Dissolution and depletion of ferromagnesian minerals from Holocene tephra layers in an acid bog,New Zealand,and implications for tephra correlation

This study examines the depletion of ferromagnesian silicate minerals from a sequence of thin, distal, mainly rhyolitic tephra layers of Holocene age preserved in an acid peat bog (Kopouatai), North Island, New Zealand. The rate of such depletion has been fast, as indicated by the complete loss of biotite from one tephra layer (Kaharoa Tephra), in which it is normally dominant, in only ca. 770 yr. Chemical dissolution is advocated as the likely cause for the depletion, with amphiboles and other mineral grains commonly showing etch pits, microcaves, and other characteristic surface solution features. Theoretical thermodynamic and kinetic models show a marked increase in the rate of dissolution of all ferromagnesian minerals under conditions of low pH (< 4), but that where silica concentrations in solution are high the relative proportions of minerals remaining are unaffected. However, where concentrations of dissolved silica are low, as in most bog environments, the relative proportions of ferromagnesian minerals are affected as well as absolute amounts being decreased. Amphiboles are depleted relative to pyroxenes, consistent with kinetic studies. The results show that the identification and correlation of tephras on the basis of relative abundances of ferromagnesian minerals alone may be unreliable, and emphasise the need to use multiple criteria in such studies.     

The solubility of iron sulphides in synthetic and natural waters at ambient temperature

A critical evaluation of literature values for the solubility products, K _sp ^NBS = [Fe²⁺][HS^–] Fe²⁺ HS^– (H _NBS ⁺ )^–1, of various iron sulphide phases results in consensus values for the pKs of 2.95 ± 0.1 for amorphous ferrous sulphide, 3.6 ± 0.2 for mackinawite, 4.4 ± 0.1 for greigite, 5.1 ± 0.1 for pyrrhotite, 5.25 ± 0.2 for troilite and 16.4 ± 1.2 for pyrite.Where the analogous ion activity products have been measured in anoxic freshwaters in which there is evidence for the presence of solid phase FeS, the values lie within the range of 2.6–3.22, indicating that amorphous iron sulphide is the controlling phase. The single value for a groundwater of 2.65 (2.98 considering carbonate complexation) agrees. In seawater four values range between 3.85 to 4.2, indicating that mackinawite or greigite may be the controlling phase. The single low value of 2.94 is in a situation where particularly high fluxes of Fe (II) and S (–II) may result in the preferential precipitation of amorphous iron sulphide. Formation of framboidal pyrite in these sulphidic environments may occur in micro-niches and does not appear to influence bulk concentrations. Calculations show that the formation of Fe₂S₂ species probably accounts for very little of the iron or sulphide in most natural waters. Previously reported stability constants for the formation of Fe (HS)₂ and (Fe (HS)₃)^– are shown to be suspect, and these species are also thought to be negligible in natural waters. In completely anoxic pore waters polysulphides also have a negligible effect on speciation, but in tidal sediments they may reach appreciable concentrations and lead to the direct formation of pyrite. Concentrations of iron and sulphide in pore waters can be controlled by the more soluble iron sulphide phase. The change in the IAP with depth within the sediment may reflect ageing of the solid phase or a greater flux of Fe (II) and S (–II) nearer the sediment surface. This possible kinetic influence on the value of IAPs has implications for their use in geochemical studies involving phase formation.     

Diagenesis, palaeoclimate and tectono-sedimentary influences on clay mineralogy and stable isotopes from Upper Cretaceous marine successions of the Basque-Cantabrian Basin (N Spain)

