Synthetic sodium bimessite, having a cation-exchange capacity (CEC) of 240 meq/100 g (cmol/kg) was transformed into Li, K, Mg, Ca, Sr, Ni, and Mn2+ cationic forms by ion exchange in an aqueous medium. Competitive adsorption studies of Ni and Ba vs. Mg showed a strong preference for Ni and Ba by bimessite. The product of Mg2+-exchange was buserite, which showed a basal spacing of 9.6 Å (22°C, relative humidity (RH) = 54%), which on drying at 105°C under vacuum collapsed to 7 Å. Of the cation- saturated bimessites with 7-Å basal spacing, only Li-, Na-, Mg-, and Ca-bimessites showed cation exchange.

Heating bimessite saturated with cations other than K produced a disordered phase between 200° and 400°C, which transformed to well-crystallized phases at 600°C. K-exchanged bimessite did not transform to a disordered phase; rather a topotactic transformation to cryptomelane was observed. Generally the larger cations, K, Ba, and Sr, gave rise to hollandite-type structures. Mn- and Ni-bimessite transformed to bixbyite-type products, and Mg-bimessite (buserite) transformed to a hausmannite-type product. Li-bimessite transformed to cryptomelane and at higher temperature converted to hausmannite. The hollandite-type products retained the morphology of the parent bimessite. The mineralogy of final products were controlled by the saturating cation. Products obtained by heating natural bimessite were similar to those obtained by heating bimessite saturated with transition elements.

Using Garfield, Washington, nontronite as the model mineral system, methods and apparatus were developed to prepare reduced suspensions in citrate-bicarbonate-dithionite (CBD) solution. These techniques were effective in removing excess, undesired solutes from reduced suspensions while maintaining a high Fe2+ content. They also enabled the preparation of dried, reduced films preferentially oriented with respect to the crystallographic c-axis. Supernatant solutions were collected and analyzed for Fe, Al, and Si, from which the extent of dissolution of the clay as a result of CBD treatment was assessed. Results indicated that very little Fe and Si were released to solution, but as much as about 8% of the total Al was solubilized. The highest levels of Al in solution were observed in CB treatments without dithionite.

Investigations were conducted to determine the hydrothermal transformations of synthetic birnessite exchanged with different metal ions. Autoclaving in a Teflon-lined stainless steel pressure vessel at 155°C for 24 hr of Mg-, Ca-, La-, and Co-saturated birnessite yielded manganese minerals having 10-Å X-ray powder diffraction (XRD) spacings. The autoclaved Mg-birnessite yielded a mineral identical to natural todorokite in its infrared (IR) spectrum and XRD patterns. High-resolution transmission electron microscopy (HRTEM) provided images having 10-, 12.5-, 15-, and 20-Å wide fringes indicating heterogeneous channel widths in the crystallographic a direction, and IR spectroscopy produced bands at 757, 635, 552, 515, 460, and 435 cm-1, confirming the product obtained by autoclaving Mg-birnessite to be todorokite. Prolonged autoclaving of Mg-birnessite yielded manganite (γ-MnOOH) as a by-product; manganite did not form when the autoclaving time was shortened to 8 hr. Also, when Ca-saturated samples were autoclaved, the product gave d-values of 10 Å, but the XRD lines were broad and heterogeneity of the channel sizes was evident from HRTEM observations. The Ca-derivative had an IR spectrum similar to that of natural todorokite. Images showing 10-Å lattice fringes were observed by HRTEM for the Ni-saturated sample, which also produced an XRD pattern similar to that of the Mg-saturated sample. Co- and Lasaturated samples did not form todorokite, although HRTEM of La-saturated samples indicated some 10-Å lattice fringes that were unstable in the electron beam. Birnessite saturated with Na, K, NH4, Cs, Ba, or Mn(II) gave products having 7-Å spacings upon autoclaving.

The feasibility of transforming palygorskite from two localities to smectite hydrothermally at temperatures ranging from 22° to 160°C was investigated in a series of laboratory experiments, in which alkalinity was maintained in the pH range of 11.4 to 12 by adding NaOH. The smectite formed was characterized by chemical, spectroscopic, and electron microscopic techniques. Smectite formed rapidly at > 100°C; the transformation was slow, however, at 22°C. The introduction of MgCO3 accelerated the alteration process, but changes in alkalinity at pH > 12 and the difference in elemental composition of the palygorskite samples did not significantly affect the alteration. A pressure of one atmosphere and a temperature of 22°C were sufficient for some transformation to occur within a few months, provided the alkalinity was maintained close to pH 12. X-ray powder diffraction characterization of the product indicated a smectite, and infrared spectroscopy indicated saponite. The alteration to smectite was appreciable even at room temperature, which suggests that the reaction can take place without any external heating.

