Role of buffer layer in electronic structures of iron phthalocyanine molecules on Au(111)

We investigate the electronic structures of one and two monolayer iron phthalocyanine (FePc) molecules on Au(111) surfaces. The first monolayer FePc is lying flat on the Au(111) substrate, and the second monolayer FePc is tilted at ～15° relative to the substrate plane along the nearest neighbour [101^-] direction with a lobe downward to the central hole of the unit cell in the first layer. The structural information obtained by first-principles calculations is in agreement with the experiment results. Furthermore, it is demonstrated that the electronic structures of FePc molecules in one-monolayer FePc/Au(111) system are perturbed significantly, while the electronic structures of FePc molecules in the second monolayer in two-monolayer FePc/Au(111) system remain almost unchanged due to the screening of the buffer layer on Au(111).     

Leachable particulate iron in the Columbia River,estuary, and near-field plume

This study examines the distribution of leachable particulate iron (Fe) in the Columbia River, estuary, and near-field plume. Surface samples were collected during late spring and summer of 2004–2006 as part of four River Influence on Shelf Ecosystems (RISE) cruises. Tidal amplitude and river flow are the primary factors influencing the estuary leachable particulate Fe concentrations, with greater values during high flow and/or spring tides. Near the mouth of the estuary, leachable particulate Fe [defined as the particulate Fe solubilized with a 25% acetic acid (pH 2) leach containing a weak reducing agent to reduce Fe oxyhydroxides and a short heating step to access intracellular Fe] averaged 770 nM during either spring tide or high flow, compared to 320 nM during neap tide, low flow conditions. In the near-field Columbia River plume, elevated leachable particulate Fe concentrations occur during spring tides and/or higher river flow, with resuspended shelf sediment as an additional source to the plume during periods of coastal upwelling and spring tides. Near-field plume concentrations of leachable particulate Fe (at a salinity of 20) averaged 660 nM during either spring tide or high flow, compared to 300 nM during neap tide, low flow conditions. Regardless of tidal amplitude and river flow, leachable particulate Fe concentrations in both the river/estuary and near-field plume are consistently one to two orders of magnitude greater than dissolved Fe concentrations. The Columbia River is an important source of reactive Fe to the productive coastal waters off Oregon and Washington, and leachable particulate Fe is available for solubilization following biological drawdown of the dissolved phase. Elevated leachable Fe concentrations allow coastal waters influenced by the Columbia River plume to remain Fe-replete and support phytoplankton production during the spring and summer seasons.     

Sulfide intrusion in the tropical seagrasses Thalassia testudinum and Syringodium filiforme

Sulfur and oxygen dynamics in the seagrasses Thalassia testudinum and Syringodium filiforme and their sediments were studied in the US Virgin Islands (USVI) in order to explore sulfide intrusion into tropical seagrasses. Four study sites were selected based on the iron concentration in sediments and on proximity to anthropogenic nutrient sources. Meadow characteristics (shoot density, above- and below-ground biomass, nutrient content) were sampled along with sediment biogeochemistry. Sulfide intrusion was high in T. testudinum, as up to 96% of total sulfur in the plant was derived from sediment-derived sulfides. The sulfide intrusion was negatively correlated to the turnover of sulfides in the sediments regulated by both plant parameters and sediment sulfur pools. Sediment iron content played an indirect role by affecting sulfide turnover rates. Leaf production was negatively correlated with sulfide intrusion suggesting that active growth reduced sulfide intrusion. Sulfide intrusion was lower in S. filiforme (up to 44%) compared to T. testudinum consistent with a higher internal nighttime oxygen concentrations found for S. filiforme. When S. filiforme can take advantage of its ability to maintain high internal oxygen concentrations, as was the case on the USVI, it could increase its success in colonizing unvegetated disturbed sediments with potentially high sulfide concentrations.     

