Annual variation of atmospheric carbonyl sulfide in the marine atmosphere in the Southern Indian Ocean

Measurements of the concentrations of carbonyl sulfide (COS) in the marine atmosphere were made over a period of two years in the southern Indian Ocean (Amsterdam Island, 37°50 S–77°31 E; March 1987–February 1988 and April 1989–February 1990). The mean atmospheric COS concentration for the whole period was 475±48 pptv (n=544). Atmospheric COS concentrations show no significant seasonal variation with a summer to winter ratio of 1.05. Taking into account the observed variability of the atmospheric COS concentration (10%), a value of 1.4 yr is estimated as a lower limit for the atmospheric COS lifetime. A comparison of the COS data at Amsterdam Island with those obtained in the Southern Hemisphere in the past 12 yr does not reveal any significant trend in the tropospheric background COS mixing ratio.     

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.     

Age and depositional environment of the Draa Sfar massive sulfide deposit, Morocco

The Draa Sfar mineralization consists of two main stratabound orebodies, Sidi M’Barek and Tazacourt, located north and south of the Tensift River (“Oued Tessift”), respectively. Each orebody is comprised by at least two massive sulfide lenses. The hosting rocks are predominantly black shales, although minor rhyolitic rocks are also present in the footwall to the southern orebody. Shales, rhyolitic volcanic rocks, and massive sulfides are all included into the Sarhlef Series, which is recognized as one of the main stratigraphic units of the Moroccan Variscan Meseta. Hydrothermal activity related with an anomalous thermal gradient, together with a high sedimentation rate in a tectonically driven pull-apart marine basin, favored the accumulation of organic-rich mud in the deepest parts of the basin and the sedimentary environment suitable for massive sulfide deposition and preservation. This took place by replacement of the hosting unlithified wet mud below the sediment–water interface. Geochemical data suggest a sedimentary environment characterized by oxic water column and anoxic sediment pile with the redox boundary below the sediment–water interface. The low oxygen availability within the sediment pile inhibited oxidation and pyritization of pyrrhotite. Biostratigraphic analysis, based on the palynological content of the hosting black shales, restricts the age of the sulfides to the Asbian substage (mid-Mississippian). This age is consistent with earlier geochronological constraints.     

Mineralogy and composition of Kuroko deposits from northeastern Honshu and their possible modern analogues from the Izu-Ogasawara (Bonin) Arc south of Japan: Implications for mode of formation

The Kuroko deposits of NE Honshu are a key type deposit for the study of volcanogenic massive sulfide deposits. However, these deposits have not been studied in detail since the early 1980's and knowledge of their mode of formation is now dated. In this study, we present the analysis of 12 samples of the Kuroko deposits, 12 samples of submarine hydrothermal minerals from the Sunrise deposit and 6 samples from Suiyo Seamount, both of which are located on the Izu-Ogasawara (Bonin) Arc, for 27 elements. For the Kuroko deposit, Cd>Sb>Ag>Pb>Hg>As>Zn>Cu are highly enriched, Au>Te>Bi>Ba>Mo are moderately enriched, In>Tl are somewhat enriched and Fe is not significantly enriched relative to the average continental crust. Within each of these deposits, a similar pattern of element associations is apparent: Zn–Pb with As, Sb, Cd, Ag, Hg, Tl and Au; Fe–Cu–Ba with As, Sb, Ag, Tl, Mo, Te and Au; Si–Ba with Ag and Au; CaSO₄. The enrichment of the chalcophilic elements in these deposits is consistent with hydrothermal leaching of these elements from the host rocks which are dominantly rhyolite–dacite in the case of the Kuroko deposits, rhyolite in the case of the Sunrise deposit and dacite–rhyolite in the case of the Suiyo Seamount deposit. However, this pattern of element enrichment is also similar to that observed in fumarolic gas condensates from andesitic volcanoes. This suggests that there may be a significant magmatic contribution to the composition of the hydrothermal fluids responsible for the formation of the Kuroko deposits, although it is not yet possible to quantify the relative contributions of these two sources of elements.The compositional data show that Sunrise and Suiyo Seamount deposits are much closer compositionally to the Kuroko deposits from NE Honshu than are the submarine hydrothermal deposits from the JADE site in the Okinawa Trough which contain, on average, significantly higher concentrations of Pb, Zn, Sb, As and Ag than each of these deposits. In spite of the greater similarity in tectonic setting of the Hokuroku Basin in which the Kuroko deposits formed to the Okinawa Trough (intracontinental rifted back-arc basin) compared to Myojin Knoll and Suiyo Seamount (active arc volcanoes), it appears that submarine hydrothermal deposits from Myojin Knoll and Suiyo Seamount are closer analogues of the Kuroko deposit than are those from the Okinawa Trough. The present data are consistent with the magmatic hydrothermal model for the formation of Kuroko-type deposits as formulated by Urabe and Marumo [Urabe, T., Marumo, K., 1991. A new model for Kuroko-type deposits of Japan. Episodes 14, 246–251].     

