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.     

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     

Study of fluoride in polluted and unpolluted estuarine environments

Mindhola River estuary, which receives industrial waste containing high concentrations of fluoride, and Purna River estuary, which is free from fluoride contamination, have been investigated. While fluoride behaved conservatively in Purna River estuary, significant deviation from the theoretical dilution line (TDL) in the chlorinity range 0·5–8‰ was observed in Mindhola River estuary due to the externally added fluoride which largely remained in solution. The excess of fluroide over the theoretically calculated value was at a maximum around a chlorinity of 3‰. High natural fluoride content of the river waters resulted in F/Cl ratios exceeding 300 × 10⁻⁵ at low chlorinities. The ratio decreased rapidly with increasing chlorinity and the value near to that of seawater was observed at chlorinities above 14‰.     

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.     

虾蟹海产品香味的前体物质的加热变化

本文研究了虾蟹海产品香味的前体物质在加热前后的变化。实验结果表明：对虾和蟹肌肉中的糖原和不饱和脂肪酸在加热前后含量下降，糖原是Ｍａｉｌｌａｒｄ反应的基础物质．不饱和脂肪酸是虾蟹肌肉香味中羰基化合物的前体物质。虾蟹肌肉中主要积累的核苷酸成分ＡＭＰ在加热后减少，而肌肉提取物中的游离氨基酸和结合氨基酸，特别是疏水氨基酸含量均增加。     

The application of isotopic and biogeochemical markers to the study of the biochemistry of organic matter in a macrotidal estuary, the Loire, France

The biogeochemistry of organic matter in a macrotidal estuary, the Loire, France, has been studied for two years during different seasons. Both particulate matter and sediment have been sampled in the riverine zone, in the maximum turbidity zone and in the ocean near the river mouth. Two techniques have been used: carbon isotopic ratio determination and analysis of lipid-marker signatures in the n-alkane, n-alkene and fatty acid series. For the period corresponding to the output of the maximum turbidity zone in the ocean, the complete change of organic matter, continental in nature in the inner estuary, pure marine in the outer estuary is well illustrated by the decrease of δ¹³C values and of carbon preference index of n-alkanes. Input sources of organic matter by continental plants, plankton and micro-organisms are discussed from biogeochemical-marker analyses data along with the processes of accumulation of particles and their evolution with the season. Some criteria for evidencing the nature of various organic-matter pools are assessed and compared in different chemical-marker series as follows: high molecular weight n-alkanes and fatty acids, perylene for continental imprints, polyunsaturated 18-, 20- and 22-carbon fatty acids, n-C₁₇, n-alkenes and squalene for algae imprints, branched iso and anteiso fatty acids, Δ11-C_18:1 for microbial imprints.     

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.     

藻类分子生物技术两年评─—与藻类活性物质研究有关的生物技术

根据１９９２年６月－１９９４年６月国内外发表资料，评述海洋藻类活性物质研究的生物技术及最新成果。认为，海洋生物活性物质研究的重心正转向与海洋生物技术有关的研究。运用生物技术筛选、提取并生产藻类活性物质已经成为这一领域的主流。综合文献表明，藻类活性物质的生物技术正走向成熟，大量的活性物质被发现，光生物反应器将成为主要的下游生产技术，通过藻类基因工程生产药物已初现端倪。     

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.