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.     

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.     

Transformation of arsenic compounds in modern intertidal sediments of Iriomote Island, Japan

The arsenic accumulation process in intertidal sediments of Iriomote Island, Japan, is analyzed as a naturally balanced arsenic-fixation system. Major and minor element chemistry is analyzed by X-ray fluorescence photometry, mineralogy is investigated by X-ray diffractometry, and four arsenic compounds are characterized by hydrogen-generated atomic absorption photometry. It is found that arsenic is accumulated by iron hydroxides/oxides precipitated following the decomposition of humic acids in the shallower sediment, and is subsequently incorporated into iron sulfide minerals at depth. The arsenic is immobile during incorporation into arsenic-bearing phases, suggesting that arsenic is unlikely to be released into the porewater under natural conditions in early diagenesis. The formation and decomposition of arsenic-bearing organic compounds appear to be associated with the formation and decomposition of arsenic in oxyhydroxides/oxides, suggesting that microbial activity may play an important role in controlling the behavior of arsenic and arsenic-bearing phases in the sediment column.     

山东省莱州-安丘铁成矿带特征及找矿方向

莱州-安丘铁成矿带位于沂沭断裂带东侧,胶北隆起的西南部。成矿带呈NE向展布,长约100 km,宽10~20km。已知区内铁矿类型主要有沉积变质型、岩浆熔离型和岩浆期后热液型,成矿除受地层控制外,还与构造、岩浆活动关系密切。通过对地质和重、磁物理场的分析,确定不同成因类型铁矿的分布范围,并且划分出不同磁异常特征,指出今后的找矿方向。     

The Cihai diabase in the Beishan region,NW China: Isotope geochronology,geochemistry and implications for Cornwall-style iron mineralization

Diabase dykes in Cihai, Beishan region, NW China are spatially and temporally associated with ‘Cornwall-type’ iron deposits. U–Pb dating of zircons from a diabase dyke using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) yields an age of 128.5 ± 0.3 Ma, indicating an Early Cretaceous crystallization age. Most of the diabases show low Mg-numbers, suggesting evolved magmas. The diabase dykes show typical ophitic or sub-ophitic textures, and are dominantly composed of phenocrysts of plagioclase (40–50%) and clinopyroxene (30–45%), with minor and varying amounts of biotite and hornblende (1–5%), and minor disseminated magnetite (∼5%). Their mineralogy reflects magma differentiation under relatively low oxygen fugacity conditions. The diabase dykes are characterized by minor variation in SiO₂ (44.67–49.76 wt.%) and MnO (0.14–0.26 wt.%), but show a marked range of Al₂O₃ (10.66–14.21 wt.%), total Fe₂O₃ (9.52–13.88 wt.%), TiO₂ (0.66–2.82 wt.%) and relatively high MgO (4.87–9.29 wt.%) with an Mg# value [atomic Mg/(Mg + Fe²⁺)] of up to 66. The Cihai diabases possibly experienced fractional crystallization of olivine + clinopyroxene and minor crustal contamination during the differentiation process. Prominent negative Nb, Ta and Ti anomalies suggest derivation from subduction-modified mantle. Furthermore, the rocks have relatively unradiogenic Sr- and Nd-isotopic ratios. These characteristics probably reflect partial melting of a subduction component in the source mantle lithosphere through heat input from an upwelling asthenospheric mantle. Such processes probably occurred within an extensional setting during the Early Cretaceous in the Beishan area. The iron-rich fluids were derived from deep sources, and the iron ores were concentrated through a convection cell driven by temperature gradients established by the intrusion of the diabase sills. The combined processes of subduction-related enrichment in the source, shallow depth of emplacement, and the involvement of large-scale circulation of basinal brines from an evaporitic source are inferred to have contributed to the formation of the ‘Cornwall-type’ mineralization in Cihai.     

北京市铁矿资源特征及开发利用建议

从北京市铁矿资源的地质矿产特征,矿床类型及其分布情况,矿石类型及其利用情况以及资源储量特征出发,重点分析了北京市铁矿资源的基本情况,从而把北京市铁矿划分为3个矿集区：库西北、库东北、库南铁矿矿集区,并对目前北京市铁矿的开发利用情况进行了分析,指出库西北,库东北铁矿矿集区在确保区内矿山企业适度发展的前提下,宜限制开采,作为战略储备,库南铁矿矿集区可以适度发展。     

华北克拉通沉积变质型铁矿床的特征与预测评价模型

华北克拉通是我国面积最大、时代最古老的陆块,地质构造演化历史复杂,也是我国重要的铁矿资源分布区.本文在系统总结该区域成矿规律的基础上,利用GIS平台提取了多元成矿有利信息(变质建造、控矿构造、矿致磁异常、氧化铁异常、自然重砂信息).在此基础上,建立了沉积变质型铁矿床的找矿预测模型,并采用MRAS系统中的证据权模块进行矿产资源定量预测.按照后验概率的大小划分了两级区域有利成矿远景区,分别是冀东、辽东、五台-吕梁三个A级成矿远景区和大青山-色尔能腾山、鲁山-舞阳、鲁西三个B级成矿远景区.这些远景区与已知矿床(点)重叠或比邻,显示远景区具有较好的成矿条件和较大的成矿潜力,应在今后的找矿勘查工作中予以充分重视.     

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.     

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.     

Dissolved iron in the Australian sector of the Southern Ocean (CLIVAR SR3 section): Meridional and seasonal trends

We report measurements of dissolved iron (dFe, <0.4 μm) in seawater collected from the upper 300 m of the water column along the CLIVAR SR3 section south of Tasmania in March 1998 (between 42°S and 54°S) and November–December 2001 (between 47°S and 66°S). Results from both cruises indicate a general north-to-south decrease in mixed-layer dFe concentrations, from values as high as 0.76 nM in the Subtropical Front to uniformly low concentrations (<0.1 nM) between the Polar Front and the Antarctic continental shelf. Samples collected from the seasonal sea-ice zone in November–December 2001 provide no evidence of significant dFe inputs from the melting pack ice, which may explain the absence of pronounced ice-edge algal blooms in this sector of the Southern Ocean, as implied by satellite ocean-color images. Our data also allow us to infer changes in the dFe concentration of surface waters during the growing season. South of the Polar Front, a comparison of near-surface with subsurface (150 m depth) dFe concentrations in November–December 2001 suggests a net seasonal biological uptake of at least 0.14–0.18 nM dFe, of which 0.05–0.12 nM is depleted early in the growing season (before mid December). A comparison of our spring 2001 and fall 1998 data indicates a barely discernible seasonal depletion of dFe (0.03 nM) within the Polar Frontal Zone. Further north, most of our iron profiles do not exhibit near-surface depletions, and mixed-layer dFe concentrations are sometimes higher in samples from fall 1998 compared to spring 2001; here, the near-surface dFe distributions appear to be dominated by time-varying inputs of aerosol iron or advection of iron-rich subtropical waters from the north.