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.     

Thermodynamic characterization of the partitioning of iron between soluble and colloidal species in the Atlantic Ocean

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.     

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.     

Analytical perspective on trace element species of interest in exploration

Analysis of soil and sediment samples, using selective extraction methods to distinguish different phases, is of particular interest in exploration geochemistry to locate deeply buried mineral deposits. There are various mechanisms of binding labile elements in the secondary environment, including physical and chemical sorption, precipitation, chelation and complexation. Phases present in soils and sediments which are likely to scavenge ‘free' elements include amorphous Mn and Fe oxides, the humic and fulvic components of humus, and clays. This paper reviews these forms of trace elements and the methods in current use to quantify them. Examples of precision data, both for control and survey samples, are given with respect to trace elements dissolved from the ‘soluble organic' component of humus, Mn oxides and amorphous Fe oxides. The high sensitivity of inductively coupled plasma mass spectrometry (ICP–MS) is required to measure accurately and precisely a large suite of trace elements, especially where only small fractions of elements are dissolved by such leaches as the commercially available Enzyme and MMI (Mobile Metal Ion) extractions. The relative standard deviations (RSD) obtained for 33 elements (e.g. Ag, Cd, In, I) in the standard reference sample (SRM), TILL-2, are in the range 0.5–8% for the hydroxylamine hydrochloride (NH₂OH·HCl) leach designed to extract hydrous Fe and Mn oxides. The corresponding RSDs for elements in the reactive Mn oxide phase extracted by the Enzyme leach are in the range 3–19% except for some trace elements at levels close to detection limit (e.g. Cd, Bi). The RSDs obtained for field duplicates are inferior to those for analytical replicates (i.e. sample splits), probably a reflection of different concentrations of the host phase. In one soil survey, the Fe extracted by a 0.25 M NH₂OH·HCl leach ranged conservatively from 0.2 to 1.7% whereas the Mn extracted by the Enzyme leach varied extensively, from 0.3 to >999 ppm. In contrast, precision, at 1–7% RSD, for field duplicates was found to be comparable with that for both analytical duplicates and the SRM, LKSD-4, for elements associated with the humic and fulvic component of humus samples sieved to <177 μm.     

环境植物样品中铜铅锌铁锰的测定

将环境植物样品在４００─５００℃灰化，用硝酸、氢氟酸和高氯酸分解，用盐酸（１＋１）提取，控制２％─３％的盐酸介质，用火焰原子吸收分光光度法测定环境植物样品中的微量铜、铅、锌、铁、锰。该方法简单、快速、可靠。对环境植物标准样品的测定结果理想。     

Change in the magnetic properties of bituminous coal intruded by an igneous dike, Dutch Creek Mine, Pitkin County, Colorado

Magnetization measurements have been made on natural coke–coal samples collected at various distances from a felsic porphyry dike in a coal seam in Dutch Creek Mine, Colorado to help characterize the nature and distribution of the iron-bearing phases. The magnetization passes through a maximum at the coke-to-coal transition about 31 cm from the dike contact. The magnetic measurements support the geochemical data indicating that magmatic fluids along with a high-temperature gas pulse moved into the coal bed. Interaction of the magmatic fluids with the coal diminished the reducing power of the thermal gas pulse from the dike to a point about 24 cm into the coal. The hot reducing gas penetrated further and produced a high temperature (400–525°C) zone (at about 31 cm) just ahead of the magmatic fluids. Metallic iron found in this zone is the principal cause of the observed high magnetization. Beyond this zone, the temperature was too low to alter the coal significantly.     

A synthesis of iron deposits in the eastern Tianshan,NW China

The northern Xinjiang region is one of the most significant iron metallogenic provinces in China.Iron deposits are found mainly within three regions:the Altay,western Tianshan,and eastern Tianshan orogenic belts.Previous studies have elaborated on the genesis of Fe deposits in the Altay orogenic belt and western Tianshan.However,the geological characteristics and mineralization history of iron deposits in the eastern Tianshan are still poorly understood.In this paper I describe the geological characteristics of iron deposits in the eastern Tianshan,and discuss their genetic types as well as metallogenic-tectonic settings,Iron deposits are preferentially distributed in central and southern parts of the eastern Tianshan.The known iron deposits in the eastern Tianshan show characteristics of magmatic Fe-Ti-V(e.g.,Weiya and Niumaoquan),sedimentary-metamorphic type(e.g.,Tianhu),and iron skarn(e.g.,Hongyuntan).In addition to the abovementioned iron deposits,many iron deposits in the eastern Tianshan are hosted in submarine volcanic rocks with well-developed skarn mineral assemblages.Their geological characteristics and magnetite compositions suggest that they may belong to distal skarns.SIMS zircon U-Pb analyses suggest that the Fe-Ti oxide ores from Niumaoquan and Weiya deposits were formed at 307.7±1.3 Ma and 242.7±1.9 Ma,respectively.Combined with available isotopic age data,the timing of Fe mineralization in the eastern Tianshan can be divided into four broad intervals:Early Ordovician-Early Silurian(476-438 Ma),Carboniferous(335-303 Ma),Early Permian(295-282 Ma),and Triassic(ca.243 Ma).Each of these episodes corresponds to a period of subduction,post-collision,and intraplate tectonics during the Paleozoic and Mesozoic time.     

Determination of picomolar iron in seawater by double Mg(OH)2 precipitation isotope dilution high-resolution ICPMS

A low-blank pre-concentration procedure is described for the analysis of picomolar iron (Fe) in seawater by isotope dilution high-resolution inductively coupled plasma mass-spectrometry (HR-ICPMS). The procedure uses a two-step Mg(OH)₂ co-precipitation procedure to extract Fe from a 50 ml seawater sample into a 100 μl 4% nitric acid (HNO₃) solution followed by HR-ICPMS measurement. The high pre-concentration ratio ( 500:1) achieved by the procedure minimizes the Fe blank due to ICPMS instrumental Fe background and results in a detection limit of  2 pM and a precision of  4% at the 50 pM Fe level. The measurement of a low-Fe seawater sample spiked with gravimetric Fe standard shows that the method can clearly distinguish 0.01 nM Fe from 0.02 nM Fe in seawater with high accuracy. The method is demonstrated by the analysis of dissolved Fe in the equatorial Pacific Ocean.     

磁铁石英岩型铁矿岩芯光谱编录研究

 对河北省昌黎县闫庄铁矿床的磁铁石英岩型铁矿石261件样品进行了光谱反射率测量，并与其铁含量进行了相关关系研究，目 的是对钻孔岩芯编录的新方法即高光谱岩芯编录在此类矿床中的可行性进行分析。研究结果表明，铁矿石反射率较低，一般为5%~20% ，铁离子的吸收峰主要表现在400~1 100 nm范围内，铁矿石中铁含量与850~900 nm的反射率均值呈现显著指数负相关关系，为高光谱 岩芯编录在此类矿床中的可行性提供了理论依据和技术途径。