The dependence of bacterial sulfate reduction on sulfate concentration in marine sediments

The effect of dissolved sulfate concentration on the rate of bacterial sulfate reduction in marine sediment from Long Island Sound was examined using a radio-sulfur technique. The experimental results show that the rate is independent of the dissolved sulfate concentration until low levels are reached (<3 mM), and that, when interpreted using a Monod-type rate law, a saturation constant, K_s, of 1.62 ± 0.16 M results. This weak dependence implies that the dissolved sulfate exerts only a limited influence on the rate of sulfate reduction in marine sediments. Given such a weak dependence, dissolved sulfate profiles in marine sediments must resemble profiles generated by models with sulfate independent kinetics. Initially, this would suggest that currently used sulfate-independent diagenetic models are appropriate in modelling sulfate profiles. However, comparison of these models with those containing weak sulfate-dependent kinetic terms shows that there exists considerable disagreement between these models when the parameter grouping $\text{(D}{}_{\mathrm{s}}\text{k)}\text{1}\text{2}\text{/w}$ is larger than ~0.2 and smaller than ~3.0. (Here D_s is the SO^;₄ diffusion coefficient, k the organic matter decay constant and w the sediment burial velocity.) When the currently used models are corrected by employing physically meaningful boundary conditions, this divergence disappears. The modelling results, therefore, confirm the conclusion that any sulfate dependence inherent to the reduction kinetics does not appreciably affect sulfate pore water profiles, and that previous diagenetic studies using strong sulfate dependent models are erroneous.     

Changes of lead and barium with time in California off-shore basin sediments

During ancient times the natural deposition fluxes of lead which can be leached with dilute acid from sediments in Santa Barbara, Santa Monica and San Pedro basins offshore from the Los Angeles Urban complex, were about 0.7, 0.1 and 0.2 μg Pb/cm² yr respectively. Since there was little difference in biological productivity in surface waters of these basins, it is proposed that clay is a major transport vehicle for sequestered soluble lead, which then explains why the lead deposition flux within the Santa Barbara basin was so much larger compared to the other basins. The fluxes of silicate mud in the basins in ancient times were about 92, 19 and 30 mg/cm² yr in Santa Barbara, Santa Monica and San Pedro basins respectively. Today deposition fluxes of acid soluble lead within these three basins are 3- to 9-fold greater, being about 2.1, 1.1 and 1.8 μg Pb/cm² yr respectively, partly in the form of directly deposited large sewage particles, which account for none, $\text{2}\text{3}$ and $\text{3}\text{4}$ of the total industrial lead deposition fluxes in the respective basins. Concentrations of leachable lead in varve dated sediment layers increase with time and isotopic compositions of these leads change in accordance with corresponding known changes of isotopic compositions of industrial lead in the Los Angeles atmosphere. Lead remaining in acid leached sediment residues originates from igneous and clay minerals, exhibiting no change in concentration or isotopic composition since pre-industrial times.Deposition fluxes of total barium in sediments among the three basins were proportional to mass deposition fluxes before 1950 in the same manner as for lead. Afterwards, there are barium concentration maxima with time in both Santa Monica and San Pedro Basin sediments which are attributable to industrial sewage rather than to episodic erosion from barium-rich sedimentary evaporite strata exposed locally along the shore. An increase of barium concentrations in present day Santa Barbara basin sediments may reflect dispersal of barium-rich drilling mud from local drilling operations.     

Sorption of metals on humic acid

The sorption on humic acid (HA) of metals from an aqueous solution containing Hg(II). Fe(III), Pb, Cu, Al, Ni, Cr(III), Cd, Zn, Co and Mn, was investigated with special emphasis on effects of pH, metal concentration and HA concentration. The sorption efficiency tended to increase with rise in pH, decrease in metal concentration and increase in HA concentration of the equilibrating solution. At pH 2.4. the order of sorption was: Hg? Fe? Pb? CuAl ? Ni ? CrZnCdCoMn. At pH 3.7. the order was: Hg and Fe were always most readily removed, while Co and Mn were sorbed least readily. There were indications of competition for active sites (CO₂H and phenolic OH groups) on the HA between the different metals. We were unable to find correlations between the affinities of the eleven metals to sorb on HA and their atomic weights, atomic numbers, valencies, and crystal and hydrated ionic radii. The sorption of the eleven metals on the HA could be described by the equation $\text{Y =}\text{100}\text{[1 + exp ? (A + BX)]}$, where Y = % metal removed by HA; X = mgHA; and A and B are empirical constants.     

