Iron oxidation state in lower mantle mineral assemblages: I. Empirical relations derived from high-pressure experiments

The oxidation state of iron can significantly influence the physical and chemical properties of lower mantle minerals. To improve methods for estimation of Fe³⁺/∑Fe, synthetic assemblages of (Mg,Fe)(Si,Al)O₃ perovskite and (Mg,Fe)O ferropericlase were synthesised from oxide starting mixtures in Re or Fe capsules at 26 GPa and 1650-1850 °C using a multianvil press. (Mg,Fe)(Si,Al)O₃ majorite was also present in some of the run products. Both electron energy loss spectra (EELS) and Mössbauer spectra were measured for each run product, and a robust fitting method was developed for Mössbauer spectra using EELS results as a standard that enabled Fe³⁺/∑Fe of (Mg,Fe)(Si,Al)O₃ perovskite to be determined from Mössbauer spectra of multiphase assemblages. There is a close to linear variation between Fe³⁺/∑Fe and Al concentration in (Mg,Fe)(Si,Al)O₃ perovskite, independent of oxygen fugacity. The concentration of Fe³⁺ in (Mg,Fe)O increases with increasing iron concentration along curves of constant oxygen fugacity, where higher oxygen fugacity stabilises greater Fe³⁺ concentrations. Fe²⁺/Mg partition coefficients calculated from chemical composition data corrected for measured Fe³⁺/∑Fe showed values nearly identical within experimental error for all samples, and independent of Al concentration and oxygen fugacity. Simple empirical relations were derived to calculate Fe³⁺/∑Fe in (Mg,Fe)(Si,Al)O₃ perovskite and (Mg,Fe)O ferropericlase samples for which no Mössbauer or EELS data were available, and tested by applying them to calculation of Fe²⁺/Mg partition coefficients from literature data for (Mg,Fe)(Si,Al)O₃ perovskite-(Mg,Fe)O assemblages where only total iron concentrations had been measured. Results showed Fe²⁺/Mg partition coefficients that were equal to existing values within experimental error, hence confirming the validity of the empirical relations.     

Geochemical indicator of original eolian grain size and implications on winter monsoon evolution

Grain size of eolian deposits from the Loess Plateau in China has been widely used to reconstruct the history of the East Asian winter monsoon. However, the grain size of bulk samples is only partially indicative to the strength of the winter monsoon because post-depositional weathering processes have significantly changed the grain size of original eolian particles. Here, non-weathered loess samples were separated into eight different particle fractions, and major chemical elements were determined in order to establish a geochemical indicator of original eolian grain size. The results show that SiO₂ and Al₂O₃ contents and the SiO₂/Al₂O₃ ratio in different fractions vary regularly with grain size, and that a good linear relation exists between the SiO₂/Al₂O₃ ratio and grain size for the fractions <50 μm. Because Al and Si are among the most stable elements and pedogenic processes in the Loess Plateau cannot affect the SiO₂/Al₂O₃ ratio, this index can be used to reflect the grain size of original eolian particles. Application of this index in the Weinan and Luochuan loess sections of the last climatic cycle shows that SiO₂/Al₂O₃ is in good agreement with median grain size (Md) in the loess units. On the contrary, SiO₂/Al₂O₃ has documented a series of fluctuations in the soil units that are not clearly indicated by the grain-size changes of bulk samples.

     

Determination of thermodynamic properties of (Fe,Mg)-pyroxenes at 1000 K by the emf method

Emf measurements were made on the cell Pt|Fe,(Fe,Mg)_xSi₂O₆,SiO₂|(ZrO₂)_0.85(CaO)_0.15|Fe,FeO|Pt at 1000 K. Using the present data, the standard free energy of formation of ferrosilite (compound FeSiO₃), from the component oxides FeO and SiO₂, is calculated to be −6.35 ± 0.80 kJ/mol. The activity-composition relation for pyroxene solid solution shows that it has a positive deviation from ideality at 1000 K. The present results are compared with the results of other workers.ΔG_mix andΔG^ex are calculated and plotted againstN_FeSiO3.     