Na-saturated bimessite was synthesized by oxidizing an alkaline MnCl2 solution with gaseous O2. Transmission electron microscopy (TEM) showed no morphological change upon K-saturation of the bimessite, but selected-area diffraction (SAD) revealed structural disorder. Stepwise heating of the K-birnessite to 800°C yielded cryptomelane, as indicated by X-ray powder diffraction (XRD). Various degrees of transformation to the final cryptomelane product were observed by TEM and SAD, but not by XRD. Unaltered bimessite formed chiefly as thin, platy crystals of apparent hexagonal outline. The cryptomelane crystals that formed by heating the K-saturated bimessite were acicular. Bimessite crystals, partially transformed to cryptomelane and displaying non-integral diffraction spots, formed plates having linear striations and rods twinned at 60° to each other. These intermediate products commonly retained some of the original hexagonal appearance of the parent bimessite. Structural disorder was detected in the partially transformed crystals by SAD. TEM revealed 6.8- and 4.8-Å spacings of the (110) and (200) planes of cryptomelane, respectively. The basal planes of bimessite layers (001) appeared to correspond topotactically to the (110) plane of cryptomelane during these transformations.

The instability of palygorskite and sepiolite under soil conditions was investigated to determine if these fibrous minerals transform directly to smectite under laboratory conditions. The treatment of 100 mg (0.12 mmole) of palygorskite with 1 mmole of NaOH solution (17 ml) at 150°C for 24 hr yielded a smectite. Analcime and smectite were formed when ≥ 3 mmole of NaOH was used. The addition of ≤ 6 mmole NaOH to sepiolite destroyed it gradually. On addition of ≥ 8 mmole NaOH, sepiolite altered to an X-ray amorphous material. In the presence of Al and Si, however, it transformed to smectite and analcime. Transmission electron microscopy, cation-exchange capacity, and X-ray powder diffraction studies of the products suggest that alteration wa. (1) via solution, o. (2) by a structural reorganization wherein the basic 2:1 silicate structural units were unchanged.

Three montmorillonites and a nontronite were reduced by sodium dithionite to obtain different amounts of Fe2+ in their octahedral sites. The mass ratio of water to clay, mw/mc was determined as a function of Fe2+ at several values of the swelling pressure, π. The value mwmc decreased markedly with increasing Fe2+ at each value of π for each clay. Moreover, curves of π vs. mwmc for the different clays were displaced downwards as Fe2+ increased. A straight line was obtained when In(π + 1) was plotted against 1/(mw/mc) however, at some oxidation states of three of the samples this line exhibited a sharp break at a specific value of 1/(w/mc. The slope of the line decreased for each clay as Fe2+ increased, and an increase in Fe2+ was accompanied by an increase in the cation exchange capacity. These observations are thought to be due to a collapse or partial collapse of the superimposed clay layers resulting from the increase in cation-exchange capacity.

The effect of Fe oxidation state on the surface charge (CEC) and solubility of smectites were studied using the <2-μm, Na+-saturated fraction of an Upton, Wyoming; a Czechoslovakian; and a New Zealand montmorillonite; and a Garfield, Washington, nontronite. The reduction of structural Fe3+ in the octahedral sheet of each clay produced a net increase in the negative surface charge of the clay. The observed cation-exchange capacities deviated from the linear relationship predicted by charge-deficit calculations, assuming changes only in the Fe2+/Fe3+ ratio, and reversibly followed Fe reduction according to a 2nd-degree polynomial function. The deviations suggest reversible changes in mineral structure and composition during Fe reduction.

These clays were susceptible to partial dissolution in citrate bicarbonate (CB) and citrate-bicarbonate-dithionite (CBD) solutions. Small amounts of Fe and Si dissolved as a result of Fe reduction in CBD, but affected <1% of the total clay mass except for the Czechoslovakian clay in which 2% of the clay dissolved. Although slightly more Fe dissolved than Si, no change in surface charge was noted. Almost no dissolution of these elements was detected in CB solution. In contrast, significant Al was detected in the CB solution, suggesting a heterogeneous dissolution mechanism. The CEC, however, was unchanged by the CB treatment. These results may be explained by the adsorption of hydrogen ions into the vacated Al3+ sites in the mineral structure. Dissolution seems to have been independent of the effects of Fe oxidation state on surface charge.