Flotation of galena. Influence of grain size,of pulp deoxygenation,and of cleaning with ammonium acetate

The flotation of < 10, 10–20, and 20–40 μm galena fractions was studied. For uncleaned galena a given collector coverage produced better floatability with increasing grain size. Nitrogen had a detrimental effect only for the < 10 μm fraction, producing at a given collector coverage a recovery smaller than that obtained with air.Galena cleaned with 400 g/l ammonium acetate had very poor floatability, although xanthate abstraction was fairly high; this confirms that strong xanthate adsorption is necessary for flotation. Formation of monothiocarbonate was small in all cases, which points to a very minor influence, if any, of this compound in the flotation process.In blank flotation tests, or for very low residual xanthate concentrations, a peak at 208 nm and a shoulder at 255 nm were observed. The former was assigned to the uncomplexed Pb²⁺ ion, and the latter was tentatively attributed to the PbOH⁺ ion.Lead in solution results from dissolution of the oxidation products of galena, as galena itself has an exceedingly low solubility. The curve for total lead in solution vs. initial xanthate concentration, had a minimum for an initial xanthate concentration of 10^?5M, the further increase in dissolved lead is attributed to formation of complexes such as PbX⁺ (X = xanthate). Dissolved lead concentrations were nearly as high for cleaned as for uncleaned galena, which indicates a high oxidation rate of the mineral.     

Biogeochemical copper anomalies on Salajar Island Indonesia

Elevated copper concentrations were detected in 20 species from the 1913 herbarium collection of W.M. Docters van Leeuwen at Utrecht. These plants had been collected from Salajar Island (near Sulawesi), Indonesia. Anomalous copper concentrations ranged from 80–600 μg/g (dry weight) in leaves of these species. Values for the same species collected outside of Salajar were invariably far lower ($\text{< 51}\text{μg/g}$) and indicated that the Salajar samples may have been growing over copper-rich substrates. The area has not yet been investigated by other geochemical methods, though extrapolation from the adjacent coast of Sulawesi of presumably similar geology indicates the possibility that the biogeochemical anomalies could be caused by copper-rich tephrites.     

Concentration of Mn and separation from Fe in sediments—I. Kinetics and stoichiometry of the reaction between birnessite and dissolved Fe(II) at 10°C

Redox reactions between Fe²⁺ in solution and Mn-oxides are proposed as a mechanism for concentration of Mn in sediments both during weathering and diagenesis in marine sediments, e.g. the formation of Mn-nodules.If such a mechanism is to be effective, then reaction rates between Fe²⁺ and Mn-oxides should be fast. The kinetics and stoichiometry of the reaction between dissolved Fe²⁺ and synthetically prepared birnessite (Mn₇O₁₃·5H₂O) were studied experimentally in the pH range 3–6.Results show a stoichiometry which at pH < 4 conforms to a simple reaction between Fe²⁺ and birnessite, releasing Mn²⁺ and Fe³⁺ to the solution. At pH > 4 FeOOH is precipitated and excess Fe²⁺ consumption compared to the theoretical stoichiometry is observed. The excess Fe²⁺ consumption is not due to a formation of a quantitative MnOOH layer but rather to adsorption.Reaction kinetics are very fast at pH < 4 and change at pH 4 to a slower mechanism. At pH > 4 the reaction is fast initially until 17% of the bimessite has dissolved and changes then to a slower stage. The later stage can be described by the equation: $\text{J = km}{}_0\text{(H}{}^{\mathrm{+}}\text{)}{}^{\mathrm{?0.45}}\text{[Fe}{}^{\mathrm{2+}}\text{]}{}^{\mathrm{\gamma }}\text{(}\text{m}\text{m}{}_0\text{)}{}^{\mathrm{\beta }}$ where J is the overall rate of Mn²⁺ release, m₀ and m the mass of birnessite at time t = 0 and t > 0, β = 6.76?0.94 pH and γ has values of 0.76 at pH 5 and 0.39 at pH 6. The rate constant k is 7.2·10^?7 moles s^?1 g^?1 (moles/1)^?0.31 at pH 5 and 9.6·10^?8 moles s^?1 g^?1 (moles/1)^0.06 at pH 6.Diffusion calculations show that the rate is controlled by surface reaction and it is tentatively proposed that the availability of vacancies in octahedral [MnO₆]sheets of the birnessite surface could be rate controlling. It is concluded that reactions between Fe(II) and birnessite, and probably other Mn-oxides, are fast enough to be important in natural environments at the earth surface.     

