Magnesium interaction with the surface of calcite in seawater

Magnesian calcite overgrowth containing 4 (+/- 2) mole percent magnesium carbonate forms on calcite exposed to natural seawater near the ocean surface. This magnesian calcite is approximately 30 percent less soluble in seawater than pure calcite. The formation of the magnesian calcite of reduced solubility may have a major influence on calcite accumulation in deep sea sediments.     

Phylum ectoprocta, order cheilostomata: microprobe analysis of calcium, magnesium, strontium, and phosphorus in skeletons

Calcium, magnesium, and strontium occur in approximately constant ratios in traverses through skeletal walls of a single mineralogy (either calcite or aragonite). Skeletal walls of more than one mineralogy have the magnesium-rich layer (calcite) surrounding the living chamber and the strontium-rich layer (aragonite) on the outside. In contrast, phosphorus may be present in greater or lesser amounts in different parts of the same calcite skeletal wall. Aragonitic crystallites appear oriented roughly perpendicular to skeletal walls, whereas calcitic crystallites are parallel to skeletal walls.     

The role of Mg2+ as an impurity in calcite growth

Magnesium is a key determinant in CaCO3 mineralization; however, macroscopic observations have failed to provide a clear physical understanding of how magnesium modifies carbonate growth. Atomic force microscopy was used to resolve the mechanism of calcite inhibition by magnesium through molecular-scale determination of the thermodynamic and kinetic controls of magnesium on calcite formation. Comparison of directly measured step velocities to standard impurity models demonstrated that enhanced mineral solubility through magnesium incorporation inhibited calcite growth. Terrace width measurements on calcite growth spirals were consistent with a decrease in effective supersaturation due to magnesium incorporation. Ca(1-x)Mg(x)CO3 solubilities determined from microscopic observations of step dynamics can thus be linked to macroscopic measurements.     

U and sr isotopes in ground water and calcite, yucca mountain, nevada: evidence against upwelling water

Hydrogenic calcite and opaline silica deposits in fault zones at Yucca Mountain, Nevada, have created considerable public and scientific controversy because of the possible development of a high-level nuclear waste repository at this location. Strontium and uranium isotopic compositions of hydrogenic materials were used to test whether the veins could have formed by upwelling of deep-seated waters. The vein deposits are isotopically distinct from ground water in the two aquifers that underlie Yucca Mountain, indicating that the calcite could not have precipitated from ground water. The data are consistent with a surficial origin for the hydrogenic deposits.     

Seawater chemistry and early carbonate biomineralization

The first appearances of aragonite and calcite skeletons in 18 animal clades that independently evolved mineralization during the late Ediacaran through the Ordovician (approximately 550 to 444 million years ago) correspond to intervals when seawater chemistry favored aragonite and calcite precipitation, respectively. Skeletal mineralogies rarely changed once skeletons evolved, despite subsequent changes in seawater chemistry. Thus, the selection of carbonate skeletal minerals appears to have been dictated by seawater chemistry at the time a clade first acquired its mineralized skeleton.     

Intercalation of sea urchin proteins in calcite: study of a crystalline composite material

Sea urchin skeletal elements are composed of single crystals of calcite. Unlike their synthetic counterparts, these crystals do not have well-developed cleavage and are consequently much more resistant to fracture. This phenomenon is due in part to the presence of acidic glycoproteins occluded within the crystals. By means of x-ray diffraction with synchrotron radiation, it is shown that the presence of the protein in synthetic calcite only slightly decreases the coherence length but significantly increases the angular spread of perfect domains of the crystals. In biogenic calcite, the coherence length is 1/3 to 1/4 as much as that in synthetic calcite and the angular spread is 20 to 50 times as wide. It is proposed that the presence of macromolecules concentrated at mosaic boundaries that are oblique to deavage planes is responsible for the change in fracture properties. These results may be important in the material sciences, because of the unusual nature of this material, namely, a composite based on the controlled intercalation of macromolecules inside single-crystal lattices.     

Carbonate compensation depth: relation to carbonate solubility in ocean waters

In situ calcium carbonate saturometry measurements suggest that the intermediate water masses of the central Pacific Ocean are close to saturation with resppect to both calcite and local carbonate sediment. The carbonate compensation depth, located at about 3700 meters in this area, appears to represent a depth above which waters are essentially saturated with respect to calcite and below which waters deviate toward undersaturation with respect to calcite.     