Submicron-sized (~3–60 nm) powders of Al-substituted magnetite were synthesized in the laboratory by precipitation methods by mixing appropriate molar volumes FeCl2, FeCl3 and AlCl3 solutions and precipitating with 20% NH4OH. Precipitates were dialyzed for 48 hr to remove excess salts and then freeze-dried. The nominal Al mole fractions [Als = Al/(Al + Fe)] in the initial precipitate ranged from 0.001 to 0.42. Portions of the resulting powders were heated sequentially in air at 400° and 500°C. Powders were examined using X-ray diffraction (XRD), transmission electron microscopy (TEM), and visible and near-IR reflectance spectroscopy. Solubilities were determined in ammonium oxalate (pH = 3) and dithionite-citrate-bicarbonate (DCB) solutions. As determined by XRD, the mineralogy of precipitated powder samples was predominantly magnetite. Powders having Als > 0.20 contained minor goethite and a poorly crystalline iron oxide phase (ferrihydrite?), and powders having Als > 0.25 also contained gibbsite. The color of the magnetites was black throughout the range of Al-substitution. Powders heated to 400°C were reddish brown; Munsell colors ranged from 5R 2/2 to 10R 3/4 for Als from 0.1–41.5%, respectively. By XRD, these powders were maghemite, but hematite was also detected by Mössbauer spectroscopy. XRD and Mössbauer data indicate powders heated to 500°C are hematite; their Munsell colors are not noticeably different from the corresponding 400°C samples. Mean crystallite dimensions (MCDs) of the magnetite powders increase with the Al mole fraction from ~10 nm for Als = 0.001% to a maximum value of 35 nm for Als = 0.15 and decrease slightly with further increasing Al substitution. Heating magnetite powders to 400°C did not change the MCDs significantly. Heating to 500°C resulted in hematites having MCDs larger than those for corresponding precursor magnetites for Als < 0.10. The opposite is true for hematites derived from magnetites having Als > 0.10. For hematite powders with Als > 0.05, MCD decreased with increasing Al-substitution. Solubilities of powders in oxalate solutions were independent of Al content and decreased in the order unheated samples (mostly magnetite) >400°C-heated samples (maghemite + hematite) >500°C-heated samples (hematite). All powders dissolved completely in DCB. The low crystallinity of the magnetite powders and the presence of ferrous iron are responsible for their relatively high solubility in oxalate solutions.

Human illness attribution is recognized as an important metric for prioritizing and informing food-safety decisions and for monitoring progress towards long-term food-safety goals. Inferences regarding the proportion of illnesses attributed to a specific commodity class are often based on analyses of datasets describing the number of outbreaks in a given year or combination of years. In many countries, the total number of pathogen-related outbreaks reported nationwide for an implicated food source is often fewer than 50 instances in a given year and the number of years for which data are available can be fewer than 10. Therefore, a high degree of uncertainty is associated with the estimated fraction of pathogen-related outbreaks attributed to a general food commodity. Although it is possible to make inferences using only data from the most recent year, this type of estimation strategy ignores the data collected in previous years. Thus, a strong argument exists for an estimator that could ‘borrow strength’ from data collected in the previous years by combining the current data with the data from previous years. While many estimators exist for combining multiple years of data, most either require more data than is currently available or lack an objective and biologically plausible theoretical basis. This study introduces an estimation strategy that progressively reduces the influence of data collected in past years in accordance with the degree of departure from a Poisson process. The methodology is applied to the estimation of the attribution fraction for Salmonella and Escherichia coli O157:H7 for common food commodities and the estimates are compared against two alternative estimators.

Bisphenol A (BPA), a monomer of polycarbonate plastics and epoxide resin, is a high-production-volume chemical implicated in asthma pathogenesis when exposure occurs to the developing fetus. However, few studies have directly examined the effect of in utero and early-life BPA exposure on the pathogenesis of asthma in adulthood. This study examines the influence of perinatal BPA exposure through maternal diet on allergen sensitization and pulmonary inflammation in adult offspring. Two weeks before mating, BALB/c dams were randomly assigned to a control diet or diets containing 50 ng, 50 μg or 50 mg BPA/kg of rodent chow. Dams remained on the assigned diet throughout gestation and lactation until postnatal day (PND) 21 when offspring were weaned onto the control diet. Twelve-week-old offspring were sensitized to ovalbumin (OVA) and subsequently challenged with aerosolized OVA. Sera, splenocytes, bronchoalveolar lavage fluid and whole lungs were harvested to assess allergen sensitization and pulmonary inflammation after OVA challenge. Serum anti-OVA IgE levels were increased two-fold in offspring exposed to 50 μg and 50 mg BPA/kg diet, compared with control animals. In addition, production of interleukin-13 and interferon-γ were increased in OVA-stimulated splenocytes recovered from BPA-exposed mice. Pulmonary inflammation, as indicated by total and differential leukocyte counts, cytokines, chemokines and pulmonary histopathology inflammatory scores, however, was either not different or was reduced in offspring exposed to BPA. Although these data suggest that perinatal BPA exposure beginning before gestation enhances allergen sensitization by increasing serum IgE and splenocyte cytokine production, a substantial impact of BPA on OVA-induced pulmonary inflammation in adulthood was not observed.

