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Since 1984, the U.S. Preventive Services Task Force (USPSTF) has issued recommendations to the public regarding preventive health services. The recommendations have substantially benefited public health. With the passage of the Affordable Care Act in 2010, recommendations assigned the highest ratings (A and B) must be covered by most private health insurers without consumer cost-sharing. This statutory requirement has been challenged in Braidwood Management Inc. v. Becerra, a case centered on the plaintiffs’ argument that USPSTF members are officers of the United States but were not appointed in accordance with the Appointments Clause of the Constitution. The Appointments Clause requires that principal officers of the United States must be appointed by the President and confirmed by the Senate. This article contends that members of the USPSTF are not principal officers of the United States, but instead serve as advisors to Congress in making preventive health recommendations. Congress established the coverage policy, not the USPSTF members. On this basis, the defendants should prevail in the case, but if they do not, the court should apply severability to permit the Secretary of Health and Human Services to directly oversee the USPSTF in the assignment of ratings for preventive health recommendations. The important work of the USPSTF should not be abridged.
Allophanes with SiO2/Al2O3 molar ratios from 1.38 to 1.92 were heated at temperatures up to 500°C, and the changes induced were investigated by means of infrared spectroscopy (IR) and X-ray powder diffraction (XRD). Heat treatment caused the IR absorption band near 1000 cm−1 due to Si-O stretching to shift towards higher frequencies, and the band near 450 cm−1 due to O-Si-O bending to increase markedly in intensity. These results are probably due to condensation of SiO tetrahedra, following breakdown of Si-O-Al linkages and dehydroxylation of SiOH groups. Concurrent intensity increase of the IR absorption at about 700 cm−1 suggested an increase in the amount of 4-coordinated Al in the heated materials. ‘Imogolite structures’ were decomposed progressively at higher temperatures and were almost absent at about 400°C, as indicated by the weakening and disappearance of the IR band at 348 cm−1 and of the XRD reflections at 2.25 and 1.40 Å. The XRD reflection at 3.3–3.45 Å shifted to about 3.6 Å, probably as a result of thermal condensation of the silica component. The observed thermal changes were much greater for samples with low SiO2Al2O3 ratios (1.38–1.51) than for those with high ratios (1.81–1.92), indicating a lower thermal stability for the former materials. Thus, the thermal stability of allophanes appears to be related to the content of ‘imogolite structures’ and to the polymerization status of the silica component.
Adsorption isotherms of HCN by Cu- and Ca-montmorillonites show that water present in the interlayer space decreases HCN adsorption.
For Ca-montmorillonite, i.r. spectra permit distinguishing between HCN interacting with the cations and molecules filling the interlayer space. Both types are removed upon outgassing. The residual water is not displaced by HCN.
On Cu-montmorillonite, species (presumably CN− ions) strongly held by the cations are observed in addition to adsorbed HCN molecules. The residual hydroxyls retained in the interlayer space are removed by the adsorption of HCN. These hydroxyls, either OH− or H2O, are characterized by two well defined stretching bands.
Infra-red spectra of samples heated below 200°C show that adsorbed HCN is involved in chemical reactions. For both clays, bands appear in the region characteristic of carbonyl and carboxyl groups; the production of ammonium is detected for Cu-montmorillonite. The reactions and the observed spectral features could be accounted for by the formation of formamide.
A new magnetic separation technique combines high magnetic fields, extreme gradients, and controlled retention time to separate feebly magnetic mineral contaminants from kaolin.
Extraction of pyrite, siderite, hematite, iron stained anatase, and mica by magnetic filtration of kaolin significantly upgrades brightness of many sub-marginal deposits and reduces consumption of reagents in processing.
The Tulameen coal field is part of an Eocene nonmarine basin which received extensive volcaniclastic sediments due to its location within an active magmatic arc. Bentonite partings in the coal originally consisted of glassy rhyolitic tephra with phenocrysts of sanidine, biotite, and quartz. During the initial alteration, which took place within the swamp or shortly after burial, glass was transformed to either smectite-cristobalite-clinoptilolite or to smectite-kaolinite. The formation of kaolinite depended on the degree of leaching of silica and alkalies in the swamp environment. Some beds are nearly 100% kaolinite and can be designated as tonsteins. The smectite shows no evidence of interlayering; the kaolinite is well ordered. During alteration, sodium, originally a component of the glass, was lost from the system.