Clay mineralogy and whole-rock stable isotopes (δ¹⁸O and δ¹³C) of Upper Cretaceous marly sediments on the Basque-Cantabrian Basin have been integrated to determine the main effects of diagenesis, palaeoclimate and tectono-sedimentary factors in sections belonging to deep- (Barrika) and platform-marine (Isla de Castro, Villamartín and Olazagutía) settings.The mean values for the clay assemblages and δ¹⁸O exhibit notable differences among the sections, partially explainable by the influence of diagenesis. The Barrika sediments, with more diagenetically advanced illite-smectite (I-S) mixed-layer (R1, 70% illite), authigenic chlorite, and low δ¹⁸O (−4.05‰ PDB), experienced higher diagenetic grade than Isla de Castro and Olazagutía, which have R0 I-S (20% illite) and heavier δ¹⁸O. Villamartín was also affected by higher diagenesis than Isla de Castro and Olazagutía, given the occurrence of R1 I-S (60% illite) and low δ¹⁸O (−4.11‰ PDB). However, the absence of other clays in Villamartín (e.g. authigenic chlorite) is indicative of less diagenetic grade than Barrika. These results show the useful integration of clay mineralogy and stable isotopes to detect different diagenetic grades in distinct marine successions of the same basin.Despite being influenced by diagenesis, the clay mineralogy partially preserves its inherited signature. This allows detection of major contents of I-S and mica, and minor kaolinite, interpreted as indicative of warm palaeoclimatic conditions. High kaolinite content in Villamartín and absence of kaolinite in Isla de Castro, though, are considered to be a product of neither diagenesis nor palaeoclimatic influences. Instead, tectono-sedimentary causes, related to unsuitable conditions for clay formation and transport from the local source areas, contributed to original clay differences. The inferred effects of diagenesis, palaeoclimate and tectono-sedimentary factors make this work important to show the potentially great variety of controls on the clay mineralogy of marine sections, which are often uncritically treated in studies concerning the Late Cretaceous.     

Origin of Fe-Ti Oxide Ores in Mafic Intrusions: Evidence from the Panzhihua Intrusion, SW China

Economic concentrations of Fe–Ti oxides occur as massive,conformable lenses or layers in the lower part of the Panzhihuaintrusion, Emeishan Large Igneous Province, SW China. Mineralchemistry, textures and QUILF equilibria indicate that oxidesin rocks of the intrusion were subjected to extensive subsolidusre-equilibration and exsolution. The primary oxide, reconstructedfrom compositions of titanomagnetite in the ores and associatedintergrowths, is an aluminous titanomagnetite (Usp₄₀) with 40wt % FeO, 34 wt % Fe₂O₃, 16·5 wt % TiO₂, 5·3 wt% Al₂O₃, 3·5 wt % MgO and 0·5 wt % MnO. This compositionis similar to the bulk composition of the oxide ore, as inferredfrom whole-rock data. This similarity strongly suggests thatthe ores formed from accumulation of titanomagnetite crystals,not from immiscible oxide melt as proposed in earlier studies.The occurrence of oxide ores in the lower parts of the Panzhihuaintrusion is best explained by settling and sorting of densetitanomagnetite in the ferrogabbroic parental magma. This magmamust have crystallized Fe–Ti oxides relatively early andabundantly, and is likely to have been enriched in Fe and Tibut poor in SiO₂. These features are consistent with fractionationof mantle-derived melts under relatively high pressures (10kbar), followed by emplacement of the residual magma at 5 kbar.This study provides definitive field and geochemical evidencethat Fe–Ti oxide ores can form by accumulation in ferrogabbro.We suggest that many other massive Fe–Ti oxide depositsmay have formed in a similar fashion and that high concentrationsof phosphorus or carbon, or periodic fluctuation of fO₂ in themagma, are of secondary importance in ore formation. KEY WORDS: ELIP; Fe–Ti oxide ore; layered intrusion; Panzhihua; QUILF     

Usefulness of geological,mineralogical, chemical and chemometric analytical techniques in exploitation and profitability studies of iron mines and their associated elements

Due to the high number of variables involved in mine profitability studies, it is often very difficult to establish connections among them in order to provide a blend of market saleable quality products. In this sense, analytical chemistry together with chemometry are essential and indispensable disciplines to tackle these studies. The aim of this work was to demonstrate the utility of these disciplines to carry out optimization studies of iron mines. For this purpose, one of the most important iron mines of the Iberian Peninsula was chosen, sited in the mountain range of Sierra Menera, near the location of Ojos Negros (Teruel, Spain). Geological, mineralogical and chemical composition of 148 samples was analyzed, corresponding to different depths of three drill holes (named TE1, TE2 and TE3). In particular, aspects concerning to chemical composition are very important, since the mean contents of certain elements, such as phosphorus, sodium and potassium, should be restricted to the established limits to prevent that companies can drive back the raw material if they do not fulfil the necessary requirements. On the other hand, the large number of analysed samples drove us to use a statistical processing of the data. Among other aspects, it provides a way to find possible connections among a high number of variables and classify samples into compositional groups sharing similar composition, in order to limit the mineralised area and to obtain enough information about the amount of those chemical elements associated to iron ores. Data obtained from all these analytical techniques were in good agreement and provide a methodology that can be of wide interest applied to different geological studies.     