A photocrosslink between basic fibroblast growth factor (bFGF155) and a high affinity ssDNA oligonucleotide was characterized by positive ion electrospray ionization mass spectrometry (ESIMS). The DNA was a 61-mer oligonucleotide photoaptamer bearing seven bromodeoxyuridines, identified by in vitro selection. Specific photocrosslinking of the protein to the oligonucleotide was achieved by 308 nm XeCl excimer laser excitation. The crosslinked protein–nucleic acid complex was proteolyzed with trypsin. The resulting peptide crosslink was purified by PAGE, eluted, and digested by snake venom phosphodiesterase/alkaline phosphatase. Comparison of the oligonucleotide vs. the degraded peptide crosslink by high performance liquid chromatography coupled to an electrospray ionization triple quadrupole mass spectrometer showed a single ion unique to the crosslinked material. Sequencing by collision induced dissociation (MS/MS) on a triple quadrupole mass spectrometer revealed that this ion was the nonapeptide TGQYKLGSK (residues 130–138) crosslinked to a dinucleotide at Tyr133. The MS/MS spectrum indicated sequential fragmentation of the oligonucleotide to uracil covalently attached to the nonapeptide followed by fragmentation of the peptide bonds. Tyr133 is located within the heparin binding pocket, suggesting that the in vitro selection targeted this negative ion binding region of bFGF155.

We recently demonstrated that C60 and C70, as well as other fullerenes, can be deposited and accumulated on surfaces using laser ablation of graphite in an Inert gas atmosphere. After learning of the work of Krätschmer et al. indicating the presence of C60 in carbon soot, we showed that samples consisting almost exclusively of C60 and C70 can be sublimed from such soot. Vibrational Raman spectra of C60 and C70 were obtained from these samples. The C60 spectrum Is consistent with the calculated spectrum of Buckmlnsterfullerene, and the strongest three lines can be assigned on the basis of frequency and polarization. The NMR spectrum of dissolved C60 was then obtained, and found to consist of a single resonance, establishing the icosahedral symmetry of this molecule. STM images of the C60 molecules on a Au(111) crystal face show that these clusters form hexagonal arrays with an intercluster spacing of 11.0 Å and are mobile at ambient temperature. Distinctly taller species evident in the arrays are believed to be C70 clusters. Vibrational Raman and infrared spectra have also been obtained for separated C60 and C70.

The synthesis and catalytic properties of hydrogenation catalysts of the RaneyR type derived from aluminum-nickel and aluminum-molybdenum-nickel RSR alloy powders have been evaluated. Two binary aluminum-nickel alloys, RSR 588, with 50 w/o Ni corresponding to currently available RaneyR commercial alloys, and RSR 587, with 28.5 w/o Ni corresponding to the proeutectic composition which produces exclusively Al3Ni as the precursor phase, were synthesized. One ternary, RSR 589, aluminum-molybdenum-nickel alloy with a nickel and molybdenum content to correspond to a commercial promoted RaneyR alloy was prepared.

The hydrogenation catalytic activity for six organic compounds representing diverse functionalities was measured in a bench scale batch liquid slurry catalytic reaction. Each catalyst was suspended in an agitated solution of the reaction (0.8 to 5M) at 22°C under a constant hydrogen over pressure of 0.86 atmospheres. A declining pressure technique was also used as a measure of catalytic activity where the catalyst was suspended in an agitated solution of the three reactants at 80°C at an initial hydrogen pressure of four atmospheres. The reactants selected consisted of acetone, nitrobenzene, itaconic acid, butyronitrile, toluene, and dextrose. The organic functionalities hydrogenated consisted of the conversion of:

(1) Carbonyl to alcohol

(2) Nitro group to amine group

(3) Double carbon bond to a single carbon bond

(4) Nitrile group to an amine group

(5) Aromatic to a hydroaromatic ring

(6) Aldehyde to an alcohol.

RSR 587 catalyst, containing 28.5 w/o nickel, provides superior hydrogenation rates over bulk cast RaneyR nickel catalysts by factors ranging from 2 to 20 for selected reactions. Rapid solidification followed by heat treatmen0t at 850°C of Al ∼42 w/o Ni powders yielded the greatest specific catalytic activity and provides a unique enrichment path for the formation of the peritectic phase, A13Ni, and subsequently the most active skeletal nickel pore structure with the least amount of waste aluminum.