A later thermal event, which affected only the southern part of the basin, metamorphosed the smectite to a regularly interstratified illite/smectite with 55% illite layers and rectorite-type superlattice (IS-type). The source of potassium was dissolution of sanidine. Vitrinite reflectance measurements of the coal suggest that the smectite was stable to 145–160°C, at which temperature it transformed to K-rectorite.
The absence of randomly interstratified intermediates, even in beds rich in potassium, suggests that the transformation of smectite to K-rectorite was controlled by a steep thermal gradient possibly resulting from local magmatism or circulating geothermal fluids.
Montmorillonite-aminocaproic acid complexes (monomer complexes) were prepared by the intercalation of 6-aminocaproic acid to various homoionic (Na+, Ca2+, Mg2+, Co2+, and Cu2+) montmorillonites. Infrared spectra of the monomer complexes indicated that the interaction between the exchangeable cations and the 6-aminocaproic acid increased in the following order: Na-, Ca-, and Mg- < Co- < Cu-montmorillonite-aminocaproic acid complex. Montmorillonite-nylon complexes (polymer complexes) were prepared by thermal treatment of the monomer complexes, which was confirmed by X-ray powder diffraction and infrared spectroscopy the results of which indicated the condensation of 6-aminocaproic acid in the interlayer space.
Thermal degradation of montmorillonite-nylon complexes was studied by thermogravimetry. It was found that the thermal stability of the polymer complexes increased in the following order: Cu- < Co- < Na- < Mg- < Ca-montmorillonite-nylon complex.
It was suggested that the difference in thermal stability depended upon the length of the polymer chain which might be influenced by the interaction between the exchangeable cations and the 6-aminocaproic acid. The activation energy for the thermal degradation of each montmorillonite-nylon complex was obtained, and the value for Cu-montmorillonite-nylon complex was smaller than that for the other cation-exchanged montmorillonite-nylon complexes.
Stable organomineral derivatives are formed by reaction of organochlorosilanes with certain phyllosilicates. Organosiloxyl functions are grafted on silanol groups present at external mineral surfaces.
Water molecules adsorbed on external mineral surfaces may cause hydrolysis of the reactant organosilicon products, with liberation of HCl. This, in turn, may react with the silicate: octahedral cations are extracted from the lattice and fresh Si-OH groups, capable of further grafting, are formed on the mineral surface.
On the other hand, when difunctional reagents such as methylvinyldichlorosilane are used and if the ratio of adsorbed water to added reactive is adequate, then polymeric species with polysiloxane chains are grafted on the mineral.
Because of its high content of silanol groups, sepiolite forms organomineral compounds having a relatively high organic matter content. With chrysotile, the amount of organic matter grafted to the silicate, is considerably smaller, but it increases appreciably if water is added to the reacting products. This is attributed to hydrolysis of the organic reactant and subsequent destruction of external “brucitic” layers by acid attack.
Investigations concerning selective sorption and fixation of K and similar cations by clay minerals and soil clays and the mechanisms of these reactions are reviewed. In particular, recent observations on selective sorption of these ions in dilute solutions by weathered micas and vermiculite in relation to the interlayer structures are discussed in detail. Also, implications of the resistance to weathering of small mica particles to cation selectivity by soils are described. Despite the increased understanding of sorption and fixation reactions, the following aspects remain unclear.
First, the mechanism of the collapse of alternate layers in vermiculite on K or Cs sorption has not been unequivocally established. Second, factors that impart stability to the central core of mica particles so that K extraction becomes progressively difficult are not known. Third, inability of Ca or Mg ions to expand interlayers of Cs-saturated vermiculite in contrast to K-saturated vermiculite is not completely understood.
X-ray diffraction and electron microscopy were employed in conjunction with core flooding experiments to investigate clay migration phenomena.
Severe water sensitivity or loss of permeability was observed in a suite of sandstones in spite of the almost total absence of montmorillonite or swelling mixed layer clays. Clay migration was found to cause total or partial plugging even in sandstones of 500 millidarcy permeability. Bacterial plugging was ruled out by prefiltering and bactericide treatments of waters.