The solubility of noble gases in water and in NaCl brine

A direct-sampling, mass-spectrometric technique has been used to measure simultaneously the solubilities of He, Ne, Ar, Kr, and Xe in fresh water and NaCl brine (0 to 5.2 molar) from 0° to 65 °C, and at 1 atm total pressure of moist air. The argon solubility in the most concentrated brines is 4 to 7 times less than in fresh water at 65 °C and 0°C, respectively. The salt effect is parameterized using the Setschenow equation.

$\text{ln}\text{[}\text{β}{}^{\mathrm{i}}{}_{\mathrm{o}}\text{(T)}\text{β}{}^{\mathrm{i}}\text{(T)}\text{= MK}{}^{\mathrm{i}}{}_{\mathrm{M}}\text{(T)}$

where M is NaCl moiarity, βⁱ_o(T) and βⁱ(T) the Bunsen solubility coefficients for gas i in fresh water and brine, and Kⁱ_M(T) the empirical salting coefficient. Values of Kⁱ_M(T) are calculated using volumetric concentration units for noble gas and NaCl content and are independent of NaCl molarity. Below about 40°C, temperature coefficients of all Kⁱ_M are negative. The value of K^He_M is a minimum at 40°C. K^Ar_M decreases from about 0.40 at 0°C to 0.28 at 65 °C. The absolute magnitudes of the differences in salting coefficients (relative to K^Ar_M) decrease from 0° to 65°C. Over the range of conditions studied, all noble gases are salted out, and K^He_M ? K^Ne_M < K^Ar_M < K^Kr_M < K^Xe_M.From the solubility data, we calculated $\text{Δ}\text{G}{}^0{}_{\mathrm{tr}}$, $\text{Δ}\text{S}{}^0{}_{\mathrm{tr}}$, $\text{Δ}\text{H}{}^0{}_{\mathrm{tr}}$ and $\text{Δ}\text{C}{}^{\mathrm{O}}{}_{\mathrm{p,tr}}$ for the transfer of noble gases from fresh water to 1 molar NaCl solutions. At low temperatures $\text{Δ}\text{S}{}^0{}_{\mathrm{tr}}$, is positive, but decreases and becomes negative at temperatures ranging from about 25°C for He to 45°C for Xe. At low temperatures, the dissolved electrolyte apparently interferes with the formation of a cage of solvent molecules about the noble gas atom. At higher temperatures, the local environment of the gas atom in the brine appears to be slightly more ordered than in pure water, possibly reflecting the longer effective range of the ionic fields at higher temperature.The measured solubilities can be used to model noble gas partitioning in two-phase geothermal systems at low temperatures. The data can also be used to estimate the temperature and concentration dependence of the salt effect for other alkali halides. Extrapolation of the measured data is not possible due to the incompletely-characterized minima in the temperature dependence of the salting coefficients. The regularities in the data observed at low temperatures suggest relatively few high-temperature data will be required to model the behavior of noble gases in high-temperature geothermal brines.     