鲁西潘店地区矽卡岩型铁矿成矿规律初探

近年来,在鲁中隆起区西北部潘店地区的铁矿勘查工作取得了重大进展。该区发育有明显的航磁异常及航空重力异常,且具有"重磁同源性"特征;通过对航磁异常的分析,可分为李屯、潘店、大张和薛官屯4个次级磁异常。勘查工作表明,区内巨厚新生界覆盖层下发育有矽卡岩型铁矿床,总体表现为"地层、岩体和构造"联合控矿的特征,即铁矿体受控于奥陶纪马家沟群碳酸盐地层、中生代燕山晚期闪长岩体、以及地层与岩体接触处形成的各种类型(构造)接触带。区内铁矿体赋存位置多样,主要为接触带赋存式、断裂充填式、层间充填式、裂隙贯入式、捕虏体构造式等;其成矿时代为早白垩世(130~131Ma),与济南、莱芜、金岭地区矽卡岩型铁矿形成时代基本一致;铁矿物质主要来源于中—基性侵入岩体。在整体表现为具有(剩余)重力异常高值处、(化极)磁异常明显部位,以及高—低电阻率转换带的地段进行铁矿勘查工作较为有利。     

高分辨率航磁方法及在大冶铁矿区的应用

本文针对危机矿山深部及周边找矿的难度大、勘探周期短的特点,提出了一套以找矿为目的,集直升机大比例尺航空物探测量、数据处理、解释为一体的高分辨率航磁方法技术.这些方法包括硬架式直升机航磁测量方法、曲面位场处理方法、精细反演解释方法等.应用该方法在湖北黄石大冶铁矿中布钻,已有两孔见富磁铁矿及伴生的铜、金矿,见矿最大厚度为14.6m.因此,高分辨率航磁方法在危机矿山进一步挖潜工作中可以实现快速找矿目的.     

光照强度对隐藻吸收铁和磷的影响

在模拟条件下,通过深入研究光照强度对隐藻生长率的影响,以及不同光照强度下藻细胞对Fe和P的吸收差异,提出了光照强度控制藻细胞对营养元素的吸收,最终限制赤潮藻爆发性增殖的作用途径.研究表明,藻细胞的生长率与光照强度之间呈指数相关关系;隐藻生长的光饱和值与光半饱和值分别为150 μmol/(m2·s)和47 μmol/(m2·s);在低光照强度下藻细胞的生长率较低,但是藻细胞却需要吸收更多的Fe和P,以及Zn、Mn、Co和Mo等微量元素,在光照强度为10 μmol/(m2·s)时,藻细胞生长率仅为光照强度150 μmol/(m2·s)时的十分之一,而藻细胞对Fe和P的吸收量分别提高了1.5倍和1倍.这些研究结果为揭示导致赤潮常在光照良好天气后发生的根本原因提供了全新的认识.     

Phosphate mineral accumulation in lake sediment to form a secondary phosphate source: A case study in lake sediment around Eppawala Phosphate Deposit (EPD) in Sri Lanka

Global phosphorus scarcity will result in significant consequences for future food security with the depletion of current phosphate reserves.Therefore,exploration of new phosphorus sources is essential to address future phosphorus scarcity.The current study investigated the geochemical potential of lake sediment around the Eppawala Phosphate Deposit(EPD)in Sri Lanka to be used as a low-grade phosphorus source for agricultural purposes.Jaya-Ganga is a man-made water canal that drains through the EPD feeding three lakes,namely,upstream Ihalahalmilla Lake and Koon Lake,and downstream Kiralogama Lake with respect to the EPD.Three cores(cores A,B,and C)were collected from the above three lakes and major oxides and minerals distributions along the cores were analyzed.Notable high enrichment of phosphorus pentoxide(P2O5)content and high P2O5 solubility values were measured in the top 60 cm sediment layer in Core B and throughout the Core C compared to the Core A.This high enrichment of P2O5 content in the same sediment columns were confirmed by the comparison with the Upper Continental Crust(UCC)values and literature survey.According to the X-ray Diffraction(XRD)results,phosphate minerals,such as fluorapatite,crandallite,and millisite were abundantly found in the same sediment columns.Therefore,these phosphate minerals can be considered as pathfinding minerals for soluble phosphates in sediment cores.Thus,sediment with high P2O5 content and high solubility in downstream Kiralogama Lake showed the potential for application of these sediments as a direct phosphate source in agricultural purposes.Furthermore,the current study has introduced a new area of interest,i.e.,soil and sediments around major phosphate deposits,for the exploration of new phosphate sources to meet future phosphorus demand.     