X-ray diffraction and electron microscopy analyses were performed on the sandstones and produced effluents. The direct cause of damage was displacement of submicroscopic natural clay crystals of needle-shaped mica and hexagonal-shaped kaolinite (Rex, 1965). The mobile clays were identified as authigenic crystals that are present on the pore walls and are dislodged by changes in water chemistry combined with water movement.
Flooding sandstones with alkali metal brines “sensitized” the cores, i.e. triggered clay dispersion upon subsequent flooding with fresh water. Flooding with divalent calcium brine prevented water sensitivity and suppressed the undesirable effect of alkali metal brines. A double layer expansion effect is suggested as the dispersion mechanism.
Montmorillonite was found to be the dominant clay mineral in surface horizons of certain soils of the North Carolina Coastal Plain whereas a 2:1–2:2 intergrade clay mineral was dominant in subjacent horizons. In all soils where this clay mineral sequence was found, the surface horizon was low in pH (below 4·5) and high in organic matter content. In contrast, data from studies of other soils of this region (Weed and Nelson, 1962) show that: (1) montmorillonite occurs infrequently; (2) maximum accumulation of the 2:1–2:2 intergrade normally occurs in the surface horizon and decreases with depth in the profile; (3) organic matter contents are low; and (4) pH values are only moderately acid (pH 5–6).
It is theorized that the montmorillonite in the surface horizon of the soils studied originated by pedogenic weathering of the 2:1–2:2 intergrade clay mineral. The combined effects of low pH (below 4·5) and high organic matter content in surface horizons are believed to be the agents responsible for this mineral transformation. The protonation and solubilization (reverse of hydrolysis) of Al-polymers in the interlayer of expansible clay minerals will occur at or below pH 4·5 depending on the charge and steric effects of the interlayer. A low pH alone may cause this solubilization and thus mineral transformation, but in the soils studied the organic matter is believed to facilitate and accelerage the transformation. The intermediates of organic matter decomposition provide an acid environment, a source of protons, and a source of watersoluble mobile organic substances (principally fulvic acids) which have the ability to complex the solubilized aluminum and move it down the profile. This continuous removal of solubilized aluminum would provide for a favorable gradient for aluminum solubilization.
The drainage class or position in a catena is believed to be less important than the chemical factors in formation of montmorillonite from 2:1–2:2 intergrade, because montmorillonite is present in all drainage classes if the surface horizon is low in pH and high in organic matter.
Clay minerals in the upper 50 cm of sediment that surround the Cu- and Ni-rich manganese nodules in the North Equatorial Pacific form two fractions: terrigenous (mostly eolian) illite, chlorite, and kaolinite, and authigenic smectite. Smectite increases with depth in box cores from 26 to 39% and from 53 to 66% in the easternmost and westernmost areas respectively, and with distance seaward from the Americas from 26 to 53% in surface deposits. The change in the amount of smectite relative to other clay minerals is due to dilution by terrigenous debris; smectite probably forms at a uniform rate over much of the North Pacific deep-sea floor. The δO18 value for the smectite is +29.6‰ which suggests that it formed authigenically at a temperature characteristic of the deep-sea floor. The smectite is an Fe-rich montmorillonite that probably forms by the low-temperature chemical combination of Fe hydroxides and silica. Silica is derived from dissolution of biogenic debris, and the Fe hydroxide is from volcanic activity at the East Pacific Rise, 4000 to 5000 km to the east. Al in the authigenic montmorillonite may be derived from the dissolution of large amounts of biogenic silica or from river-derived Al that is adsorbed on Fe-Mn hydroxides in the oceans. The Fe-montmorillonite contains relatively abundant Cu, Zn, and Mn and is of possible economic importance as a source of these and other metals.
Retention of basic components of a crude oil by clay-containing reservoir sandstone was studied by flowing crude oil through cores and monitoring the concentration of bases in the effluent. Cores that were H-saturated, H-saturated then aged, and Na-saturated retained 0·82, 0·82, 0·70, and 0·20 meq base/100 g, respectively. Barium exchange capacity values were 0·86, 0·71, and 0·83 meq/100 g. Subsequent floods with water, toluene, and chloroform-acetone removed oil that had increasing concentrations of base and N, indicating that the basic fraction of crude oil was the most difficult fraction to extract from clay mineral surfaces. Retained bases were nitrogenous and the most tenaciously held bases had base/N ratios approaching unity.