The system iron-enstatite-water at high pressures and temperatures—formation of iron hydride and some geophysical implications

The system iron-enstatite-water was investigated at pressures around 5 GPa and at temperatures ranging from 1000 to 1200°C, using several different kinds of starting materials. Quenched samples showed the coexistence of iron, olivine and pyroxene. Synthesis of the Fe-containing olivine in the run products proves that a series of reactions, Fe + H₂O → FeH_x + FeO and FeO + MgSiO₃ → (Mg, Fe)₂SiO₄, have taken place. Spherical “balls of iron” were observed in the 1200°C run. This strongly indicates that the melting temperature of iron decreased by ～ 500 K by the possible dissolution of hydrogen. Following geophysical implications are derived from these experimental results. If water was retained in the hydrous minerals in the primordial material, the iron-water reaction is expected to occur throughout the core-formation process. The reaction product FeH_x will melt and then sink to form a proto-core and iron oxide will be dissolved in the Earth's mantle. The dissolution of hydrogen in the Earth's core is a natural consequence of the core-formation process.     

The Adhi Kot breccia and implications for the origin of chondrules and silica-rich clasts in enstatite chondrites

The Adhi Kot EH4 enstatite chondrite breccia consists of silica-rich clasts (12+mn; 5 vol.%), chondrule-rich clasts (55+mn; 10 vol.%) and matrix (35+mn; 10 vol.%). The silica-rich clasts are a new kind of enstatite chondritic material, which contains more cristobalite (18–28 wt.%) than enstatite (12–14 wt.%), as well as abundant niningerite and troilite. The bulk atomic Mg/Si ratios of the clasts (0.22–0.40) are much lower than the average for enstatite chondrites (0.79). Kamacite and martensite (with 8–11 wt.% Ni and a martensitic structure) occur in all three breccia components. The clasts have kamacite-rich rims, and kamacite-rich aggregates occur in the matrix.A unidirectional change in the ambient pS₂/pO₂ ratio in the region of the solar nebula where Adhi Kot agglomerated can explain many of the breccia's petrologic features. If this region initially had a very high pS₂/pO₂ ratio in a gas of non-cosmic composition, sulfurization of enstatite and metallic Fe (e.g., MgSiO₃ + 2Fe + C + 3H₂S = MgS + SiO₂ + 2FeS + H₂O + CH₄) may have occurred, producing abundant niningerite, free silica and troilite at the expense of enstatite and metallic Fe. The Ni content of the residual metal would have increased, perhaps to ～ 8–10 wt.%. The silica-rich clasts agglomerated under these conditions; a significant fraction of the originally produced niningerite was lost (perhaps by aerodynamic size-sorting processes), lowering the clasts' bulk Mg/Si ratios.The pS₂/pO₂ ratio then decreased (perhaps because of infusion of additional H₂O) and sulfurization of metallic Fe and enstatite ceased. The chondrule-rich clasts agglomerated under these conditions, acquiring little free silica and niningerite. An episode of chondrule formation occurred at this time (by melting millimeter-sized agglomerates of this relatively silica-poor enstatite chondrite material and concomitant fractionation of an immiscible liquid of metallic Fe,Ni and sulfide). The chondrule-rich clasts agglomerated many such chondrules. Subsequently, the matrix agglomerated, acquiring the few remaining chondrules. Kamacite-rich aggregates formed, after the cessation of metal sulfurization, and agglomerated with the matrix. The kamacite-rich clast rims were acquired at this time.The components of Adhi Kot accreted to the EH chondrite parent body, where the breccia was assembled, buried beneath additional accreting material, and metamorphosed at temperatures of ? 700°C. Impact-excavation of the breccia and deposition onto the surface caused the formation of martensite from taenite inside the clasts and the matrix. At the surface, impact-melting produced an albite glass spherule, which was incorporated into the matrix. However, the absence of solar-wind-implanted rare gases in bulk Adhi Kot indicates that the breccia spent little time in a regolith.     

