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The crystallization of calcium carbonate minerals plays an integral role in the water chemistry of terrestrial ecosystems. Humic substances, which are ubiquitous in natural waters, have been shown to reduce or inhibit calcite crystal growth in experiments. The purpose of this study is to quantify and understand the kinetic effects of hydrophobic organic acids isolated from the Florida Everglades and a fulvic acid from Lake Fryxell, Antarctica, on the crystal growth of calcite (CaCO3). Highly reproducible calcite growth experiments were performed in a sealed reactor at constant pH, temperature, supersaturation (Ω = 4.5), PCO2(10−3.5atm), and ionic strength (0.1 M) with various concentrations of organic acids. Higher...
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In situ Al-silicate formation, also known as “reverse weathering,” is an important sink of many of the major and minor cations in seawater (e.g. Mg, K, and Li). However, the importance of this sink in global geochemical cycles and isotopic budgets of these elements remains poorly constrained. Here, we report on the potassium isotopic composition (41K/39K) of deep-sea sediment pore-fluids from four (Integrated) Ocean Drilling Program sites (1052, U1378, U1395 and U1403) to characterize potassium isotopic fractionation associated with the formation of authigenic Al-silicate minerals in marine sediments and its role in elevating the 41K/39K of seawater relative to bulk silicate Earth. Isotopic ratios are obtained by...
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The fate of arsenic in groundwater depends largely on its interaction with mineral surfaces. We investigated the kinetics of As(III) oxidation by aquifer materials collected from the USGS research site at Cape Cod, MA, USA, by conducting laboratory experiments. Five different solid samples with similar specific surface areas (0.6–0.9 m2 g−1) and reductively extractable iron contents (18–26 μmol m−2), but with varying total manganese contents (0.5–3.5 μmol m−2) were used. Both dissolved and adsorbed As(III) and As(V) concentrations were measured with time up to 250 h. The As(III) removal rate from solution increased with increasing solid manganese content, suggesting that manganese oxide is responsible for the oxidation...
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A suite of elements (B, Na, Mg, S, K, Ca, V, Mn, Cr, Sr, and Ba) was measured in aragonitic shells of the estuarine bivalve Corbula amurensis, the Asian clam, using the Sensitive High-Resolution Ion MicroProbe with Reverse Geometry (SHRIMP RG). Our initial intent was to explore potential geochemical proxy relationships between shell chemistry and salinity (freshwater inflow) in northern San Francisco Bay (SFB). In the course of this study we observed variations in shell trace element to calcium ([M]/Ca) ratios that could only be attributed to internal biological processes. This paper discusses the nature and sources of internal trace element variability in C. amurensis shells related to the shell organic fraction...
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Lead concentrations and isotope ratios measured in river water colloids and streambed sediment samples along 426 km of the Sacramento River, California reveal that the influence of lead from the historical mining of massive sulfide deposits in the West Shasta Cu-mining district (at the headwaters of the Sacramento River) is confined to a 60 km stretch of river immediately downstream of that mining region, whereas inputs from past leaded gasoline emissions and historical hydraulic Au-mining in the Sierra Nevadan foothills are the dominant lead sources in the remaining 370 km of the river. Binary mixing calculations suggest that more than 50% of the lead in the Sacramento River outside of the region of influence of...
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Pb2+ and Zn2+ adsorption was studied in batch experiments with material collected from a shallow, unconfined aquifer of glacial outwash sand and gravel in Falmouth, Massachusetts, USA. The aquifer solids contain primarily quartz with minor amounts of alkali feldspars and ferromagnetic minerals. Pb2+ and Zn2+ adsorption experiments with various grain size and mineral fractions of the aquifer solids showed that: 1) Zn2+ adsorption was independent of grain size, but Pb2+ was preferentially adsorbed by the <64 ??m size fraction and 2) Pb2+ adsorption decreased after removal of the paramagnetic, Fe-bearing mineral fraction, but Zn2+ adsorption was unaffected. Pb2+ and Zn2+ adsorption on mineral separates from the aquifer...
