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.     

Etch patterns on calcareous sediment grains: petrographic evidence of marine dissolution of carbonate minerals

Scanning electron microscopy reveals that carbonate grains in sublittoral sediments in the North Sea have surfaces with a microscopic etch relief. In structurally complex skeletal grains, the relief grades into marginal corrosion zones. The etch patterns are caused by dissolution of calcium carbonate, taking place at the shallow sea floor. Carbonate phases affected are calcite, aragonite, and a spectrum of magnesian calcites.     

Crystal orientation and plate structure in echinoid skeletal units

The submicroscopic morphology of magnesian calcite skeletal units of echinoids, revealed by scanning electron microscopy, was compared with crystal orientation data obtained by x-ray methods and with macroscopic morphology. The Perischoechinoidea and the Euechinoidea differ with regard to the shapes of their trabeculae. Nearly all plates and spines are single crystals. A variety of diJfferent directional relations of c- and a-axes to the main morphological directions are found for different species; adjacent plates with identical c-axis orientation differ strongly in orientation of their a-axes. Fracture surfaces of single trabeculae show cleavage planes and zonal layers attributed to changes in secretion conditions.     

Marine Diagenesis of Shallow Marine Lime-Mud Sediments: Insights from dgrO18 and dgrC13 Data

Shallow marine lime-mud sediments of the Ste. Genevieve Formation (Mississippian), in part of the Illinois Basin, underwent at least three diagenetic changes: (i) local dolomitization in seawater or a brine, producing dolostone having average deltaC(13) of +2.5 per mille and deltaO(18) of +1.9 per mille (versus PDB-1); (ii) more usually cementation of unreplaced CaCO(3), in intrasediment seawater, yielding isotopically marine lime mudstone mainly composed of calcite, 4-micron or finer, with deltaO(18) of from -1 to +1 per mille; (iii) later partial alteration of CaCO(3), in permeable dolomitic rocks, by isotopically "lighter" waters, to calcite with an estimated deltaO(18) of -10 per mille or less. Isotope data appraised by petrographic analysis thus suggest "submarine" cementation of these carbonates in shallow marine conditions.     

Ion pairing of magnesium sulfate in seawater: determined by ultrasonic absorption

Data from ultrasonic absorption in synthetic and natural seawater can be used to calculate pairing of magnesium and sulfate ions in seawater. Calculation under the assumption that data from ion pairing in single salt solution can be applied to seawater solution results in a value of 9.2 percent for the amount of magnesium paired with sulfate and 17.5 percent for sulfate paired with magnesium.     

Pelagic sedimentation of aragonite: its geochemical significance

The relative importance of the pelagic flux of aragonite, as compared to calcite, to the deep-sea floor has been evaluated by means of a quantitative x-ray diffraction study of samples collected from sediment traps and from an unusually shallow portion of the open Atlantic Ocean (the Rio Grande Rise). The results suggest that the aragonite flux constitutes at least 12 percent of the total flux of calcium carbonate on a worldwide basis. The presence of high-magnesium calcite in several samples suggests that some of the calcareous material falling to the deep-sea floor may be derived from the long-distance transport of debris from shallow-water beenthic organisms as well as from the settling of planktonic remains. This observation supports the contention that 12 percent represents a minimum value. Aragonite and high-magnesium calcite transported laterally from shallow-water regions, upon dissolution during settling into deeper water, may contribute to the neutralization of excess anthropogenic carbon dioxide added to the oceans.     

Skeletal low-magnesium calcite in living scleractinian corals

The skeletons of living specimens of the scleractinian coral Porites lobata have been found to contain up to 46 +/- 5 percent low-magnesium calcite even though free of gross detrital inclusions and boring or encrusting organisms. The calcite crystals occur in the interior of skeletal structures, have dimensions of 20 micrometers or less, and are surrounded by typical aragonite needles. Biogenic deposition seems to be the most likely source of the calcite, although the evidence does not rule out diagenesis of metastable.     