Reaction microstructures in corundum‐ and kyanite‐bearing mafic mylonites from the Takahama metamorphic rocks,western Kyushu,Southwest Japan

High‐grade mylonites occur in the Takahama metamorphic rocks, a member of the high‐pressure low‐temperature type Nagasaki Metamorphic Rocks, western Kyushu, Japan. Mafic layers within the mylonites retain reaction microstructures consisting of margarite aggregates armoring both corundum and kyanite. The following retrograde reaction well accounts for the microstructures in the CaO–Al₂O₃–SiO₂–H₂O system: 3Al₂O₃ + 2Al₂SiO₅ + 2Ca₂Al₃Si₃O₁₂(OH) + 3H₂O = 2Ca₂Al₈Si₄O₂₀(OH)₄ (corundum + kyanite + clinozoisite + fluid = margarite). Mass balance analyses and chemical potential modeling reveal that the chemical potential gradients present between kyanite and corundum have likely driven the transport of the CaO and SiO₂ components. The mylonitization is considered to take place chronologically after peak metamorphism and before the above reaction, based on the following features: approximately constant thickness of the margarite aggregates, random orientation of margarite, and local modification of garnet composition at a boudin neck that formed during mylonitization. The estimated peak temperature of 640°C and the pressure–temperature conditions of the above reaction indicate that the mylonitization took place at temperature between 530 and 640°C at pressures higher than 1.2 GPa, approximately equivalent to the depth of the lower crust of island arcs.     

Chemical evidence of water movements in the deepest part of Lake Leman (Lake Geneva)

Regular surveys of bottom water chemistry (SiO₂, O₂, Fe, Mn) have been carried from 1978 to 1986 in the deepest 30 m of Lake Léman (max. depth 309 m) including interface waters sampled with a Jenkins Mortimer corer. When compared to normal chemical gradients near bottom, i.e. O₂ decrease and SiO₂ increase, three types of anomalies (lens, interface, and behaviour) have been observed on O₂ and SiO₂, the most sensitive chemical species. These anomalies were found throughout the year, in several stations of the deepest part of the lake and even along the slope of the lake basin. Major anomalies (O₂ + 3 to 10 mg ·l^–1; SiO₂ -1 to 2 mg·l^–1) were generally found at the sediment water interface and may extend 10–20 m above the sediment and last 10 weeks. Others marked lens anomalies could be observed for 3 to 4 months. Several mechanisms are probably responsible for this injection of surface waters along the lake slope (accumulation of turbid water on lake banks after severe windstorms; river density currents due to temperature and/or turbidity difference with lake waters). These water-inputs do not represent important volumes ( 1% total lake volume) but, when occuring at the interface, they ensure a sufficient oxygen level to prevent diffusion of phosphate and ammonia from pore waters when winter lake overturns do not reach bottom layers (from 1972 to 1980). Complete overturns, as observed in 1980/81, are connected with major interface anomalies (bottom O₂ moves up from 2 to 10 mg·l^–1) occuring before surface mixing reaches the deepest layers.     

Stability relations of ilmenite and ulvöspinel in the Fe-Ti-O system and application of these data to lunar mineral assemblages