Light hydrocarbons in Red Sea brines and sediments

Light hydrocarbon (C₁-C₃) concentrations in the water from four Red Sea brine basins (Atlantis II, Suakin, Nereus and Valdivia Deeps) and in sediment pore waters from two of these areas (Atlantis II and Suakin Deeps) are reported. The hydrocarbon gases in the Suakin Deep brine (T = ~ 25°C, $\text{Cl}{}^{\mathrm{?}}\text{= ~ 85‰}$, $\text{CH}{}_4\text{=}\text{~ 71}\text{1}$) are apparently of biogenic origin as evidenced by $\text{C}{}_1\text{(C}{}_2\text{+ C}{}_3$) ratios of ~ 1000. Methane concentrations (6–8 μl/l) in Suakin Deep sediments are nearly equal to those in the brine, suggesting sedimentary interstitial waters may be the source of the brine and associated methane.The Atlantis II Deep has two brine layers with significantly different light hydrocarbon concentrations indicating separate sources. The upper brine (T = ~ 50°C, $\text{Cl}{}^{\mathrm{?}}\text{= ~ 73‰}$, CH₄ = ~ 155 μl/l) gas seems to be of biogenic origin [$\text{C}{}_1\text{(C}{}_2\text{+ C}{}_3\text{) = ~1100}$], whereas the lower brine (T = ~ 61°C, $\text{Cl}{}^{\mathrm{?}}\text{= ~ 155‰}$, CH₄ = ~ 120μl/l) gas is apparently of thermogenic origin [$\text{C}{}_1\text{(C}{}_2\text{+ C}{}_3\text{) = ~ 50}$]. The thermogenic gas resulting from thermal cracking of organic matter in the sedimentary column apparently migrates into the basin with the brine, whereas the biogenic gas is produced in situ or at the seawater-brine interface. Methane concentrations in Atlantis II interstitial waters underlying the lower brine are about one half brine concentrations; this difference possibly reflects the known temporal variations of hydrothermal activity in the basin.     

Uranium isotopes in rivers,estuaries and adjacent coastal sediments of western India: their weathering,transport and oceanic budget

The two major river systems on the west coast of India, Narbada and Tapti, their estuaries and the coastal Arabian sea sediments have been extensively studied for their uranium concentrations and ${}^{238}\text{U}{}^{238}\text{U}$ activity ratios.The ²³⁸U concentrations in the aqueous phase of these river systems exhibit a strong positive correlation with the sum of the major cations, σ Na + K + Mg + Ca, and with the HCO₃^? ion contents. The abundance ratio of dissolved U to the sum of the major cations in these waters is similar to their ratio in typical crustal rocks. These findings lead us to conclude that ²³⁸U is brought into the aqueous phase along with major cations and bicarbonate. The strong positive correlation between ²³⁸U and total dissolved salts for selected rivers of the world yield an annual dissolved ²³⁸U flux of 0.88 × 10¹⁰g/yr to the oceans, a value very similar to its removal rate from the oceans, 1.05 × 10¹⁰g/yr, estimated based on its correlation with HCO₃^? contents of rivers.In the estuaries, both ²³⁸U and its great-grand daughter ²³⁴U behave conservatively beyond chlorosities 0.14 g/l. These data confirm our earlier findings in other Indian estuaries. The behavior of uranium isotopes in the chlorosity zone 0.02–0.14 g/l, was studied in the Narbada estuary in some detail. The results, though not conclusive, seem to indicate a minor removal of these isotopes in this region. Reexamination of the results for the Gironde and Zaire estuaries (Martin et al., 1978a and b) also appear to confirm the conservative behavior of U isotopes in unpolluted estuaries. It is borne out from all the available data that estuaries beyond 0.14 g/l chlorosities act neither as a sink nor as a source for uranium isotopes, the behavior in the low chlorosity zones warrants further detailed investigation.A review of the uranium isotope measurements in river waters yield a discharge weighted-average ²³⁸U concentration of 0.22 μg/l with a ${}^{234}\text{U}{}^{238}\text{U}$ activity ratio of 1.20 ± 0.06ismissing. The residence time of uranium isotopes in the oceans estimated from the ²³⁸U concentration and the ${}^{234}\text{U}{}^{238}\text{U}$ A. R. of the rivers yield conflicting results; the material balance of uranium isotopes in the marine environment still remains a paradox. If the disparity between the results is real, then an additional ²³⁴U flux of about 0.25 dpm/cm₂·10³ yr into the oceans (about 20% of its river supply) is necessitated.     