青海南部熔积岩的发现:对寻找VMS型矿床的重要启示

熔积岩指的是侵入、混合到未固结或弱固结的湿沉积物中的熔浆分解、原位形成的一类特殊岩石。正确地认识该类岩石,有利于增进人们对岩浆-水(沉积物)相互作用过程的理解,恢复古环境。在青海南部沱沱河地区发现了一套角砾为撕片状、锯齿状及浑圆状的安山岩,胶结物为铁硅质组合的特殊熔积岩。研究表明,该熔积岩的角砾为岩浆遇水后快速淬火、裂解的产物,铁硅质组合为海底喷气沉积形成的含铁建造;且安山岩与含铁建造发生混合时,含铁建造尚未固结。该套熔积岩的发现,改变了长期以来对开心岭铁矿为火山热液交代安山岩而形成的认识,对于在矿区寻找VMS型矿床、区域内寻找海底热水喷流沉积型矿床具有重要的启示意义。     

力马河镍矿Re-Os同位素研究

四川力马河镍矿是峨眉山大火成岩省一个重要的岩浆硫化物矿床。本文通过对其主要岩、矿石类型Re、Os及其同位素组成的分析,综合探讨了成矿岩体原始岩浆性质、矿石硫化物成因、成矿机制及Re-Os同位素等时线年龄。结果表明,力马河镍矿不同类型岩矿石样品初始Os同位素组成是不均一的,富硫化物的网脉状矿石及其选纯硫化物Os同位素组成初值差异较小,其等时线年龄为265±35 Ma、与岩体锆石SHRIMP年龄263±3 Ma基本相当;硫化物含量较低的岩、矿石样品间初始Os同位素组成差异较大,其表观等时线年龄大于成矿年龄。分析认为,岩矿样品初始Os同位素组成的不均一是由含较高放射成因187Os丰度的硫化物熔体和含较低放射成因187Os丰度的硅酸盐熔体不同比例混合造成的。混合模型分析表明,硫化物含量超过30％的矿石样品初始187Os/188Os基本接近,硫化物含量低于30％的岩矿石样品初始187Os/188Os随硫化物含量上的不同差异很大,为岩浆硫化物矿床Re-Os等时线年龄可能出现多组年龄解的现象提供了一种可能的解释。成矿岩体中含放射成因187Os丰度最低的岩石样品γOs（t=260Ma）在5左右、Cu/Pd比值在7000左右,表明是基本没有受到地壳混染及硫化物熔离影响的原始岩浆结晶分异产物,估计原始岩浆Os含量在1×10－9左右,为苦橄质岩浆。矿石硫化物Re/Os比值显著高于任何赋矿橄榄岩,γOs（t=260Ma）高达110左右,综合分析揭示了力马河镍矿硫化物为二次熔离成因,模式分析认为,矿石硫化物是由原始岩浆经历R=2000左右的硫化物熔离后、其亏损岩浆再经R=200左右的硫化物熔离形成,与二次熔离相对应,成矿岩浆也经历了两次混染作用,分别为上、下地壳7％左右的混染。     

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.     

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.