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A series of analyses were undertaken to determine a precise difference between sea-water strontium and the Eimer and Amend SrCO3 standard. A mean difference between the sea-water composite and the Eimer and Amend SrCO3 of 0.00107 ?? 0.000042 was obtained. ?? 1971.
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The Eh-pH diagrams for the equilibrium concentrations in aqueous solution at 25°C of native sulphur and all the various sulphur-containing ions and acids from which the ions are produced have been constructed for systems having a total sulphur concentration of 0.1 molar. The composite of these diagrams indicates that elemental sulphur, H2S, HS− HSO4− and SO4 are the species that predominate in the environments that might be found in nature. This indication is in agreement with the composition of all sulphur-containing minerals.
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Study of the interferences of silica and sulfate in the flame-photometric determination of calcium in thermal waters has led to the development of a method requiring no prior chemical separations. The interference effects of silica, sulfate, potassium, sodium, aluminum, and phosphate are overcome by an addition technique coupled with the use of magnesium as a releasing agent. ?? 1963.
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Clay minerals and methanogens are ubiquitous and co-exist in anoxic environments, yet it is unclear whether methanogens are able to reduce structural Fe(III) in clay minerals. In this study, the ability of methanogen Methanosarcina barkeri to reduce structural Fe(III) in iron-rich smectite (nontronite NAu-2) and the relationship between iron reduction and methanogenesis were investigated. Bioreduction experiments were conducted in growth medium using three types of substrate: H2/CO2, methanol, and acetate. Time course methane production and hydrogen consumption were measured by gas chromatography. M. barkeri was able to reduce structural Fe(III) in NAu-2 with H2/CO2 and methanol as substrate, but not with acetate....
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A 6 mm-diameter dark spherule, 15434,28, from the regolith on the Apennine Front at the Apollo 15 landing site has a homogeneous glass interior with a 200 ??m-thick rind of devitrified or crystallized melt. The rind contains abundant small fragments of Apollo 15 olivine-normative mare basalt and rare volcanic Apollo 15 green glass. The glass interior of the spherule has the chemical composition, including a high FeO content and high CaO/Al2O3, of a mare basalt. Whereas the major element and Sc, Ni, and Co abundances are similar to those of low-Ti mare basalts, the incompatible elements and Sr abundances are similar to those of high-Ti mare basalts. The relative abundance patterns of the incompatible trace elements...
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The chemistry of seawater at conditions of 350° to 500°C, 220 to 1000 bars (22 to 100 MPa) is controlled by reactions involving magnesium hydroxide sulfate (MHSH) and anhydrite. During progressive heating from 350° to 500°C at 1000 bars (100 MPa), MHSH with a ratio of 1.25 is formed via precipitation from solution and via reaction of solution with pre-existing anhydrite. During adiabatic expansion the MHSH extracts additional SO4 from seawater and converts to a stoichiometry in which . These reactions control and greatly change the concentrations of Ca, Mg, SO4 in solution and produce significant ionizable hydrogen, attaining 11.7 mmoles kg−1 at maximum conditions.
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Present day anthropogenic fluxes of some heavy metals to central Chesapeake Bay appear to be intermediate to those of the southern California coastal region and those of Narragansett Bay. The natural fluxes, however, are in general higher. On the bases of Pb-210 and Pu-239 + 240 geochronologies and of the time changes in interstitial water compositions, there is a mixing of the upper 30 or so centimeters of the sediments in the mid-Chesapeake Bay area through bioturbation by burrowing mollusks and polychaetes. Coal, coke and charcoal levels reach one percent or more by dry weight in the deposits, primarily as a consequence of coal mining operations. ?? 1978.
