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Aquatic Geochemistry (v.4, #3-4)
Hadean Ocean Carbonate Geochemistry by John W. Morse; Fred T. Mackenzie (pp. 301-319).
Relatively soon (∼0.2 Ga) after the Earthformed, it is likely that major oceans appeared in ahot (∼100°C) reducing environment where carbondioxide was probably the dominant atmospheric gas,with PCO2, values reaching perhaps in excess of 10atm. During the Hadean Eon between 4.3 and 3.8 Ga BP,major changes in the concentration of atmosphericCO2 and associated temperature changes had aprofound influence on the carbonate geochemistry ofthe Hadean Ocean. Although no rocks are known to havesurvived prior to the Archean Eon, it is stillpossible to calculate approximate values for importantseawater parameters during the Hadean Eon based onother sources of information and reasonableassumptions about processes such as weatheringreactions.Our calculations are based on a linear temperaturechange from 100°C to 70°C and logPCO2 change from 1 to -1.5 over the Hadean Eon. Over this range in temperature and P CO2, theinfluence of T is relatively small, but changes inP CO2 result in large compositional variations inthe carbonate chemistry of Hadean seawater. In theearly Hadean, seawater pH was probably about5.8 ± ∼ 0.2, DIC may have reached close to 130 mM,and alkalinity was perhaps close to 30 mM. By thelate Hadean, seawater pH probably had changed to closeto neutral (∼6.8), and DIC and alkalinity were closerto present-day values. Even large uncertainties inNa+ + Cl-, K+ and Mg2+concentrations produce relatively small uncertaintiesin our calculated values for the carbonic acid system. However, larger uncertainties result from reasonableranges for Ca2+ concentrations and the saturationstate of Hadean seawater with respect to calcite.Our calculations support the hypothesis that acarbonate chemistry of seawater roughly similar tothat of modern oceans could have been acquired veryearly in Earth history. If seawater composition werebuffered by reactions involving carbonates andsilicates, then the composition of late Hadean-earlyArchean seawater was not vastly different from that oftoday. Thus, by the conclusion of the Hadean Eon, ifnot before, environmental conditions at the Earth's surface, including temperature and seawatercomposition, were sufficiently equable for theevolution of life, including the Archaebacteria: theextreme halophiles and thermophiles and methanogens.Contrary to the hypothesis of an early Na-bicarbonateocean, our calculations suggest the possibility thatthe early oceans of Earth were a NaCl-dominatedaqueous solution, with somewhat higher DIC andalkalinity concentrations, higher saturation state,and the possibility of lower calcium concentrations.The time course of approach of Hadean seawater to acarbonate composition closer to that of today isdifficult to predict. It is distinctly possible thatthe concentration of calcium in seawater did not reachlevels like that of modern seawater until the latePrecambrian and thus constrained the timing of the"Big Bang" of organic evolution, the emergence of theshelled invertebrates at the beginning of thePhanerozoic.
Dissolution Enthalpies of Magnesian Calcites by William D. Bischoff (pp. 321-336).
A series of synthetic and biogenicmagnesian calcites was dissolved in weak acetic acidsolutions to measure the enthalpies of dissolution at25°C. For the synthetic phases, heat releasedwas 33.5 kJ/mol for calcite, decreasing to 33 kJ/molfor a phase of 2 mol % MgCO3, and increasing to35 kJ/mol for a phase of 15 mol %. Values of excessenthalpies, ΔHxs, calculated using calciteand magnesite end-members, average about -1 kJ/mol forthe synthetic phases. Total entropies of solidsolution formation, ΔSSS, also werecalculated using available data on Gibbs free energiesof formation and these excess enthalpies. Values ofΔSSS range from -2 J/(mol-K) at 2 mol % to-5 J/(mol-K) at 15 mol % MgCO3. These negativevalues of ΔHxs and ΔSSSsuggest that some form of ordering (cation?) isobtained in the synthetic phases, and that vibrationalentropies of the solid solution are diminished incomparison to the end-members.In contrast, biogenic samples generally have positivevalues of ΔHxs, increasing from +1 kJ/molat 5 mol % to +3 kJ/mol at 20 mol % MgCO3. Mostvalues of ΔSSS are equal (within errors)to values expected from configurational enthalpyalone. Thus, in most biogenic materials cationordering probably is not obtained, and most phases aremore typical of equivalent-site solid solutions.