中国大别山东南缘首次发现大坝陨坑构造

简介首次在大别山东南缘安徽省境内发现的大坝陨坑构造。经初步评价,知陨坑呈椭圆形,长轴呈北北东向,长约19km,短轴长约12km,最大坑深约2km,是一个有中央隆起区的复杂型陨坑。在卫片上陨坑显示环形影像,地貌形态为一洼地。陨坑基座保存尚好,可对它直观和追索陨坑构造边界。形成于230Ma左右的各类撞击变质岩石系列齐全,其中含有柯石英等典型的撞击变质矿物及撞击碎理等超微构造,特别是在陨坑基座内壁普遍发现有鉴别陨坑构造最可靠的标志——干裂自角砾岩,都证明大坝环形影像是一个典型的陨星撞击坑构造。它的发现,具有很大的科学及经济意义,对今后褶皱山区寻找和研究陨坑构造具有示范和指导作用,同时大大丰富了建设大别山世界地质公园的地质依据。无庸置疑此发现将促进大别山旅游业的发展及陨星撞击科普知识的传播。     

Oceanic iron fertilization: one of strategies for sequestration atmospheric CO2

Carbon cycle is connected with the most important environmental issue of Global Change.As one of the major carbon reservoirs, oceans play an important part in the carbon cycle. In recent years, iron seems to give us a good news that oceanic iron fertilization could stimulate biological productivity as CO2 sink of human-produced CO2. Oceanic iron fertilization experiments have verified that adding iron into high nutrient low chlorophyll (HNLC) seawaters can increase phytoplankton production and export organic carbon, and hence increase carbon sink of anthropogenic CO2, to reduce global warming. In sixty days, the export organic carbon could reach 10 000 times for adding iron by model prediction and in situ experiment, i.e. the atmospheric CO2 uptake and inorganic carbon drawdown in upper seawaters also have the same magnitude. Therefore, oceanic iron fertilization is one of the strategies for increasing carbon sink of anthropogenic CO2. The paper is focused on the iron fertilization, especially in situ o     

A community-wide intercomparison exercise for the determination of dissolved iron in seawater

The first large-scale international intercomparison of analytical methods for the determination of dissolved iron in seawater was carried out between October 2000 and December 2002. The exercise was conducted as a rigorously “blind” comparison of 7 analytical techniques by 24 international laboratories. The comparison was based on a large volume (700 L), filtered surface seawater sample collected from the South Atlantic Ocean (the “IRONAGES” sample), which was acidified, mixed and bottled at sea. Two 1-L sample bottles were sent to each participant. Integrity and blindness were achieved by having the experiment designed and carried out by a small team, and overseen by an independent data manager. Storage, homogeneity and time-series stability experiments conducted over 2.5 years showed that inter-bottle variability of the IRONAGES sample was good (< 7%), although there was a decrease in iron concentration in the bottles over time (0.8–0.5 nM) before a stable value was observed. This raises questions over the suitability of sample acidification and storage.     

Manganese and iron distributions off central California influenced by upwelling and shelf width

