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.     

青岛文昌鱼的生活史──年龄、生长和死亡研究

于１９８９年８月－１９９０年７月对青岛文昌鱼的生活史进行研究。结果表明：（１）青岛文昌鱼种群由４个齿组组成，它至少生产４ａ以上，甚至可达６ａ左右。（２）在Ⅰ、Ⅱ齿时生长较快，平均年生长１３－１５ｍｍ，Ⅲ龄后生长速度减慢，即使同一年龄组的文晶鱼，在不同季节其生长速度也不同。（３）在冬春采集的文昌鱼中Ⅲ龄组的峰值较小。（４）繁殖季节过后，老龄文昌鱼因衰老而死亡。     

Rates of Deglaciation during the Last Glaciation and Holocene in the Cordillera Vilcanota-Quelccaya Ice Cap Region, Southeastern Perú

Moraine chronology is combined with digital topography to model deglacial rates of paleoglacier volumes in both the Huancané Valley on the west side of the Quelccaya Ice Cap and the Upismayo Valley on the northwest side of the Cordillera Vilcanota. The fastest rates of deglaciation (39×10⁻⁵ to 114×10⁻⁵ km³ yr⁻¹ and 112×10⁻⁵ to 247×10⁻⁵ km³ yr⁻¹ for each valley, respectively) were calculated for the most recent paleoglaciers, corresponding to the last few centuries. These results are consistent with observations in the Venezuelan Andes showing high rates of deglaciation since the Little Ice Age. These rates also fall within the range of 20th century rates of deglaciation measured on the Quelccaya Ice Cap (29×10⁻⁵ to 220×10⁻⁵ km³ yr⁻¹, Brecher and Thompson, 1993; Thompson, 2000). These results imply that rates of deglaciation may fluctuate significantly over time and that high rates of deglaciation may not be exclusive to the late 20th century. Equilibrium line altitude (ELA) depressions for the ice volumes of the last glaciation modeled here were computed as 230 m for the Quelccaya Ice Cap and 170 m for the Cordillera Vilcanota. Maximum ELA depressions are lower than previously published: <500 m for the Cordillera Vilcanota and <400 m for the Quelccaya Ice Cap. These lower values could imply a topographic control over paleoglacier extent.     

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.     

古气候演化特征、驱动与反馈及对现代气候变化研究的启示意义

古气候与现代气候变化研究如何有效结合,特别是古气候研究如何为理解现代气候变化过程提供背景条件、边界约束和理论框架,值得深入探讨。文章以现代、历史时期、全新世、晚第四纪和新生代为时间基线,回顾阐述了过去气候演变特征、成因机制及其对现代气候变化研究的启示意义,探讨了过去与现代气候变化融合研究中存在的不确定性。过去气候演化过程的研究,加深了人们对地球气候系统运行机制的理解。研究表明,各个时期中,地球气候经历了不同相位、幅度和速率的变化,气候系统各分量之间发生了复杂的相互作用,以地表温度为代表的地球表面热力环境演化是各不同阶段气候变化的基本表现形式。全球温度变化不仅受到太阳输出辐射、地球轨道参数和地球构造运动等的影响,而且与地球表层水圈中的海洋、冰冻圈中的大陆冰盖、生物圈中的海洋浮游生物和陆地植被,以及大气圈中的温室气体、粉尘气溶胶、水汽和云等活跃组分之间,存在着多尺度复杂反馈作用。在同一时间尺度上,气候系统分量的互馈通路可能是同向的、可比的,各分量之间的对应关系或具有一致性,研究结论对于预估未来气候变化有借鉴意义;但在不同时间尺度上,气候系统各分量之间的相互联系机制可能难有一致性和可比性,古今互鉴,就需要慎重。

     

Late Holocene environmental conditions in Coronation Gulf,southwestern Canadian Arctic Archipelago: evidence from dinoflagellate cysts,other non‐pollen palynomorphs,and pollen

Boxcore 99LSSL‐001 (68.095° N, 114.186° W; 211 m water depth) from Coronation Gulf represents the first decadal‐scale marine palynology and late Holocene sediment record for the southwestern part of the Northwest Passage. The record was studied for organic‐walled microfossils (dinoflagellate cysts, non‐pollen palynomorphs), pollen, terrestrial spores, and sediment characteristics. ²¹⁰Pb, ¹³⁷Cs, and three accelerator mass spectrometry ¹⁴C dates constrain the chronology. Three prominent palaeoenvironmental zones were identified. During the interval AD 1470–1680 (Zone I), the climate was warmer and wetter than at present, and environmental conditions were more favourable to biological activity and northward boreal forest migration, with reduced sea‐ice and a longer open‐water (growing) season. The interval AD 1680–1940 (Zone II) records sea‐ice increase, and generally cool, polar conditions during the Little Ice Age. During AD 1940–2000 (Zone III), organic microfossils indicate an extended open‐water season and decreased sea‐ice, with suggested amelioration surpassing that of Zone I. Although more marine studies are needed to place this record into an appropriate context, the succession from ameliorated (Zone I) to cooler, sea‐ice influenced conditions (Zone II) and finally to 20th‐century warming (Zone III) corresponds well with several terrestrial climatic records from the neighbouring mainland and Victoria Island, and with lower‐resolution marine records to the west. Copyright © 2011 John Wiley & Sons, Ltd.     

Geoarchaeological evidence on a Late Bronze Age earthquake,Ohrid Basin (North Macedonia)

Geoarchaeological investigations on the northeastern shore of Lake Ohrid revealed 3.5 m thick deepwater lacustrine sediments overlying terrestrial vegetation macrofossils, worked wood and abundant potsherds dated to the Late Bronze Age (LBA). Distinct contact of deepwater sediment with the sub-aerial weathered limestone bedrock point to a sudden increase in lake level. According to radiocarbon data, catastrophic flooding occurred shortly after 1214 yr bc. Because the area is located in a highly active seismic zone, we propose that this event was caused by tectonically induced, metre-scale coseismic subsidence related to faults bordering the Ohrid alluvial plain. Moreover, this event coincides well with a dramatic switch in the habitation and settlement strategy in the region. More important, however, is the finding that the age of the proposed massive tectonic event and change in habitation lies within the interval of the proposed ‘earthquake storm’ in the eastern Mediterranean dated to 1225–1175 bc. As the Ohrid-Korça zone belongs to the same tectonic province, a relationship between the abovementioned earthquakes and the proposed event can be expected. This research therefore might provide the first direct evidence of a large-scale earthquake event linkable to the LBA collapse of Europe's first urban civilisation in the Aegean.