Geochemical and hydrogeological contrasts between shallow and deeper aquifers in two villages of Araihazar, Bangladesh: Implications for deeper aquifers as drinking water sources

Sediment and groundwater profiles were compared in two villages of Bangladesh to understand the geochemical and hydrogeological factors that regulate dissolved As concentrations in groundwater. In both villages, fine-grained sediment layers separate shallow aquifers (< 28 m) high in As from deeper aquifers (40-90 m) containing < 10 μg/L As. In one village (Dari), radiocarbon dating indicates deposition of the deeper aquifer sediments > 50 ka ago and a groundwater age of thousands of years. In the other village (Bay), the sediment is < 20 ka old down to 90 m and the deeper aquifer groundwater is younger, on the order of hundreds of years. The shallow aquifers in both villages that are high in As contain bomb-³H and bomb-¹⁴C, indicating recent recharge. The major and minor ion compositions of the shallow and deeper aquifers also differ significantly. Deeper aquifer water is of the Na⁺-HCO₃^- type, with relatively little dissolved NH₄⁺ (76 ± 192 μmol/L), Fe (27 ± 43 μmol/L) and Mn (3 ± 2 μmol/L). In contrast, shallow aquifer water is of the Ca²⁺-Mg²⁺-HCO₃^- type, with elevated concentrations of dissolved NH₄⁺ (306 ± 355 μmol/L), Fe (191 ± 73 μmol/L), and Mn (27 ± 43 μmol/L). In both villages, the quantity of As extractable from deeper aquifer sands with a 1 mol/L phosphate solution (0.2 ± 0.3 mg/kg, n = 12; 0.1 ± 0.1 mg/kg, n = 5) is 1 order of magnitude lower than P-extractable As from shallow deposits (1.7 ± 1.2 mg/kg, n = 9; 1.4 ± 2.0 mg/kg, n = 11). The differences suggest that the concentration of P-extractable As in the sediment is a factor controlling the concentration of As in groundwater. Low P-extractable As levels are observed in both deeper aquifers that are low in As, even though there is a large difference in the time of deposition of these aquifers in the two villages. The geochemical data and hydrographs presented in this study suggest that both Holocene and Pleistocene deeper aquifers that are low in As should be a viable source of drinking water as long as withdrawals do not exceed recharge rates of ∼1 cm/yr.     

Solubilities of some hydrous REE phosphates with implications for diagenesis and sea water concentrations

Solubility product determinations suggest that the hydrous phosphates of the rare earths, REPO₄ · $\text{xH}{}_2\text{O}$, are important in controlling the sea water REE concentrations. Two of these solids, rhabdophane, (P6₂22) and “hydrous xenotime”, (14₁/amd), have been synthesized at 100°C via the acid hydrolysis of the respective REE pyrophosphate. The solubility products at infinite dilution were determined to be $\text{pK}{}^0\text{= 24.5}$, (La at 25°C); 26.0, (Pr at 100°C); 25.7, (Nd at 100°C): and 25.5, (Er at 100°C). On the basis of calculations involving the reaction of RE³⁺ with apatite to form the hydrous phosphate, the lanthanum concentration in sea water is predicted to be about 140 pmol/L. Laboratory experiments support the hypothesis that apatite is a substrate for reactions with dissolved REE.     

