agent particles that are signatures of particular methods of growth and post-growth processing (often referred to as “weaponization”). The detection of these signatures in a sample of a bio-weapon (BW) agent can aid the attribution by indicating: (1) the level of sophistication of the producer, (2) the access to particular types of agent weaponization information, (3) the likelihood that the material could be or has been produced at a significant scale, (4) and by providing essential sample matching data for ascertaining a putative relationship with other samples obtained in other venues. An example of the use of biologicals in forensic science is DNA, amplied by the Polymerase Chain Reaction (PCR) technique, legally admissible in courtas evidence. DNA evidence is successfully used in the court to convict or clear people of crimes because each persons DNA is unique. High-resolution techniques are being applied to investigations; such as Environmental scanning electron microscopy (ESEM) is used for taking high-resolution images under hydrated conditions; this avoids any artifacts associated with the critical point drying process that is required under normal Scanning Electron Microscopy (SEM) operations. ESEM is also equipped with Energy Dispersive X-ray (EDX) microanalysis and Backscatter capabilities. SEM is a standard “workhorse” technique for characterizing particulate samples, found in many laboratories worldwide. It provides excellent imaging of the surfaces of agent particles and other material in a sample, and is used for identifying likely agent particles for analysis by other instruments. When combined with EDX, the elemental composition of the material in the imaged region can be determined. These techniques continue to signature libraries of correlations between analyses and growth and processing conditions of growth, it will be necessary to develop an information system which combines types of data to determine unique signatures.

Assessment of Proton Microbeam Analysis of 11B for Quantitative Microdistribution Analysis of Boronated Neutron Capture Agents in Biological Tissues

Abstract Bench, G., Grant, P. G., Ueda, D. L., Autry-Conwell, S. A., Hou, Y. and Boggan, J. E. Assessment of Proton Microbeam Analysis of 11B for Quantitative Microdistribution Analysis of Boronated Neutron Capture Agents in Biological Tissues. Radiat. Res. 160, 667–676 (2003). The 11B(p,α)8Be* nuclear reaction was assessed for its ability to quantitatively map the in vivo subcellular distribution of boron within gliosarcomas treated with a boronated neutron capture therapy agent. Intracranial 9L gliosarcomas were produced in Fischer 344 rats. Fourteen days later, the majority of the rats were treated with f-boronophenylalanine and killed humanely 30 or 180 min after intravenous injection. Freeze-dried tumor cryosections were imaged using the 11B(p,α)8Be* nuclear reaction and proton microbeams obtained from the nuclear microprobe at Lawrence Livermore National Laboratory. The 11B distributions within cells could be imaged quantitatively with spatial resolutions down to 1.5 μm, minimum detection limits of 0.8 mg/kg, and acquisition times of several hours. These capabilities offer advantages over α-particle track autoradiography, electron energy loss spectroscopy, and secondary ion mass spectrometry (SIMS) for quantification of 11B in tissues. However, the spatial resolution, multi-isotope capability, and analysis times achieved with SIMS are superior to those achieved with 11B(p,α)8Be* analysis. When accuracy in quantification is crucial, the 11B(p,α)8Be* reaction is well suited for assessing the microdistribution of 11B. Otherwise, SIMS may well be better suited to image the microdistribution of boron associated with neutron capture therapy agents in biological tissues.