Keywords: magnesian calcite; enthalpy; entropy; dissolution; calorimetry; carbonates
Recrystallization of Magnesian Calcite Overgrowths on Calcite SeedsSuspended in Seawater by Jane S. Tribble; Fred T. Mackenzie (pp. 337-360).
The formation and subsequent reactions of magnesiancalcite overgrowths on calcite were investigated bymeans of closed system seeded precipitationexperiments. These experiments demonstrated that(1) thin overgrowths of magnesian calcite are precipitatedon calcite seeds suspended in seawater;(2) the solubilities of the coatings increase outward from theseed crystals as a linear function of the log ofrelative coating thickness;(3) during the period ofthese experiments (up to 5.5 months), the magnesiancalcite coatings continued to increase in thickness,but became less soluble in composition. Thestabilization reaction, referred to asrecrystallization, can be described by the followingequation:Cax Mg(1-x) CO3 + [z + y(x + z)]Ca2++ 2yHCO3- ]= (1 + y)Ca(x + z)Mg(1 - x -z)CO3 + [z + y(x + z - 1)]Mg2++ y CO2 + yH20;]4) recrystallization rate is dependent on solutionsaturation state, with a reaction order of 3.2 forartificial seawater and 4.0 for natural seawater; and(5) by the cessation of the closed system experiments,overgrowth compositions approached that of the stablecalcite (a few mol % MgCO3).Armoring of suspended carbonate particles in thesurface oceans with magnesian calcite overgrowthswould provide an effective barrier to release of theoceanic supersaturation with respect to calcite. Thicknesses of such coatings would be limited by therecrystallization rate of the magnesian calcite. Estimates based on the recrystallization ratesdetermined in this work indicate coatings on the orderof 0.02 µm in thickness could form on particles asthey sink through the mixed layer. According to thesecalculations, the total amount of carbon precipitatedannually in magnesian calcite overgrowths iscomparable to the riverine flux of dissolved carbon tothe oceans. Field observations of severalinvestigators indicate the likely presence ofmagnesian calcite coatings on planktonic particles,and provide evidence for possible recrystallization ofbiogenic magnesian particles in the marineenvironment.
Keywords: magnesian calcite; overgrowth; precipitation; recrystallization; seawater; supersaturation
Failure to Precipitate Dolomite at 25 °C fromDilute Solution Despite 1000-Fold Oversaturation after32 Years by Lynton S. Land (pp. 361-368).
Dolomite failed to precipitate despite more than1000-fold oversaturation (IAP approximately10-13.8) from dilute solution (ionic strength =0.025) at 25 °C after 32 years.
Distribution and Fluxes of Calcium Carbonatealong the Continental Margin in the Gulf of Biscay by Roland Wollast; Lei Chou (pp. 369-393).
Compositions of major components in suspended matter,collected by centrifugation, in situ pumping andsediment traps, in the Gulf of Biscay during the OMEXproject were determined and compared. The resultsshow a strong and rapid decrease in the concentrationof biogenic fraction in the upper 200 m of the watercolumn which may be attributed to the preferentialremoval of this component due to the production offaecal pellets and to the formation of marine snow. Concurrent decrease with depth of the organic andinorganic carbon contents demonstrate the importanceof the respiration of organic matter and thedissolution of calcium carbonate in the oceanic carboncycling. Lithogenic and carbonate fluxes across thecontinental slope in the Goban Spur area wereevaluated based on sediment trap records. The rate ofproduction of calcium carbonate in the surface waters(100 g CaCO3 m-2y-1), deduced from theprimary production measurements, is much largercompared to the fluxes of this component observed inthe sediment traps (5–21 g CaCO3 m-2y-1)and to its rate of burial (9–31 gCaCO3 m-2y-1). It strongly suggeststhe occurrence of carbonate dissolution, even inwaters oversaturated with respect to the mineral phaseconsidered. This is likely to be associated with therespiration of organic matter within the faecalpellets, or at the surface of biogenic calcite oraragonite
Keywords: carbonate dissolution; suspended matter; particulate organic matter; inorganic carbon cycle; vertical fluxes; lateral transport; sediment traps; Gulf of Biscay
Carbon-Nitrogen-Phosphorus Cyclingin Tomales Bay, California by S. V. Smith; J. T. Hollibaugh (pp. 395-402).
