The solubility of iron sulphides in synthetic and natural waters at ambient temperature   总被引：1，自引：1，他引：0  

W. Davison 《Aquatic Sciences - Research Across Boundaries》1991,53(4):309-329

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.  相似文献   

电感耦合等离子体发射光谱法同时测定玻璃中铝钙铁钾镁钠钛硫   总被引：2，自引：2，他引：0  

杜米芳 《岩矿测试》2008,27(2):146-148

通过选择分析谱线、处理样品方法和消除干扰因素等实验,建立了电感耦合等离子体发射光谱法同时测定玻璃中的Al2O3、CaO、Fe2O3、K2O、MgO、Na2O、TiO2和SO3的方法,克服了利用常规化学法测定玻璃中各氧化物步骤繁琐、耗时长、工作量大的不足。方法的回收率为95.0%~103.0%,精密度(RSD,n=10)为0.20%~1.72%。方法具有快速、简便、线性范围宽等优点,分析误差满足常规化学分析法的要求。用于钠钙硅玻璃及其制品的分析,结果令人满意。  相似文献   

Anoxic nitrification: Evidence from Humber Estuary sediments (UK)   总被引：3，自引：0，他引：3  

Rebecca Bartlett  Robert J.G. Mortimer  Katherine Morris 《Chemical Geology》2008,250(1-4):29-39

Conventional understanding of the nitrogen cycle in marine sediments has changed in recent years with the discovery of an alternative pathway for ammonia oxidation via the reduction of manganese oxides (during anoxic nitrification). In anoxic sediments, the potential for manganese oxides to serve as oxidant for nitrification may be considerable yet previous work on manganese-rich sediments has suggested anoxic nitrification may not be significant. In this study, the potential for anoxic nitrification in a range of sediment types was investigated. Laboratory incubation of sediment from three sites on the Humber Estuary, a microbially diverse environment, showed anoxic accumulation of nitrate, nitrite and dinitrogen gas, with and without the addition of synthetic manganese oxides. Incubation experiments confirmed anoxic nitrification as microbially mediated, with heat-killed controls yielding negative results. The anoxic nitrification reaction significantly depleted ammonia concentrations, and occurred simultaneously with manganese-, iron- and sulphate reduction, and methanogenesis. Taken in conjunction with other studies, results suggest anoxic nitrification may not only be dependent on total manganese concentrations but on manganese dynamics. Anoxic nitrification may be explained as a non-steady state reaction, dependent on the recent stability of a sediment system. Physical perturbation of sediments may cause the redistribution and/or introduction of manganese oxides and promote anoxic nitrification. The significance and persistence of anoxic nitrification is likely to depend on the frequency and magnitude of sediment perturbation, which explains why the reaction varies so widely across studied sites, and why it may not occur in some manganese-rich sediment.  相似文献   

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

M. Dolores Petit-Dominguez  M. Isabel Rucandio  Almudena Galan-Saulnier  Rosario Garcia-Gimenez 《Journal of Geochemical Exploration》2008

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.  相似文献   

Oceanic iron fertilization: one of strategies for sequestration atmospheric CO₂   总被引：2，自引：1，他引：2  

Song Jinming 《海洋学报(英文版)》2003,22(1):57-68

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  相似文献   

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

Andrew R. Bowie  Eric P. Achterberg  Peter L. Croot  Hein J.W. de Baar  Patrick Laan  James W. Moffett  Simon Ussher  Paul J. Worsfold 《Marine Chemistry》2006

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.  相似文献   

Manganese and iron distributions off central California influenced by upwelling and shelf width   总被引：4，自引：1，他引：4  

Zanna Chase  Kenneth S. Johnson  Virginia A. Elrod  Joshua N. Plant  Steve E. Fitzwater  Lisa Pickell  Carol M. Sakamoto 《Marine Chemistry》2005,95(3-4):235-254

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.  相似文献   

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   总被引：3，自引：0，他引：3  

Koji Suzuki  Akira Hinuma  Hiroaki Saito  Hiroshi Kiyosawa  Hongbin Liu  Toshiro Saino  Atsushi Tsuda 《Progress in Oceanography》2005,64(2-4):167

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.  相似文献   

Thermodynamic characterization of the partitioning of iron between soluble and colloidal species in the Atlantic Ocean   总被引：2，自引：1，他引：2  