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This work compares and models the adsorption of selenium and other anions on a neutral to alkaline surface (amorphous iron oxyhydroxide) and an acidic surface (manganese dioxide). Selenium adsorption on these oxides is examined as a function of pH, particle concentration, oxidation state, and competing anion concentration in order to assess how these factors might influence the mobility of selenium in the environment. The data indicate that 1. 1) amorphous iron oxyhydroxide has a greater affinity for selenium than manganese dioxide, 2. 2) selenite [Se(IV)] adsorption increases with decreasing pH and increasing particle concentration and is stronger than selenate [Se(VI)] adsorption on both oxides, and 3. 3) selenate...
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The solubility of sphalerite (ZnS) was measured in KCl-HCl-H2O solutions at 300-600??C and 0.5-2.0 kbar. The silicate assemblage K-feldspar-muscovite (or andalusite)-quartz was used to buffer the solution to acid conditions, resulting in the total solubility reaction 2K+ + KAl2AlSi3O10(OH)2 + 6SiO2 + ZnS + nCl- = ZnCln(2-n) + 3KAlSi3O8 + H2S. (muscovite) (quartz) (sphalerite) (K-feldspar) A computer retrieval technique was used to derive average chloride ligand numbers for chlorozinc species at 0.25-2.0 molal total chloride. This technique mathematically solves for the average ligand number using a series of pertinent chemical relations at P and T. Mono- and di-chlorozinc species were found to predominate throughout...
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Sulfur and oxygen fluxes were quantified in the seasonally varying anoxic marine sedimentary system of Cape Lookout Bight, N.C., U.S.A. Over the three year study period, 1981-1983, the mean annual sulfate reduction rate was determined to be 18.2 ?? 1.6 moles ?? m-2 ?? y-1. This value, added to the estimate of the detrital sulfur input of 1.2 ?? 4.4 gave a total sulfur input of 19.4 ?? 4.7 moles ?? m-2 ?? y-1. The sulfide flux to the sediment-water interface, measured in anaerobic benthic chambers was 4.6 ?? 0.5 moles ?? m-2 ?? y-1, and represented 37% of the annual oxygen uptake rate of 25.2 ?? 2.8 moles ?? m-2 ?? y-1. The sulfide burial rate, determined to be 15.5 ?? 3.1 moles ?? m-2 ?? y-1, was within 5% of the...
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Hickory trees concentrate the rare-earth elements in their leaves to a phenomenal degree and may contain as much as 2300 p.p.m. of total rare earths based on the dry weight of the leaves. The average proportions of the individual elements (atomic percent of the total rare-earth elements) in the leaves are: Y 36, La 16, Ce 14, Pr 2, Nd 20, Sm 1, Eu 0.7, Gd 3, Tb 0.6, Dy 3, Ho 0.7, Er 2, Tm 0.2, Yb 1, and Lu 0.2. The similarity in the proportions of the rare-earth elements in the leaves and in the exchange complex of the soil on which the hickory trees grow indicates that the trees do not fractionate the rare earths appreciably. The variation of the rare-earth elements in the leaves and soils can be explained generally...
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If analytical errors are responsible for the scatter of points on a 230Th-234U-238U isochron diagram, the isochron should be fitted by a technique that 1. (1) weights the points according to their analytical errors and error correlations, and 2. (2) either takes into account the presence of some of the same data in two coupled XY isochrons or (equivalently) uses a single, three-dimensional XYZ isochron. A method based on maximum-likelihood estimation is presented that fulfills these requirements, and the relevant equations for errors in age and initial 234U 238U are given. Equations for estimating the necessary isotope-ratio errors and error-correlations for both alpha-spectrometric and mass-spectrometric data are...
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The solubility of amorphous silica in aqueous salt solutions at 25° to 300°C can be calculated using information on its solubility in pure water and a model in which the activity of water in the salt solution is defined to equal the effective density. pe, of “free” water in that solution. At temperatures of 100°C and above, pe closely equals the product of the density of the solution times the weight fraction of water in the solution. At 25°C, a correction parameter must be applied to pe that incorporates a term called the apparent cation hydration number, h. Because of the many assumptions and other uncertainties involved in determining values of h, by the model used here, the reported numbers are not necessarily...