Total alignment of calcite at acidic polydiacetylene films: cooperativity at the organic-inorganic interface

Biological matrices can direct the absolute alignment of inorganic crystals such as calcite. Cooperative effects at an organic-inorganic interface resulted in similar co-alignment of calcite at polymeric Langmuir-Schaefer films of 10,12-pentacosadiynoic acid (p-PDA). The films nucleated calcite at the (012) face, and the crystals were co-aligned with respect to the polymer's conjugated backbone. At the same time, the p-PDA alkyl side chains reorganized to optimize the stereochemical fit to the calcite structure, as visualized by changes in the optical spectrum of the polymer. These results indicate the kinds of interactions that may occur in biological systems where large arrays of crystals are co-aligned.     

壳聚糖衍生物阻垢缓蚀的量子化学研究

针对线型高分子具有重复单元的结构特点,提出一种优化算法.以壳聚糖(CTS)和羧甲基壳聚糖(CM-CTS)为例,利用GaussView 6.0软件对两种分子进行了量子化学计算,对其分子结构、前线轨道能级、电子云密度、原子电荷分布、作用基团空间密度和链柔性进行分析,初步探讨了它们的阻垢缓蚀性能.计算结果表明,CTS和CM-...     

Synthetic calcareous pseudomorphs formed from siliceous microstructures

Individuals of the diatom Coscinodiscus have been treated hydrothermally in the presence of lime and carbon dioxide with the result that they have been pseudomorphed by calcite. The silica of the original diatoms has been replaced while the intricate reticulations of the alveoli have been preserved down to submicroscopic detail.     

High-magnesian calcite: leaching of magnesium in the deep sea

The high-magnesian calcite fraction of a shallow-water carbonate sand was converted to low-magnesian calcite after transport to the deep sea; strontium was also leached from the carbonate. Oxygen isotopic ratios indicate that loss of magnesium and strontium took place during recrystallization of the carbonate in the deep sea; this process did not alter textures of skeletal fragments. Previously, high-magnesian, calcite was thought only to dissolve in the deep sea.     

钙质结核的微形态及矿物学特征

土壤中的钙质结核可分为软结核、硬结核和钙质硬盘３种形态，其化学组成以ＣａＣＯ３为主，矿质全量组成的各氧化物平均含量水平的顺序为：ＣａＯ〉ＳｉＯ２〉Ａｌ２Ｏ３〉Ｆｅ２Ｏ３〉ＭｇＯ〉Ｋ２Ｏ〉Ｎａ２Ｏ〉ＴｉＯ２〉ＭｎＯ〉Ｐ２Ｏ５。但在某些软结核中，ＳｉＯ２含量仍大于ＣａＯ含量。微形态分析结果表明，软结核为碳酸盐颗粒的胶结体，常嵌埋较多的土壤基质、石英、长石等粗颗粒；硬结核多为碳酸盐和方解石的胶结体，许多     

Amino acids in the proteins from aragonite and calcite in the shells of Mytilus californianus

Hydroxylysine and hydroxyproline are absent in the calcified proteins of Mytilus. The organic matrices from the calcite layers have a consistently higher ratio of acidic to basic amino acids than the aragonitic shell units. The uncalcified shell units periostracum and outer ligament, have very few acidic residues, which may in part account for the lack of mineralization.     

Direct fabrication of large micropatterned single crystals

Micropatterning of single crystals for technological applications is a complex, multistep process. Nature provides alternative fabrication strategies, when crystals with exquisite micro-ornamentation directly develop within preorganized frameworks. We report a bio-inspired approach to growing large micropatterned single crystals. Micropatterned templates organically modified to induce the formation of metastable amorphous calcium carbonate were imprinted with calcite nucleation sites. The template-directed deposition and crystallization of the amorphous phase resulted in the fabrication of millimeter-sized single calcite crystals with sub-10-micron patterns and controlled crystallographic orientation. We suggest that in addition to regulating the shape, micropatterned frameworks act as sites for stress and impurity release during the amorphous-to-crystalline transition. The proposed mechanisms may have direct biological relevance and broad implications in materials synthesis.     