Jay T. Cullen  Bridget A. Bergquist  James W. Moffett 《Marine Chemistry》2006,98(2-4):295-303

Recent electrochemical measurements have shown that iron (Fe) speciation in seawater is dominated by complexation with strong organic ligands throughout the water column and have provided important thermodynamic information about these compounds. Independent work has shown that iron exists in both soluble and colloidal fractions in the Atlantic Ocean. Here we have combined these approaches in samples collected from a variety of regimes within the Atlantic Ocean. We measured the partitioning of Fe between soluble (< 0.02 μm) and colloidal (0.02 to 0.4 μm) size classes and characterized the concentrations and conditional stability constants of Fe ligands within these size classes. Results suggest that equilibrium partitioning of Fe between soluble and colloidal ligands is partially responsible for the distribution of Fe between soluble and colloidal size classes. However, a significant fraction of the colloidal Fe was inert to ligand exchange as soluble Fe concentrations were generally lower than values predicted by a simple equilibrium partitioning model.In surface waters, strong ligands with conditional stability constants of 10¹³ relative to total inorganic Fe appeared to dominate speciation in both the soluble and colloidal fractions. In deep waters these ligands were absent, and instead we found ligands with stability constants 12–15 fold smaller that were predominantly in the soluble pool. Nevertheless, significant levels of colloidal Fe were found in these samples, which we inferred must be inert to coordination exchange.  相似文献   

Primary production in the eastern tropical Pacific: A review   总被引：2，自引：12，他引：2  

J. Timothy Pennington  Kevin L. Mahoney  Victor S. Kuwahara  Dorota D. Kolber  Ruth Calienes  Francisco P. Chavez   《Progress in Oceanography》2006,69(2-4):285

The eastern tropical Pacific includes 28 million km² of ocean between 23.5°N and S and Central/South America and 140°W, and contains the eastern and equatorial branches of the north and South Pacific subtropical gyres plus two equatorial and two coastal countercurrents. Spatial patterns of primary production are in general determined by supply of macronutrients (nitrate, phosphate) from below the thermocline. Where the thermocline is shallow and intersects the lighted euphotic zone, biological production is enhanced. In the eastern tropical Pacific thermocline depth is controlled by three interrelated processes: a basin-scale east/west thermocline tilt, a basin-scale thermocline shoaling at the gyre margins, and local wind-driven upwelling. These processes regulate supply of nutrient-rich subsurface waters to the euphotic zone, and on their basis we have divided the eastern tropical Pacific into seven main regions. Primary production and its physical and chemical controls are described for each.Enhanced rates of macronutrient supply maintains levels of primary production in the eastern tropical Pacific above those of the oligotrophic subtropical gyres to the north and south. On the other hand lack of the micronutrient iron limits phytoplankton growth (and nitrogen fixation) over large portions of the open-ocean eastern tropical Pacific, depressing rates of primary production and resulting in the so-called high nitrate-low chlorophyll condition. Very high rates of primary production can occur in those coastal areas where both macronutrients and iron are supplied in abundance to surface waters. In these eutrophic coastal areas large phytoplankton cells dominate; conversely, in the open-ocean small cells are dominant. In a ‘shadow zone’ between the subtropical gyres with limited subsurface ventilation, enough production sinks and decays to produce anoxic and denitrified waters which spread beneath very large parts of the eastern tropical Pacific.Seasonal cycles are weak over much of the open-ocean eastern tropical Pacific, although several eutrophic coastal areas do exhibit substantial seasonality. The ENSO fluctuation, however, is an exceedingly important source of interannual variability in this region. El Niño in general results in a depressed thermocline and thus reduced rates of macronutrient supply and primary production. The multi-decadal PDO is likely also an important source of variability, with the ‘El Viejo’ phase of the PDO resulting in warmer and lower nutrient and productivity conditions similar to El Niño.On average the eastern tropical Pacific is moderately productive and, relative to Pacific and global means, its productivity and area are roughly equivalent. For example, it occupies about 18% of the Pacific Ocean by area and accounts for 22–23% of its productivity. Similarly, it occupies about 9% of the global ocean and accounts for 10% of its productivity. While representative, these average values obscure very substantial spatial and temporal variability that characterizes the dynamics of this tropical ocean.  相似文献