Sedimentary iron monosulfides: Kinetics and mechanism of formation

The reaction between hydrous iron oxides and aqueous sulfide species was studied at estuarine conditions of pH, total sulfide, and ionic strength to determine the kinetics and formation mechanism of the initial iron sulfide. Total, dissolved and acid extractable sulfide, thiosulfate, sulfate, and elemental sulfur were determined by spectrophotometric methods. Polysulfides, S₄^2? and S₅^2?, were determined from ultraviolet absorbance measurements and equilibrium calculations, while product hydroxyl ion was determined from pH measurements and solution buffer capacity.Elemental sulfur, as free and polysulfide sulfur, was 86% of the sulfide oxidation products; the remainder was thiosulfate. Rate expressions for the reduction and precipitation reactions were determined from analysis of electron balance and acid extractable iron monosulfide vs time, respectively, by the initial rate method. The rate of iron reduction in moles/liter/minute was given by $\text{d(}\text{reduction}\text{Fe)}\text{dt}\text{= kS}{}_{\mathrm{t}}{}^{0.5}\text{(J}{}^{\mathrm{+}}\text{)}{}^{0.5}\text{A}{}_{\mathrm{FeOOH}}{}^1$ where S_t was the total dissolved sulfide concentration, (H⁺) the hydrogen ion activity, both in moles/ liter; and A_FeOOH the goethite specific surface area in square meters/liter. The rate constant, k, was 0.017 ± 0.002m^?2 min^?1. The rate of reduction was apparently determined by the rate of dissolution of the surface layer of ferrous hydroxide. The rate expression for the precipitation reaction was $\text{d(FeS)}\text{dt}\text{= kS}{}_{\mathrm{t}}{}^1\text{(H}{}^{\mathrm{+}}\text{)}{}^1\text{A}{}_{\mathrm{FeOOH}}{}^1$ where $\text{d(FeS)}\text{dt}$ was the rate of precipitation of acid extractable iron monosulfide in moles/liter/minute, and k = 82 ± 18 mol^?1l²m^?2 min^?1.A model is proposed with the following steps: protonation of goethite surface layer; exchange of bisulfide for hydroxide in the mobile layer; reduction of surface ferric ions of goethite by dissolved bisulfide species which produces ferrous hydroxide surface layer elemental sulfur and thiosulfate; dissolution of surface layer of ferrous hydroxide; and precipitation of dissolved ferrous specie and aqueous bisulfide ion.     

Gibbsite solubility and thermodynamic properties of hydroxy-aluminum ions in aqueous solution at 25°C

Solubility curves were determined for a synthetic gibbsite and a natural gibbsite (Minas Gerais, Brazil) from pH 4 to 9, in 0.2% gibbsite suspensions in 0.01 M NaNO₃ that were buffered by low concentrations of non-complexing buffer agents. Equilibrium solubility was approached from oversaturation (in suspensions spiked with Al(NO₃)₃ solution), and also from undersaturation in some synthetic gibbsite suspensions. Mononuclear Al ion concentrations and pH values were periodically determined. Within 1 month or less, data from over-and undersaturated suspensions of synthetic gibbsite converged to describe an equilibrium solubility curve. A downward shift of the solubility curve, beginning at pH 6.7, indicates that a phase more stable than gibbsite controls Al solubility in alkaline systems. Extrapolation of the initial portion of the high-pH side of the synthetic gibbsite solubility curve provides the first unified equilibrium experimental model of Al ion speciation in waters from pH 4 to 9.The significant mononuclear ion species at equilibrium with gibbsite are Al³⁺, AlOH²⁺, Al(OH)⁺₂ and Al(OH)^?₄, and their ion activity products are $\text{1K}{}_{50}\text{= 1.29 × 10}{}^8$, $\text{1K}{}_{\mathrm{s1}}\text{= 1.33 × 10}{}^3$, $\text{1K}{}_{\mathrm{s2}}\text{= 9.49 × 10}{}^{\mathrm{?3}}$ and $\text{1K}{}_{\mathrm{s4}}\text{= 8.94 × 10}{}^{\mathrm{?15}}$. The calculated standard Gibbs free energies of formation (ΔG°_f) for the synthetic gibbsite and the A1OH²⁺, Al(OH)⁺₂ and Al(OH)^?₄ ions are ?276.0, ?166.9, ?216.5 and ?313.5 kcal mol^?1, respectively. These ΔG°_f values are based on the recently revised ΔG°_f value for Al³⁺ (?117.0 ± 0.3 kcal mol_?1) and carry the same uncertainty. The ΔG°_f of the natural gibbsite is ?275.1 ± 0.4 kcal mol^?, which suggests that a range of ΔG°_f values can exist even for relatively simple natural minerals.     