In July 2002, a combination of underway mapping and discrete profiles revealed significant along-shore variability in the concentrations of manganese and iron in the vicinity of Monterey Bay, California. Both metals had lower concentrations in surface waters south of Monterey Bay, where the shelf is about 2.5 km wide, than north of Monterey Bay, where the shelf is about 10 km wide. During non-upwelling conditions over the northern broad shelf, dissolvable iron concentrations measured underway in surface waters reached 3.5 nmol L⁻¹ and dissolved manganese reached 25 nmol L⁻¹. In contrast, during non-upwelling conditions over the southern narrow shelf, dissolvable iron concentrations in surface waters were less than 1 nmol L⁻¹ and dissolved manganese concentrations were less than 5 nmol L⁻¹. A pair of vertical profiles at 1000 m water depth collected during an upwelling event showed dissolved manganese concentrations of 10 decreasing to 2 nmol L⁻¹, and dissolvable iron concentrations of 12–20 nmol L⁻¹ in the upper 100 m in the north, compared to 3.5–2 nmol L⁻¹ Mn and 0.6 nmol L⁻¹ Fe in the upper 100 m in the south, suggesting the effect of shelf width influences the chemistry of waters beyond the shelf.These observations are consistent with current understanding of the mechanism of iron supply to coastal upwelling systems: Iron from shelf sediments, predominantly associated with particles greater than 20 μm, is brought to the surface during upwelling conditions. We hypothesize that manganese oxides are brought to the surface with upwelling and are then reduced to dissolved manganese, perhaps by photoreduction, following a lag after upwelling.Greater phytoplankton biomass, primary productivity, and nutrient drawdown were observed over the broad shelf, consistent with the greater supply of iron. Incubation experiments conducted 20 km offshore in both regions, during a period of wind relaxation, confirm the potential of these sites to become limited by iron. There was no additional growth response when copper, manganese or cobalt was added in addition to iron. The growth response of surface water incubated with bottom sediment (4 nmol L⁻¹ dissolvable Fe) was slightly greater than in control incubations, but less than in the presence of 4 nmol L⁻¹ dissolved iron. This may indicate that dissolvable iron is not as bioavailable as dissolved iron, although the influence of additional inhibitory elements in the sediment cannot be ruled out.     

Responses of phytoplankton and heterotrophic bacteria in the northwest subarctic Pacific to in situ iron fertilization as estimated by HPLC pigment analysis and flow cytometry

To verify the hypothesis that the growth of phytoplankton in the Western Subarctic Gyre (WSG), which is located in the northwest subarctic Pacific, is suppressed by low iron (Fe) availability, an in situ Fe fertilization experiment was carried out in the summer of 2001. Changes over time in the abundance and community structure of phytoplankton were examined inside and outside an Fe patch using phytoplankton pigment markers analyzed by high-performance liquid chromatography (HPLC) and flow cytometry (FCM). In addition, the abundance of heterotrophic bacteria was also investigated by FCM. The chlorophyll a concentration was initially ca. 0.9 μg l⁻¹ in the surface mixed layer where diatoms and chlorophyll b-containing green algae (prasinophytes and chlorophytes) were predominant in the chlorophyll biomass. After the iron enrichment, the chlorophyll a concentration increased up to 9.1 μg l⁻¹ in the upper 10 m inside the Fe patch on Day 13. At the same time, the concentration of fucoxanthin (a diatom marker) increased 45-fold in the Fe patch, and diatoms accounted for a maximum 69% of the chlorophyll biomass. This result was consistent with a microscopic observation showing that the diatom Chaetoceros debilis had bloomed inside the Fe patch. However, chlorophyllide a concentrations also increased in the Fe patch with time, and reached a maximum of 2.2 μg l⁻¹ at 5 m depth on Day 13, suggesting that a marked abundance of senescent algal cells existed at the end of the experiment. The concentration of peridinin (a dinoflagellate marker) also reached a maximum 24-fold, and dinoflagellates had contributed significantly (>15%) to the chlorophyll biomass inside the Fe patch by the end of the experiment. Concentrations of 19′-hexanoyloxyfucoxanthin (a prymnesiophyte marker), 19′-butanoyloxyfucoxanthin (a pelagophyte marker), and alloxanthin (a cryptophyte marker) were only incremented a few-fold increment inside the Fe patch. On the contrary, chlorophyll b concentration reduced to almost half of the initial level in the upper 10 m water column inside the Fe patch at the end of the experiment. A decrease with time in the abundance of eukaryotic ultraphytoplankton (<ca. 5 μm in size), in which chlorophyll b-containing green algae were possibly included was also observed by FCM. Overall, our results indicate that Fe supply can dramatically alter the abundance and community structure of phytoplankton in the WSG. On the other hand, cell density of heterotrophic bacteria inside the Fe patch was maximum at only ca. 1.5-fold higher than that outside the Fe patch. This indicates that heterotrophic bacteria abundance was little respondent to the Fe enrichment.