Fluxes of metals to a manganese nodule radiochemical,chemical, structural,and mineralogical studies

Fluxes of metals to the top and bottom surfaces of a manganese nodule were determined by combining radiochemical (²³⁰Th,²³¹Pa,²³²Th,²³⁸U,²³⁴U) and detailed chemical data. The top of the nodule had been growing in its collected orientation at 4.7 mm Myr^?1 for at least 0.5 Myr and accreting Mn at 200 μg cm^?2 kyr^?1. The bottom of the nodule had been growing in its collected orientation at about 12 mm Myr^?1 for at least 0.3 Myr and accreting Mn at about 700 μg cm^?2 yr^?1. Although the top of the nodule was enriched in iron relative to the bottom, the nodule had been accreting Fe 50% faster on the bottom.²³²Th was also accumulating more rapidly in the bottom despite a 20-fold enrichment of²³⁰Th on the top.The distribution of alpha-emitting nuclides calculated from detailed radiochemical measurements matched closely the pattern revealed by 109-day exposures of alpha-sensitive film to the nodule. However, the shape and slope of the total alpha profile with depth into the nodule was affected strongly by²²⁶Ra and²²²Rn migrations making the alpha-track technique alone an inadequate method of measuring nodule growth rates.Diffusion of radium in the nodule may have been affected by diagenetic reactions which produce barite, phillipsite and todorokite within 1 mm of the nodule surface; however, our sampling interval was too broad to document the effect. We have not been able to resolve the importance of nodule diagenesis on the gross chemistry of the nodule.     

The effect of crystal field stabilization on the olivine→spinel transition in the system Mg2SiO4 - Fe2SiO4

Crystal field stabilization (CFS) plays a significant role in determining equilibrium phase boundaries in olivine→spinel transformations involving transition-metal cations, including Fe²⁺ which is a major constituent of the upper mantle. Previous calculations for Fe₂SiO₄ ignored pressure and temperature dependencies of crystal field stabilization enthalpies (CFSE) and the electronic configurational entropy (S _CFS). We have calculated free energy changes (ΔG _CFS) due to differences of crystal field splittings between Fe₂SiO₄ spinel and fayalite from: ΔG _CFS=?ΔCFSE?TΔS _CFS, as functions of P and T, for different energy splittings of t _2g orbital levels of Fe²⁺ in spinel. The results indicate that ΔG _CFS is always negative, suggesting that CFS always promotes the olivine→spinel transition in Fe₂SiO₄, and expands the stability field of spinel at the expense of olivine. Because of crystal field effects, transition pressures for olivine→spinel transformations in compositions (Mg_1?x Fe _x )₂SiO₄ are lowered by approximately 50x kbar, which is equivalent to having raised the olivine→spinel boundary in the upper mantle by about 15 km.     

Post-depositional metal enrichment processes inside manganese nodules from the north equatorial Pacific

Interiors of manganese nodules from siliceous ooze beneath the Pacific equatorial high-productivity region, when examined by scanning electron microscopy (SEM) and electron microprobe, display post-depositional recrystallization textures and metalliferous oxide bands (diameter 1–10 μm, 30–40 wt.% Mn, 4–5% Ni, 3–4% Cu). SEM has revealed biogenic siliceous matter in all stages of degradation and dissolution within nodule interiors, creating cavities and voids. Often these miniature vugs contain authigenic phillipsite crystallites which are coated with delicate clusters of crystalline Mn-Fe oxides (todorokite) containing significant amounts of Ni and Cu. We postulate the following diagenetic processes and mechanism of uptake of transition metals inside manganese nodules: (1) palagonite + biogenic silica + pelagic clay → phillipsite + montmorillonite; (2) biogenic matter + amorphous FeOOH or δ-MnO₂ → Fe_aq²⁺ and/or Mn^IIMn^IV oxide (todorokite); (3) aerated seawater or δ-MnO₂ + Fe_aq²⁺ → FeOOH and/or todorokite (deposited on phillipsite); (4) (Ni^II and Cu^II) organic chelates (adsorbed on clays, etc.) + amorphous FeOOH or δ-MnO₂ → Ni-Cu-todorokite + phillipsite, etc.This mechanism explains the well-known positive Mn-Ni-Cu and negative Fe-Ni, Fe-Cu correlations in nodules. By analogy with terrestrial todorokites, which require about 8 wt.% Mn to be in the divalent state to stabilize the crystal structure, as much as 8 wt.% (Ni + Cu) could be accommodated in todorokite-bearing deep-sea manganese nodules. However, although such nodules beneficiate Ni and Cu with respect to marine sediments and seawater, they remain undersaturated in these divalent cations.     