The stable isotopic composition (Cl/Cl) of dissolved chloride in rainwater

The stable isotopic composition of dissolved Cl^-${\text{Cl}}^{-}$ in rainwater was measured from a coastal and an interior location in eastern Canada. At the interior Bonner Lake, Ontario, site the δ³⁷Cl values of dissolved Cl^-${\text{Cl}}^{-}$ in precipitation ranged from −3.5‰ to −1.2‰ (SMOC) with an amount-weighted annual average of −2.3‰. At the coastal site, Bay D’Espoir, Newfoundland, δ³⁷Cl values of dissolved Cl^-${\text{Cl}}^{-}$ values ranged from −3.1‰ to 0.0‰ with an amount-weighted annual average of −1.3‰. These negative δ³⁷Cl values provide evidence that atmospheric HCl is ³⁷Cl depleted, presumably from acidification of sea-salt aerosols. Accordingly, dissolved Cl^-${\text{Cl}}^{-}$ in the headwaters of two montane rivers in Western Canada had similarly depleted δ³⁷Cl values. These results have implications to the interpretation of the isotopic compositions of dissolved Cl^-${\text{Cl}}^{-}$ in surface waters, formation fluids, and groundwaters.     

Total nitrogen content of deep sea basalts

Various models have been suggested concerning the origin and evolution of the earth's atmosphere. An estimate of the nitrogen content of the mantle could further constrain atmospheric models. Total nitrogen content was determined by thermal neutron activation analysis via ¹⁴N(n,p)¹⁴C. The ¹⁴C was converted to carbon dioxide and counted in miniature low level proportional counters. The total nitrogen content of U.S.G.S. standards BCR-1 and G-2 as determined by different laboratories is variable, probably due to atmospheric adsorption by the finely ground samples. Total nitrogen content was determined in deep sea basalt glasses from three regions: East Pacific Rise ($\text{15 ± 4, 18 ± 4}$, and $\text{7 ±}\text{ppm}\text{2 N}$), Mid-Atlantic Rift (FAMOUS Region:$\text{22 ± 5, 18 ± 3}$, and $\text{10 ± 2}\text{ppm}\text{N}$) and the Juan de Fuca Ridge ($\text{17 ± 4}\text{ppm}\text{N}$). Matrix material from the same samples as the glasses was available from the East Pacific Rise ($\text{37 ± 6, 26 ± 4}$, and $\text{34 ± 6}\text{ppm}\text{N}$) and the Mid-Atlantic Rift ($\text{39 ± 4}\text{ppm}\text{N}$) which are about 50 to 100% greater than the associated glasses. The increased matrix abundance may be due to incorporation of chemically bound nitrogen from sea water rather than dissolved molecular nitrogen. The nitrogen content of the FAMOUS samples are inconsistent with the model of Langmuir et al. (1977) for petrogenesis based on trace element data. Factors which can affect the observed nitrogen content in the basalts and the interpretation in terms of the mantle nitrogen abundance are discussed (e.g. partial melting and degassing of the basalts). A lower limit of about 2 ppm N in the mantle can be estimated.     

The geochemistry of the stable isotopes of silicon

One hundred thirty two new measurements of the relative abundances of the stable isotopes of silicon in terrestrial materials are presented. The total variation of ^δ30Si found is 6.2%., centered on the mean of terrestrial mafic and ultramafic igneous rocks, δ³⁰Si = ?0.4%.. Igneous rocks show limited (1.1%.) variation; coexisting minerals exhibit small, systematic silicon isotopic fractionations that are roughly $\text{1}\text{3}$ the magnitude of concomitant oxygen isotopic fractionations at 1150°C. In both igneous minerals and rocks, δ³⁰Si shows a positive correlation with silicon content, as does δ¹⁸O. Opal from both sponge spicules and sinters is light, with $\text{}\text{?}\text{gd}{}^{30}\text{Si}\text{= ?2.3}$ and ?1.4%., respectively. Large ^δ30Si values of both positive and negative sign are reported for the first time from clay minerals (?2.3 to +1.8%.), opaline phytoliths (?1.4 to +2.8%.), and authigenic quartz (+ 1.4%.). All highly fractionated samples were precipitated from solution at low temperatures; however, aqueous silicon is not measurably fractionated relative to quartz at equilibrium. A kinetic isotope fractionation of ≈3.5%. is postulated to occur during the low temperature precipitation of opal and, possibly, poorly ordered phyllosilicates, with the silicate phase being enriched in ²⁸Si. This fractionation, coupled with a Rayleigh precipitation model, is capable of explaining most non-magmatic δ³⁰Si variations. Chert ^δ30Si values are largely inherited, but the primary opal ^δ30Si values can be modified by isotopic equilibration of silicate silicon and dissolved silicon during the transformation of opal into quartz.