The fO₂ stability relations of ilmenite and ulvöspinel were determined using C-O H-N gas-flow apparatus with fO₂ measured by a solid ceramic (calcia-zirconia) oxygen electrolyte cell. For Fe+TiO₂ + 1/2 O₂ =FeTiO₃ (from 850°–1050°C), 1/2 log fO₂=(−11,250/T) + 0.98 and for Fe+FeTiO₃ + 1/2 O₂ =Fe₂TiO₄ (from 850°–1210°C), 1/2 logfO₂ = (−12,170/T) + 1.93. These curves lie at significantly higher values of ?O₂ than determined by previous investigators (i.e., 3/4 and1/4 order of magnitude for ilmenite and ulvöspinel, respectively). In addition, for Fe+ 2TiO₂ + 1/2 O₂ =FeTi₂O₅ (1210°C), ΔG_r⁰=−45.8 ± 0.6 kcal. The QFI curve crosses the ulvöspinel reduction curve at ∼950°C and is at lower values of fO₂ below this temperature. The occurrences of fayalite reduction to SiO₂ + Fe in lunar rock 14053, as well as a new finding of this assemblage in 14072, are evidence for extreme sub-solidus reduction, whereas ulvöspinel breakdown alone occurs under less reducing conditions. The ‘complete’ reduction of ulvöspinel to TiO₂ + Fe occurs in 2 steps: first, to ilmenite + Fe and then, however more slowly, to rutile + Fe. Thus, the presence of ulvöspinel but lack of ilmenite reduction in lunar rocks cannot be used as evidence that the fO₂ was between the associated curves — only upper limits of fO₂ can be inferred.     

High-pressure phase transformations in the system of MgSiO3-FeSiO3

Two synthetic pyroxenes (FeSiO₃, MgSiO₃) and five natural pyroxenes with compositions of about Fs₈₀En₂₀, Fs₆₀En₄₀, Fs₅₀En₅₀, Fs₄₀En₆₀, and Fs₂₀En₈₀ have been subjected to pressures up to250 ± 50kbars at a temperature of about1500 ± 200°C in a diamond anvil cell heated by an infrared laser beam. After quenching and unloading X-ray data analysis indicates that (1) those with Mg less than 50% undergo the following reactions: 2(Mg,Fe)SiO₃ (pyroxene) → (Mg,Fe)₂SiO₄ (spinel) + SiO₂ (stishovite) → 2(Mg,Fe)O (magnesiowu¨stite) + SiO₂ (stishovite) with increase of pressure, and (2) those with Mg higher than 60%, undergo the following reactions: 2(Mg,Fe)SiO₃ (pyroxene) → (Mg,Fe)₂SiO₄ (spinel) + SiO₂ (stishovite) → 2(Mg,Fe)SiO₃ (hexagonal phase) → 2(Mg,Fe)O (magnesiowu¨stite) + SiO₂ (stishovite) with increase of pressure.     

Iron oxidation state in lower mantle mineral assemblages: II. Inclusions in diamonds from Kankan, Guinea

Inclusions of ferropericlase and former (Mg,Fe)(Si,Al)O₃ perovskite in diamonds from Kankan, Guinea believed to originate in the lower mantle were studied using Mössbauer spectroscopy to determine Fe³⁺/ΣFe. Fe³⁺ concentration in the (Mg,Fe)(Si,Al)O₃ inclusion is consistent with empirical relations relating Fe³⁺/ΣFe to Al concentration, supporting the inference that it crystallised in the perovskite structure at lower mantle conditions. In ferropericlase there is a nearly linear variation of trivalent cation abundance with monovalent cation abundance, suggesting a substitution of the form Na_0.5M_0.5³⁺O (M=Fe³⁺, Cr³⁺, Al³⁺). Excess positive charge is likely balanced by cation vacancies, where their abundance is observed to increase with increasing iron concentration, consistent with high-pressure experiments. The abundance of cation vacancies is related to oxygen fugacity, where ferropericlase inclusions from Kankan and São Luiz (Brazil) are inferred to have formed at conditions more oxidising than Fe-(Mg,Fe)O equilibrium, but more reducing than Re-ReO₂ equilibrium. Fe²⁺/Mg partition coefficients between (Mg,Fe)(Si,Al)O₃ and ferropericlase were calculated for inclusions co-existing in the same diamond using Mössbauer data and empirical relations based on high-pressure experimental work. Most values are consistent with high-pressure experiments, suggesting that these inclusions equilibrated at lower mantle conditions. The measured ferropericlase Fe³⁺ concentrations are consistent with diamond formation in a region of redox gradients, possibly arising from the subduction of oxidised material into reduced lower mantle. Reduction of carbonate to form ferropericlase and diamond is consistent with a slight shift of Kankan δ¹³C values to isotopically heavy compositions compared to the worldwide dataset, and could supply the oxygen necessary to satisfy the high Fe³⁺ concentration in (Mg,Fe)(Si,Al)O₃ perovskite, as well as account for the high proportion of ferropericlase in the lower mantle paragenesis. The heterogeneity of lower mantle diamond sources indicates that the composition of lower mantle diamonds do not necessarily reflect those of the bulk mantle.     