Subaerial diagenesis of carbonate sediments: efficiency of the solution-reprecipitation process

Interaction between percolating groludwaters and aragonitic carbonate sediments within the vadose zone of the coral cap of Barbados, West Indies, results in dissolution of aragonite and concurrent reprecipitation as low-magnesium calcite. Comparison of the ratios of strontium to calcium in groundwater, aragonitic carbonate, and recrystallized calcite indicates that locally the solution-reprecipitation process is operating at an efficiency greater than 90 percent.     

Bulk chemical characteristics of dissolved organic matter in the ocean

Dissolved organic matter (DOM) is the largest reservoir of reduced carbon in the oceans. The nature of DOM is poorly understood, in part, because it has been difficult to isolate sufficient amounts of representative material for analysis. Tangential-flow ultrafiltration was shown to recover milligram amounts of >1000 daltons of DOM from seawater collected at three depths in the North Pacific Ocean. These isolates represented 22 to 33 percent of the total DOM and included essentially all colloidal material. The elemental, carbohydrate, and carbon-type (by (13)C nuclear magnetic resonance) compositions of the isolates indicated that the relative abundance of polysaccharides was high ( approximately 50 percent) in surface water and decreased to approximately 25 percent in deeper samples. Polysaccharides thus appear to be more abundant and reactive components of seawater DOM than has been recognized.     

Freezing resistance in some Antarctic fishes

Measurements of serum freezing points in three Antarctic marine fishes indicated that they do not freeze in the -1.87 degrees C seawater because their blood is isosmotic to seawater. Concentrations of sodium chloride, urea, and free amino acids in the serum accounted for only half of the freezing-point depression of the serum. A protein containing carbohydrate was isolated which accounted for 30 percent of the freezing-point depression of the serum.     

Fluoride in seawater: measurement with lanthanum fluoride electrode

Fluoride ion concentrations are quickly and easily determined in seawater by means of a fluoride-selective electrode. Samples require little pretreatment; a determination takes 15 minutes; error limits are 5 percent; equipment required is rugged, inexpensive, and motion-insensitive; and minimum demands are made on the operator.     

Mineralogic and petrologic implications of viking geochemical results from Mars: interim report

Chemical results from four samples of martian fines delivered to Viking landers 1 and 2 are remarkably similar in that they all have high iron; moderate magnesium, calcium, and sulfur; low aluminum; and apparently very low alkalies and trace elements. This composition is best interpreted as representing the weathering products of mafic igneous rocks. A mineralogic model, derived from computer mixing studies and laboratory analog preparations, suggests that Mars fines could be an intimate mixture of about 80 percent iron-rich clay, about 10 percent magnesium sulfate (kieserite?), about 5 percent carbonate (calcite), and about 5 percent iron oxides (hematite, magnetite, maghemite, goethite?). The mafic nature of the present fines (distributed globally) and their probable source rocks seems to preclude large-scale planetary differentiation of a terrestrial nature.     

Constraints on the formation of sedimentary dolomite

The experimental replacement of calcite and aragonite by dolomite under a variety of conditions indicates that dolomitization can take place in marine and lacustrine environments under two conditions: (i) low dissolved sulfate concentrations and (ii) insubstantial contemporaneous silica diagenesis. Common sites for dolomite formation are areas where the dissolved sulfate concentration is reduced by microbial sulfate reduction, through the mixing of seawater with large amounts of fresh water, or where low-sulfate alkaline lacustrine environments prevail. Even under these conditions, dolomite formation may be inhibited by the concurrent transformation of opal-A (amorphous silica) to opal-CT (disordered cristobalite and tridymite), whereas the subsequent transformation of opal-CT to quartz favors the formation of dolomite.     

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.     