Thermodynamic properties,low-temperature heat-capacity anomalies,and single-crystal X-ray refinement of hydronium jarosite, (H<Subscript>3</Subscript>O)Fe<Subscript>3</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)<Subscript>6</Subscript>

Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO₄ solutions. Single-crystal XRD refinement with R₁=0.0232 for the unique observed reflections (|F_o| > 4_F) and wR₂=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, V^o=160.11(4) cm³, and fractional positions for all atoms except the H in the H₃O groups. The chemical composition of this sample is described by the formula (H₃O)_0.91Fe_2.91(SO₄)₂[(OH)_5.64(H₂O)_0.18]. The enthalpy of formation (H^o_f) is –3694.5 ± 4.6 kJ mol^–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H₂O, and -MgSO₄. The entropy at standard temperature and pressure (S^o) is 438.9±0.7 J mol^–1 K^–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (C_p) data between 273 and 400 K were fitted to a Maier-Kelley polynomial C_p(T in K)=280.6 + 0.6149T–3199700T^–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol^–1. Speciation and activity calculations for Fe(III)–SO₄ solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the C_p data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in C_p, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H₃O)Fe₃(SO₄)₂(OH)₆ was estimated: G^o_f= –3226.4 ± 4.6 kJ mol^–1, H^o_f=–3770.2 ± 4.6 kJ mol^–1, S^o=448.2 ± 0.7 J mol^–1 K^–1, C_p (T in K)=287.2 + 0.6281T–3286000T^–2 (between 273 and 400 K).     

Organic biomarkers for tracing carbon cycling in the Gulf of Papua (Papua New Guinea)

Sediment traps were deployed in the Gulf of Papua in June–July 1997, to determine fluxes of organic matter and inorganic elements from the photic zone to deeper waters at the base of the continental slope and in the northern Coral Sea. Three stations, ranging from 900 to 1500 m depth, had “shallow” traps at 300 m below the water surface and “deep” traps set 100 m above the bottom. Infiltrex II water samplers collected particulate and dissolved organic matter from the Fly, Purari and Kikori rivers, and near-surface water from the shelf of the Gulf of Papua. Samples were analysed for molecular organic biomarkers to estimate the sources of organic carbon and its cycling processes.Dry weight fluxes from the shallow traps ranged from 115 to 181 mg m⁻² day⁻¹ and particulate organic carbon (POC) fluxes ranged from 1.2 to 1.9 mM OC m⁻² d⁻¹ with molar organic carbon to particulate nitrogen ratios (C/N) ranging from 6.0 to 6.5. Fluxes in deep traps were likely influenced by both early diagenesis and entrapment of resuspended shelf sediments. Dry weight fluxes in deep traps ranged from 106 to 574 mg m⁻² day⁻¹ and POC fluxes ranged from 0.6 to 1.5 mM OC m⁻² d⁻¹, with C/N ratios ranging from 8.5 to 10.8. ¹³C/¹²C ratios were −20.2‰ to −21.7‰ in all trap samples, indicating that most of the settling POC was “marine-derived”. Shallow traps had δ¹⁵N values of 6.3‰ to 7.2‰ while the values in deep traps were 4.9–5.0‰, indicating the N-rich near-surface OC was less degraded than that in the deep traps. The biogenic lipids consisted of hydrocarbon, sterol and fatty acid biomarkers indicative of marine zooplankton, phytoplankton and bacteria. Sterol markers for diatoms and dinoflagellates were abundant in the water samples. Highly branched isoprenoid alkenes, usually attributable to diatoms, were also detected in both water and shallow traps. Traces of C₂₆–C₃₄ n-alcohols indicative of land–plant biomarkers, were found in river water samples and in the shallow sediment traps. A large unresolved complex mixture (UCM) of hydrocarbons, and a uniform distribution of n-alkanes, indicative of petroleum hydrocarbons, were also detected in the traps. Hopane and sterane biomarkers detected in the trap oil were characteristic of a marine carbonate source, and the aromatic hydrocarbon composition distinguished at least two different oil signatures.We concluded that mass and POC fluxes were similar to those reported for other continental shelves and marginal oceans in tropical and subtropical regions. There was a dramatic decrease in POC as particles sank, due to zooplankton repackaging and photochemical and bacterial decomposition. Carbon isotopic and biomarker patterns showed most of the POC in the sediment traps was marine-sourced with only traces of terrestrial input. There was a significant flux of petroleum, which may signal the existence of natural petroleum seeps in this region.     