Tetravalent uranium in calcite

X-ray absorption spectroscopy and x-ray fluorescence microprobe studies of 35-million-year-old calcite from a Mississippi Valley-type zinc ore deposit indicate substitution of tetravalent uranium for divalent calcium. Thus, tetravalent uranium has a stable location in calcite deposited under reducing conditions. This result validates uranium-series dating methods (including uranium/lead dating) for ancient calcite and shows that calcite provides a sink for uranium in deep groundwater aquifers and anoxic lacustrine and marine basins.     

Polycrystalline echinoderm calcite and its fracture mechanics

Polycrystalline calcite was revealed by scanning electron microscopy of fractured skeletal ossicles of the sea star Echinaster spinulosus (Echinodermata, Asteroidea). Whisker-like calcite crystals were observed in specimens that were loaded in stress relaxation before being fractured; rapidly broken surfaces were smooth and glassy. The crystallites were 1300 angstroms wide and at least 3600 angstroms long and were packed together in lamellae. The lamellae were wound into spirals that formed the trabecular bars. All the crystallites in an ossicle appear to be aligned in the same direction. Geometric considerations indicate that the requirement for packing the crystallites smoothly may explain the high magnesium ion concentration of echinoderm calcite.     

Peptides enhance magnesium signature in calcite: insights into origins of vital effects

Studies relating the magnesium (Mg) content of calcified skeletons to temperature often report unexplained deviations from the signature expected for inorganically grown calcite. These "vital effects" are believed to have biological origins, but mechanistic bases for measured offsets remain unclear. We show that a simple hydrophilic peptide, with the same carboxyl-rich character as that of macromolecules isolated from sites of calcification, increases calcite Mg content by up to 3 mole percent. Comparisons to previous studies correlating Mg content of carbonate minerals with temperature show that the Mg enhancement due to peptides results in offsets equivalent to 7 degrees to 14 degrees C. The insights also provide a physical basis for anecdotal evidence that organic chemistry modulates the mineralization of inorganic carbonates and suggest an approach to tuning impurity levels in controlled materials synthesis.     

Trilobite Eyes: Calcified Lenses in vivo

The corneal lenses preserved in the eyes of some of the Paleozoic trilobites (Arthropoda) are constructed of calcite that is crystallographically oriented to behave like glass. The calcareous lenses are capable of forming inverted images over a large depth of field and must have been present in the living trilobites.     

冶炼厂区镉污染土壤中镉的形态分配及其影响因素

对湖北省大冶有色金属公司铜冶炼厂附近３４个不同污染程度的酸性和石灰性土壤中Ｃｄ的形态分配规律，及其影响因素进行研究。结果表明，污染土壤中Ｃｄ中的活性很高，无论是酸性土壤，还是石灰性土壤，均以Ｅｘｃｈ－Ｃｄ含量为最高。不同类型土壤中Ｃｄ形态分配规律分别为，酸性土壤：Ｅｓｃｈ－＞ＳＢＯ－＞ＷＢＯ－＞ＯｘＭｎ－；而在石灰性土壤中，则为：Ｅｘｃｈ－＞Ｃａｒｂ－＞ＷＢＯ－＞ＯｘＭｎ－。但由于碳酸钙对Ｃｄ的直接吸持和有机质对Ｃｄ吸持的增加，使Ｅｘｃｈ－分配系数明显低于酸性土壤。土壤各组分对Ｃｄ的亲和能力不同，其中以氧化锰组分对Ｃｄ的亲和能力最强，其次是碳酸钙和有机质。土壤中Ｃｄ的形态分配受一些土壤基本性状的制约，Ｅｘｃｈ－Ｃｄ的分配系数与土壤ｐＨ，氧化锰和粘粒含量密切相关；ＳＢＯ－Ｃｄ的分配系数则主要受土壤中氧化物含量和存在形态的影响。     

Calcite: rates of dissolution in a vertical profile in the central pacific

Rate of dissoluton of calcium carbonate (calcite) was determined for a vertical profile 5000 mizeters deep in the central Pacific by measuring the loss of weight of optical calcite spheres arrayed on a mooring. Waters of the Pacific are undersaturated in all but the upper several hundred meters. A sharp increase in the rate of dissolution occurs at a depth of about 3700 meters, which corresponds closely to the depth below which calcite hias been dissolved from the sediments.