UNMINERALIZED FOSSIL BACTERIA

Unmineralized bacterial cells, mostly Micrococcus sp., but including also Streptococcus sp. and Actinomyces sp., were found in enormous numbers in lake beds of the Newark Canyon Formation of Early Cretaceous age, Eureka County, Nevada. The micrococci are black, and have an average diameter about 0.5 micro. Similar black micrococci (0.4 to 0.7 micro) were found in profusion in the bottom mud of Green Lake, New York. About 80 percent of this mud consists of minute idiomorphic calcite crystals and about 20 percent of these contain enormous numbers of the black micrococci. It is suggested that the Early Cretaceous bacterial cells owe their preservation to occlusion in calcite crystals that grew in a black, bacterial mud in a meromictic lake in which part of the Newark Canyon Formation accumulated.     

Metals in estuarine sediments: factor analysis and its environmental significance

Q-mode factor analysis has been used to partition the variability of environmentally active metals in Delaware Bay sediments. Three factors, identified as a natural background source, an oceanic or seawater source, and an estuarine source, account for 96 percent of the metal variability.     

Salicornia bigelovii Torr.: An Oilseed Halophyte for Seawater Irrigation

The terrestrial halophyte, Salicornia bigelovii Torr., was evaluated as an oilseed crop for direct seawater irrigation during 6 years of field trials in an extreme coastal desert environment. Yields of seed and biomass equated or exceeded freshwater oilseed crops such as soybean and sunflower. The seed contained 26 to 33 percent oil, 31 percent protein, and was low in fiber and ash (5 to 7 percent). The oil and meal were extracted by normal milling equipment, and the oil was high in linoleic acid (73 to 75 percent) and could replace soybean oil in chicken diets. The meal had antigrowth factors, attributed to saponins, but could replace soybean meal in chicken diets amended with the saponin antagonist, cholesterol. Salicornia bigelovii appears to be a potentially valuable new oilseed crop for subtropical coastal deserts.     

Modern cyanobacterial analogs of paleozoic stromatoporoids

Recent and subfossil calcareous structures resembling cystose and subclathrate Paleozoic stromatoporoids have been discovered in a sea-linked, stratified, alkaline crater lake on Satonda Island, Indonesia. The structures are produced by mats of coccoid cyanobacteria growing along the lakeshore from the water surface down to the O(2)-H(2)S interface located at a depth of 22.8 meters. Calcification of the mats is controlled by seasonal changes in calcium carbonate supersaturation in the epilimnion. The internally complex structures are a product of two different calcification processes: (i) periodic in vivo calcification of the surficial cyanobacterial layers by low-Mg calcite, and (ii) early postmortem calcification of the cyanobacterial aggregates below the mat surface by microbially precipitated aragonite. The finding supports the idea that Paleozoic stromatoporoids represent fossilized cyanobacteria (stromatolites). It also implies that the stromatoporoid-generating epicontinental seas during the early Paleozoic may have been more alkaline and had a higher carbonate mineral supersaturation than modern seawater.     

Fluorine Is a Major Constituent of the Marine Sponge Halichondria moorei

Fluorine constitutes about 10 percent of the dry weight of the marine sponge Halichondria moorei. The fluorine occurs as potassium fluorosilicate, which is a potent anti-inflammatory agent. A closely related sponge living in the same habitat does not contain any fluorine. The habitat was found to be free of fluorine except for the small amount naturally present in seawater.     

Venting of carbon dioxide-rich fluid and hydrate formation in mid-okinawa trough backarc basin

Carbon dioxide-rich fluid bubbles, containing approximately 86 percent CO(2), 3 percent H(2)S, and 11 percent residual gas (CH(4) + H(2)), were observed to emerge from the sea floor at 1335- to 1550-m depth in the JADE hydrothermal field, mid-Okinawa Trough. Upon contact with seawater at 3.8 degrees C, gas hydrate immediately formed on the surface of the bubbles and these hydrates coalesced to form pipes standing on the sediments. Chemical composition and carbon, sulfur, and helium isotopic ratios indicate that the CO(2)-rich fluid was derived from the same magmatic source as dissolved gases in 320 degrees C hydrothermal solution emitted from a nearby black smoker chimney. The CO(2)-rich fluid phase may be separated by subsurface boiling of hydrothermal solutions or by leaching of CO(2)-rich fluid inclusion during posteruption interaction between pore water and volcanogenic sediments.