Orthorhombic perovskite phases observed in olivine,pyroxene and garnet at high pressures and temperatures

Ferromagnesian silicate olivines, pyroxenes and garnets with Mg/(Mg + Fe)?0.3 (molar) have been found to transform to high-pressure phases characterized by the orthorhombic perovskite structure when compressed to pressures above 250 kbar in a diamond-anvil press and heated to temperatures above 1,000°C with a YAG laser. The zero-pressure density of the perovskite phase of (Mg,Fe)SiO₃ is about 3–4% greater than that of the close-packed oxides, rocksalt plus stishovite. For (Mg,Fe)₂SiO₄ compounds, the perovskite plus rocksalt phase assemblage is 2–3% denser than the mixed oxides. The experimental synthesis of such high-density perovskite phases in olivine, pyroxene and garnet compounds suggests that (Mg,Fe)SiO₃-perovskite is the dominant mineral phase in the earth's lower mantle.     

Oxygen isotope fractionation in mantle minerals

The increment method is adopted to calculate oxygen isotope fractionation factors for mantle minerals, particularly for the polymorphic phases of MgSiO₃ and Mg₂SiO₄. The results predict the following sequence of¹⁸O-enrichment:pyroxene (Mg, Fe, Ca)₂Si₂O₆>olivine (Mg, Fe)₂SiO₄ > spinel (Mg, Fe)₂SiO₄> ilmenite (Mg, Fe, Ca) SiO₃>perovskite (Mg, Fe, Ca) SiO₃. The calculated fractionations for the calcite-perovskite (CaTiO₃) System are in excellent agreement with the experimental calibrations. If there would be complete isotopic equilibration in the mantle, the spinel-structured silicates in the transition zone are predicted to be enriched in¹⁸O relative to the perovskite-structured silicates in the lower mantle but depleted in¹⁸O relative to olivines and pyroxenes in the upper mantle. The oxygen isotope layering of the mantle might result from differences in the chemical composition and crystal structure of mineral phases at different mantle depths. Assuming isotopic equilibrium on a whole earth scale, the chemical structure of the Earth’s interior can be described by the following sequence of¹⁸O-enrichment:upper crust>lower crust>upper mantle>transition zone>lower mantle>core. Project supported by the National Natural Science Foundation of China and the Chinese Academy of Sciences.     

The northwestern Ethiopian Plateau flood basalts: Classification and spatial distribution of magma types