Tomales Bay, California, has been the site oflong-term study of carbon-nitrogen-phospho-rus fluxes in the coastal zone. It has also one of severalcoastal sites being used for comparison of C-N-Pbiogeochemical fluxes. The site releases phosphorusand consumes dissolved nitrogen. It also producesdissolved inorganic carbon, mostly as elevatedalkalinity. The overall interpretation placed on thebiogeochemical fluxes is as follows. The system is netheterotrophic; that is, it consumes more organicmatter than it produces. A pathway of consumption thatis of particular importance to the nitrogen cycle isdenitrification. The combination of net heterotrophyand denitrification is the simultaneous release ofdissolved inorganic phosphorus and the uptake ofdissolved inorganic nitrogen. Much of the dissolvedinorganic carbon released during the net heterotrophyis bound in alkalinity, apparently the result ofsulfate reduction.Because this work can be traced by to the trainingthat one of the authors (SVS) received from KeithChave, it is appropriate to present a summary of theTomales Bay research in memory of Keith.
The Multiple Sources and Patterns of Methane inNorth Sea Waters by Gregor Rehder; Robin S. Keir; Erwin Suess; Thomas Pohlmann (pp. 403-427).
The methane concentration in the atmosphere andsurface water was surveyed along 58° N acrossthe North Sea. In addition, the vertical methanedistribution in the water column was determined at sixstations along the transect. The methane contents ofthe surface water as well as in the water column wereextremely inhomogeneous. Input by freshwater fromriver discharge and injection of methane from thesediment were both observed. The survey continued fromthe western side of the North Sea to the Elbe Riverestuary. The Elbe River appears to have low methaneconcentrations compared to other European rivers, itsaverage input into the North Sea is estimated to be70 nmol s-1 of methane. Near 58° N,1°40' E, an abandoned drill site releases about 25 % ofthe North Sea's emission of methane to the atmosphere.The advective methane transport induced by watercirculation was assessed for May 16, 1994, using a 3-DNorth Sea circulation model. For the period of thissurvey, the North Sea's source strength foratmospheric methane is estimated using in situwind velocities. In comparison to the advectivetransport by the water circulation, the gas flux tothe atmosphere appears to be the dominant sink ofNorth Sea methane. This flux is estimated to bebetween 1500 · 106 mol a-1 and 3100 ·106mol a-1, depending on the relationbetween wind speed and gas transfer velocity.
Keywords: methane; trace gases; North Sea; air-sea exchange
The Cold Carbonate Connection Between Mono Lake, Californiaand the Bransfield Strait, Antarctica by Michael J. Whiticar; Erwin Suess (pp. 429-454).
Ikaite is a rare form of carbonate – calciumcarbonate hexahydrate (CaCO3·6H2O) and isthe precursor to thinolites. Metastable 'ikaite'crystals, discovered in unconsolidated marinesediments in the King George Basin in the BransfieldStrait, Antarctica, are related to diageneticremineralization reactions of organic matter. StableC, O, and H-isotopes track the response of ikaitecrystals, during growth, to changing interstitialfluid conditions as a result of bacterial sulphatereduction and methanogenesis. Ikaites form inpreference over calcite or aragonite at the prevailingsurface sediment conditions of -1.6 °C and 200bar in the King George Basin.The calcareous tufa towers of the terrestrial,hypersaline Mono Lake of northern California areCaCO3-precipitates formed by the influx ofsubmerged springs of calcium-rich freshwaters enteringthe alkaline lake (ΣCO2 = 0.5 m, pH =9.8). Under current climatic conditions the mineralcalcite precipitates, but during the colder Tiogaglacial period of Late Wisconsian age (12,000 to 9,000years BP), and possibly present day during the winterseason, the monoclinic calcium carbonate hexahydrate(ikaite) was the dominant phase formed. Thesepaleo-ikaites have since recrystallized to form thecalcitic pseudomorph 'thinolites'. They are foundelsewhere in recent and ancient sediments of polarregions, e.g., as 'glendonites'. The environmentaloccurrence of ikaites and their pseudomorphs deem themas potential paleoclimatic indicators of coldenvironments. The larger crystals are typicallyrestricted to colder, deeper organic-rich sediments orin moderately evaporitic basins. In these cases, theikaite formation and decomposition may be influencedby additives such as phosphate or amino acids.