The importance of iron speciation (Fe+2/Fe+3) in determining mineral assemblages: an example from the high‐grade aluminous metapelites of southeastern Madagascar

Metapelitic granulites from the Anosyen domain of southeastern Madagascar are exposed in three intercalated formations: the Amparihy, Bakika and Ihosy formations. Although mineralogically distinct from each other, the rocks from these formations show very similar bulk‐rock compositions when measured on a Fe_T basis. The preserved mineral assemblages thus do not reflect differences in the ratios of the main rock‐forming oxides (i.e. Al₂O₃:Fe_T:MgO), but instead reflect variations in the pre‐metamorphic oxidation state of the protolith rocks. These differences in oxidation state are manifested via differences in iron speciation – either Fe⁺² or Fe⁺³. The relatively reduced rocks of the Amparihy Formation preserve the assemblage bi–sp–sill–g–cd, which contrasts markedly with the mostly garnet and spinel‐absent bi–cd–sill–mt assemblages preserved in the strongly oxidized rocks of the Ihosy Formation. Compositionally intermediate rocks of the Bakika Formation are garnet bearing, but sillimanite‐absent, and contain the assemblage sp–g–cd–mag. Modelling of these rocks in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O system suggests that they evolved along a heating and cooling P–T path with only limited decompression accompanying cooling on the retrograde path. Peak temperatures and pressures of ～880–920 °C and 6–6.5 kbar are inferred for the majority of the Anosyen domain, with slightly lower peak temperatures (～840 °C) estimated in the extreme northwest of the area. The high‐temperature and relatively low‐pressure nature of metamorphism suggests high geothermal gradients existed during orogenesis, which in southern Madagascar is related to the amalgamation of Gondwana (580–520 Ma). Although metamorphic temperatures may have been augmented via thermal advection from the emplacement of the syn‐ to post‐tectonic Ambalavao suite, the high geothermal gradients nevertheless suggest thin and consequently hot lithosphere existed prior to orogenesis.     

Sunrise Hill unconformity: A newly discovered regional hiatus between Archaean granites and greenstones in the northeastern Pilbara Craton

Contacts between Archaean granites and greenstones in the northeastern part of the Pilbara Craton have been described as intrusive and tectonic. New field observations in the Shay Gap region demonstrate that greenstones of the Gorge Creek Group unconformably overlie the Muccan and Warrawagine batholiths. Regionally, the unconformity is marked by a persistent but relatively thin basal clastic sequence, locally with a granite boulder conglomerate, overlain by ore‐bearing banded iron‐formation, fine‐grained clastic rocks and chert. The granite basement is dated at 3443 ± 6 Ma. The precise age of the hiatus is unknown but its maximum effect might have been the removal of a substantial thickness of Early to Middle Archaean strata.     

Iron porphyrins in the Permian Kupferschiefer of the lower Rhine Basin, N.W. Germany

Immature samples of the Permian Kupferschiefer from the Lower Rhine Basin in N.W. Germany were analysed for tetrapyrrole pigment type and abundance. The sediment, thought to have been deposited in a marine regime with enhanced salinity, was found to contain high concentrations of metalloporphyrins. The porphyrins are complexed to nickel (Ni) and oxovanadium (V=0), but high abundances of iron (Fe) porphyrins were also detected using UV/visible spectroscopy and mass spectrometry. The presence in the latter of series of aetioporphyrins, cycloalkanoporphyrins, di-cycloalkanoporphyrins and benz-cycloalkanoporphyrins was confirmed by accurate mass measurements; HPLC co-injection of deoxophylloerythroetioporphyrin (C₃₂ DPEP) with the demetallated iron porphyrins indicated its presence in the sediment as an iron complex. The study provides the first evidence for the occurrence of Fe porphyrins in geological samples other than coals and lignites, and reports the highest concentrations in sedimentary organic matter to date.