Atmospheric Disturbances that Generate Intermittent Turbulence in Nocturnal Boundary Layers

Using the unprecedented observational facilities deployed duringthe 1999 Cooperative Atmosphere-Surface Exchange Study (CASES-99),we found three distinct turbulent events on the night of 18October 1999. These events resulted from a density current,solitary wave, and internal gravity wave, respectively. Our studyfocuses on the turbulence intermittency generated by the solitarywave and internal gravity wave, and intermittent turbulenceepisodes associated with pressure change and wind direction shiftsadjacent to the ground. Both the solitary and internal gravitywaves propagated horizontally and downward. During the passage ofboth the solitary and internal gravity waves, local thermal andshear instabilities were generated as cold air was pushed abovewarm air and wind gusts reached to the ground. These thermal andshear instabilities triggered turbulent mixing events. Inaddition, strong vertical acceleration associated with thesolitary wave led to large non-hydrostatic pressure perturbationsthat were positively correlated with temperature. The directionaldifference between the propagation of the internal gravity waveand the ambient flow led to lateral rolls. These episodic studiesdemonstrate that non-local disturbances are responsible for localthermal and shear instabilities, leading to intermittentturbulence in nocturnal boundary layers. The origin of thesenon-local disturbances needs to be understood to improve mesoscalenumerical model performance.     

The implications for paleodietary and paleoclimatic reconstructions of intrapopulation variability in the oxygen and carbon isotopes of teeth from modern feral horses

We analyzed the isotopic patterns found in the tooth enamel of modern feral horses from Shackleford Banks, North Carolina (USA), which has a temperate climate and supports primarily C₄ grasslands. Enamel δ¹³C values averaged −4.1‰ with a standard deviation (1σ) of 1.7‰, which corresponds to an average diet of 66 ± 12% C₄ plants. Our results differ from dietary reconstructions from 1978 to 1981, which found that horses consumed 91% C₄ plants. This suggests that horses have increased their consumption of C₃ forbs, likely as a result of the removal of cattle, sheep, and goats from the island. Shackleford surface waters had δ¹⁸O values that averaged −3.3 ± 0.5‰ and −1.3 ± 1.8‰ on the western and eastern ends of the island, respectively. Tooth enamel samples averaged 27.3 ± 1.5‰ and displayed the same range of δ¹⁸O values as surface waters. The variability of both δ¹⁸O and the δ¹³C values among individuals within this population demonstrates that horses from relatively homogenous temperate environments can display a wide range of isotopic values. Given the observed range of isotopic values for modern horses, we suggest that researchers use the mean values of multiple (≥9) equids when attempting to reconstruct average paleodiets and/or paleoenvironmental conditions.     

Trace Element Determination by ICP-AES and ICP-MS: Developments and Applications Reported During 2004 and 2005

This review describes significant developments in trace element determination using inductively coupled plasma-atomic emission spectrometry (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS) that were reported in 2004 and 2005. It focuses on the application of ICP techniques to geological and environmental samples; fundamental studies in ICP-MS and ICP-AES instrumentation are not included. The literature reviewed indicated that the majority of new publications concerned advances in ICP-MS analysis rather than ICP-AES. However, ICP-AES developments are still being published, particularly in the areas of sample preconcentration and sample introduction. The trend in increasing publication of developments in hyphenated speciation techniques looks set to persist as knowledge of elemental speciation becomes critical for many environmental studies. Collision or reactions cells were the most reported technique for spectral interference removal in ICP-MS, probably reflecting the growing adoption of cell instruments in laboratories during the last few years.     

Impact of Carbonate Precipitation on Riverine Inorganic Carbon Mass Transport from a Mid-continent, Forested Watershed

Physiochemical controls on the carbonate geochemistry of large river systems are important regulators of carbon exchange between terrestrial and marine reservoirs on human time scales. Although many studies have focused on large-scale river carbon fluxes, there are few investigations of mechanistic aspects of carbonate mass balance and transport at the catchment scale. We determined elemental and carbonate geochemistry and mass balances for net carbonate dissolution fluxes from the forested, mid-latitude Huron River watershed, established on carbonate-rich unconfined glacial drift aquifers. Shallow groundwaters are near equilibrium with respect to calcite at pCO₂ values up to 25 times atmospheric values. Surface waters are largely groundwater fed and exhibit chemical evolution due to CO₂ degassing, carbonate precipitation in lakes and wetlands, and anthropogenic introduction of road salts (NaCl and CaCl₂). Because the source groundwater Mg²⁺/HCO₃ ^? ratio is fairly constant, this parameter permits mass balances to be made between carbonate dissolution and back precipitation after groundwater discharge. Typically, precipitation does not occur until IAP/K calcite values exceed 10 times supersaturation. Stream chemistry changes little thereafter even though streams remain highly supersaturated for calcite. Our data taken together with historical United States Geological Survey (USGS) data show that alkalinity losses to carbonate precipitation are most significant during periods of lowest discharge. Thus, on an annual basis, the large carbon flux from carbonate dissolution in soil zones is only decreased by a relatively small amount by the back precipitation of calcium carbonate.