The extensive, complex, continental flood basalt (CFB) province which occurs in Ethiopia and Yemen consists of Oligocene prerift volcanism related to the Africa–Arabia continental break-up. Basalts from the northwestern Ethiopian Plateau exhibit a particularly large range of compositions and, for the first time in the Afro-Arabian CFB province, low-Ti basalts have been encountered. Major and some trace element data have been used to identify distinct geochemical groups and evaluate the role of differentiation processes. Three magma types have been distinguished: two high-Ti groups (HT1 and HT2) and one low-Ti group (LT). The transitional to tholeiitic LT suite exhibits low TiO₂ (1–2.6%), Fe₂O₃^* (10.5–14.8%), CaO/Al₂O₃ (0.4–0.75), Nb/La (0.55–0.85) and high SiO₂ (47–51%). In contrast, the HT2 suite exhibits high TiO₂ (2.6–5%), Fe₂O₃^* (13.1–14.7%), CaO/Al₂O₃ (0.9–1.43), Nb/La (1.1–1.4) and low SiO₂ (44–48.3%). The HT1 series is intermediate between the LT and HT2 groups. These three groups of lavas originated from different parental magmas. They display distinct differentiation trends, either controlled by the removal of a shallow level gabbroic (Pl+Ol+Cpx) assemblage (LT and HT1 suites) or by deeper Ol+Cpx fractionation (HT2 suite). Most of this thick continental flood lava pile was emplaced over a short time interval (about 1–2 Ma). The three contrasted magma types do not reflect a temporal evolution of their sources but rather a strong spatial control. Indeed, the northwestern Plateau may be subdivided into two different subprovinces as all the low-Ti basalts are located in the northern part of the plateau, and the high-Ti basalts are exposed in the eastern and southern parts. The LT and HT1 basalts display compositional ranges similar to those of the low- and high-Ti groups from other main CFB provinces (e.g. Parana, Deccan, Karoo, Siberia, …). However, the HT2 group exhibits extreme OIB-like compositions. This unusual geochemical signature suggests the involvement of deep mantle in the genesis of the HT2 magmas. The LT compositions rather reflect the participation of the continental lithosphere, through mantle derived melts and/or crustal contamination.     

Structure refinement of astrophyllite

The crystal structure of astrophyllite K₂Na(Fe, Mn, Mg,□)₇[Ti₂(Si₄O₁₂)₂|O₃](OH, F)₄ has been refined. The dimensions of the triclinic unit cell are: a = 0.5359(2) nm,b = 1.1614(4) nm, c = 1.1861(4) nm, α= 113.16(2)°, β= 103.04(2)°,γ= 94.56(2)°,V = 0.6495(5) nm³, Z= 1, space group P1, R=0.057 for 5308 reflections |F_o|>3σ|F_o|. According to structural and compositional differences the monoclinic astrophyllite K₂NaNa(Fe, Mn)₄Mg₂Ti2[Si₄O₁₂]₂(OH)₄(OH, F)₂ and astrophyllite should be considered as two different mineral species. Astrophyllite, monoclinic astrophyllite, bafertisite and lamprophyllite contain heteropolyhedral sheets which topologically are related with Si, O sheets of mica where one or several SiO₄ tetrahedra are replaced by TiO _n polyhedra. Therefore this heterophyllotitanosilicate series represents a kind of functional substitution in inorganic crystals.     

Results of Hydrochemical Studies of Lake Azabach'e (Kamchatka)

The nutrient basis of Lake Azabach'e is studied. The distribution of pH and the concentrations of O₂, P_min, Fe, N–NH⁺ ₄, N–NO^– ₃, Si, and organic forms of N and P are considered. The chemical basis of biological production of Lake Azabach'e is assessed. It is found that the amount of Si is excessive everywhere and that phytoplankton production is limited by phosphate and mineral nitrogen deficiency in virtually equal degrees.     

Hydrothermal silica chimney fields in the Galapagos Spreading Center at 86°W

Silica chimneys were discovered in 1985 at 86°W in the rift valley of the Galapagos Spreading Center at 2600 m depth (“Cauliflower Garden”). The inactive chimneys lack any sulfides and consist almost entirely of amorphous silica (up to 96 wt.% SiO₂, opal-A); Fe and Mn oxides are minor constituents. Oxygen isotope data show that formation of the silica chimneys took place at temperatures between 32°C (+29.9‰ δ¹⁸O) and 42°C (+27.8‰ δ¹⁸O).Th/Udating reveals a maximum age of 1440 ± 300y. Amorphous silica solubility relations indicate that the silica chimneys were formed by conductive cooling of pure hydrothermal fluids or by conductive cooling of a fluid/seawater mixture. Assuming equilibrium with quartz at 500 bars, initial fluid temperatures of more than 175°C (i.e., a concentration of > 182 ppm SiO₂) were required to achieve sufficient supersaturation for the deposition of amorphous silica at 40°C and 260 bars. If the silica chimneys originate from the same or a similar fluid as higher-temperature ( < 300°C) sulfide-silica precipitates found nearby (i.e., 2.5 km away), then subsurface deposition of sulfides may have occurred.     