Biomineralization in Agglutinating Foraminifera: An Analytical SEM Investigation of External Wall Composition in Three Small Test Forms by Miriam A Bertram; James P Cowen (pp. 455-468).
The walls of many deep-sea foraminiferal tests containabiogenic and biogenic, precipitated and agglutinated,components. Both environmental and genetic factorscan contribute to the great diversity in test form andcomposition in benthic foraminifera. Yet, smallspecimen size and the remoteness of the deep-seaenvironment have limited our ability to describe therelative influence of these biological and chemicalfactors. The use of fossilized foraminiferal tests aspaleo-indicators requires that we understand thecontrols on test composition. Test wall morphologyand composition were examined inforaminifera that colonized experimental substratesdeployed on a seamount in the central North Pacific. Three types of agglutinated forms were identified. Atriserial (Eggerella-like) and two-chambered(Hyperammina-like) form contained a Ca-rich(CaCO3) precipitate and the chamber walls of anencrusting two-chambered form was Ba-rich(BaSO4). We discuss the composition of thesebiologically precipitated minerals in the context ofthe environmental conditions during the life of theseforaminifera.
Keywords: iron phosphorous calcite barite cement
Relationship of Water Chemistry to Serum ThyroidHormones in Captive Sharks with Goitres by Gerald L. Crow; Marlin J. Atkinson; Benny Ron; Shannon Atkinson; Arleene D. K. Skillman; George T. F. Wong (pp. 469-480).
Captive whitetip reef sharks, Triaenodon obesus,at Sea Life Park (SLP) Hawaii, Waimanalo, Hawaii develop goitre, whereas, T. obesus at the Waikiki Aquarium (WAQ), Honolulu,Hawaii do not develop goitre. To determine theeffects of natural concentrations of iodine on thereduction of goitre, two sharks from SLP with goitrewere placed in an enclosed coastal lagoon with naturalseawater. Using ultrasound measurements the twogoitres were initially 11.4 cm and 14.6 cm in depthand after 3 months decreased to 4.7 cm and 5.7 cm. Radioimmunoassay analysis of the thyroid hormoneT3 sera concentrations were initially 0.22 ng/mland 0.33 ng/ml and increased to 1.84 ng/ml after beingplaced in the lagoon. Sera T4 were initially0.93 ng/ml and 0.99 ng/ml and increased dramaticallyto 17 ng/ml and 56 ng/ml. Over the six month samplingperiod, two resident sharks in the lagoon with normalthyroids had sera T3 concentrations from 0.89ng/ml to 1.1 ng/ml, and sera T4 concentrationsfrom 3.1 ng/ml to 7.9 ng/ml. The hypothyroidcondition in the SLP goitred-sharks is likely linkedto the low environmental iodide (<0.005 μM), andhigh nitrate (111 μM) of SLP water. The WAQwell-water facility was characterized by anoxic waterwith high iodide (0.60 μM), total iodine (1.90μM), and typical nitrate (24.6 μM)concentrations of interstitial groundwater. Thedifference of iodide concentration of SLP and WAQ tankwater (<0.005 μM versus 0.60 μM) wasdirectly related to the hydrogeology of the well-watersources. To avoid goitre in marine aquarium systems,we recommend maintaining iodide concentrations of atleast 0.15 μM.
Keywords: Triaenodon obesus; whitetip reef shark; goitre; thyroid gland; thyroid hormones; serum T3; serum T4; iodide; iodate; iodine; saltwater well chemistry