Influence of oxygen pressure on defect concentrations in olivine with a fixed cationic ratio

The variation of the point-defect concentrations with oxygen partial pressure, P_O2, and temperature are derived for forsterite, Mg₂SiO₄, and Mg-rich olivine (Mg,Fe)₂SiO₄ assuming the cation/cation ratios are fixed. These dependencies differ from the open-system situation in which matter is easily transferable between forsterite or olivine and other solid phases. The details depend on whether the cation/cation ratio is exactly stoichiometric, or, if non-stoichiometric, the nature of the majority defects at precise oxygen stoichiometry. One generality which emerges is that regardless of the cation/cation stoichiometry the dominant defects in forsterite at low P_O2 are free electrons, Mg and Si interstitials; at high P_O2 the majority defects are holes, Mg and Si vacancies. In Mg-rich olivine the same defect species exist at the extremes of oxygen partial pressure with the exception of trivalent Fe on Mg sites replacing holes. At low P_O2, therefore, both behave as n-type conductors. The models also suggest that in the P_O2 range around precise oxygen stoichiometry the electrical conductivity in both materials can be a complex function of P_O2.     

Geochemistry of the Late Paleozoic radiolarian cherts within the NE Jiangxi ophiolite melange and its tectonic significance

Major and trace elements are presented for the late Paleozoic radiolarian cherts, which were spatially associated with the NE Jiangxi ophiolite melange. These chert samples show relatively low SiO₂ (78.40%-89.28%) and high Al₂O₃ (3.42%-11.02%). Low Si/Al ratios (6.3-23) and tight negative correlation between Si/Al and Al₂O₃ of the samples indicate that they are muddy cherts containing high and variable contents of pelitic detritus. Geochemically, they are characterized by Al₂O3/(Al2O3+Fe₂O3) = 0.51-0.90, shale-normalized La_n/Ce_n = 0.76-1.11, Ce/Ce* = 0.91-1.22, V<20_μg/g, V/Y<2.6 and Ti/V>40, resembling those of cherts formed in the continental margin regimes. It is therefore concluded that these late Paleozoic radiolarian muddy cherts were most likely formed in a continental margin regime, and not genetically related to the ophiolite suite in NE Jiangxi. It is also unlikely that an oceanic basin existed between the Yangtze and Cathaysia blocks during the late Paleozoic.     

Coupling of early diagenetic processes and sedimentary dynamics in tropical shelf environments: the Gulf of Papua deltaic complex

Tropical mobile mud belts represent a major class of biogeochemical and diagenetic systems characterized by extensive and frequent physical reworking of fine-grained, organic-rich deposits underlying oxygenated waters. Large regions of the Gulf of Papua, Papua New Guinea deltaic complex are dominated by such conditions. A reworked mud belt lies within the inner shelf between 10 and 20 m depth on a sedimentary clinoform derived from coalescing deltas. Deposits across the topset are typically suboxic, nonsulfidic over the upper 0.5–1 m, and have low to moderate maximum pore water concentrations of dissolved Fe(II) and Mn(II) (100–200, but up to 800 μM). Sediments are reactive, with surficial ΣCO₂ production 0.1–0.3 mM d⁻¹ and benthic O₂ fluxes 23±15 mmol m⁻² d⁻¹ (upper 20 cm). The highest rates occur within inner topset deposits (10–20 m) and near the high accumulation rollover region of the topset–foreset beds (40–50 m). Lower rates are found inshore along intertidal channels—mangrove fringe and within scoured or exposed consolidated deposits of the middle topset region. Remineralization rate patterns are independent of relative dominance by terrestrial or marine carbon in sediments. Dissolved O₂ usually penetrates 2–5 mm into surface sediments when macrofaunal burrows are absent. More than 75% of the highly reactive sedimentary Fe(III) pool (350–400 μmol g⁻¹) is typically diagenetically reduced in the upper 0.5 m. Pore water can be measureably depleted at depths >0.5 m, but dissolved H₂S generally remains below detection over the upper 1–2 m. As in other deltaic topset regions, concentration gradients often indicate that compared to many marine deposits of similar sediment accumulation rates, relatively refractory C_org is supplied to the SO₄ reducing zone. Sedimentary C/S ratios are 4–6 within the suboxic topset regions but decrease to <3 in offshore foreset beds where sulfidic diagenesis dominates. Only 15–20% of the diagenetically reduced Fe(II) is pyritic and a maximum of 10–25% is carbonate, implying that most Fe(II) is associated with authigenic or lithogenic silicates or oxides. The dominance of suboxic, nonsulfidic diagenetic processes reflect coupling between delivery of oxide-rich terrestrial debris, remobilization and reoxidation of deposits, and repetitive entrainment/remineralization of both labile and refractory organics. Distinct sedimentary indicators of reactive, suboxic mobile mud belts within tropical climatic zones are: abundant total highly reactive Fe (ΣFeR )>300 μmol g⁻¹; most reactive Fe is diagenetically reduced (ΣFe(II)/ΣFeR0.7–0.8); the proportion of diagenetically reduced Fe present as pyrite is low (Py–Fe(II)<0.2); C/S 4–8; and C_org/particle surface area <0.4 (mg C m⁻²). These depositional environments must be most common in tropical climates during high sea stand.     

GEOSECS AtlanticSi profiles

Measurements of five cosmogenic³²Si vertical profiles in Atlantic waters (27°N to 60°S) are presented. The amounts of dissolved SiO₂ extracted range from 2 to 54 g; the amounts of water from which SiO₂ was extracted range between 540 kg and 270, 000 kg. In additon, SiO₂ recovered from four surface particulate composites (64°N to 61°S) were also analyzed for³²Si.³²Si measurements were made by milking and counting the daughter activity, ³²P. The net³²P activities range from 0.7 to 6.8 cph; typical errors in measurements of the³²P activities are 20–30%.The³²Si concentrations vary from 0.6 dpm/10⁶ kg of water in the North Atlantic surface waters to 235 dpm/10⁶ kg at 400 m depth in the circumpolar waters. The vertical profiles of³²Si at the five Atlantic stations approximately follow the Si profiles but the depth gradients are different. This would be expected also considering the in-situ release mechanisms due to dissolution and advection/diffusion from the bottom waters. Except for the circumpolar station 89, where the Si and³²Si profiles show the effect of marked vertical mixing (nearly depth independent profiles), the profiles show the following features: (1) specific activities of³²Si (³²Si/SiO₂ ratios) are lowest at intermediate depths, and (2) on an average the surface specific activities are higher, by 2–4 times, than the bottom water values. These data are consistent with generation of the highest specific activity³²Si waters at the surface, where Si concentrations are lowest and precipitation adds cosmogenic³²Si scavenged from the troposphere. Rapid removal of biogenic silica to the water-sediment interface, without much dissolution during transit, leads to the second regime of high³²Si specific activities.The³²Si inventories in the water column in the latitude belt 27°N-27°S are in the range (1–1.4) × 10⁻² dpm³²Si/cm², which is consistent with the expected fallout of cosmogenic³²Si. However, the³²Si column inventories south of 40°S are higher by a factor of 5–7, whereas the corresponding Si inventories increase by only a factor of 3. This excess³²Si in the Southern Ocean cannot be explained by direct fallout from the stratosphere or by melting of Antarctic snow and ice. Instead, this excess is maintained primarily by the southward deep-water transport of³²Si dissolved from sinking particulates.