Iron and Sulfur Chemistry in a Stratified Lake: Evidence for Iron-Rich Sulfide Complexes

A four month study of a man-made lake used for hydroelectric power generation in northeastern Pennsylvania USA was conducted to investigate seasonal anoxia and the effects of sulfide species being transported downstream of the power generation equipment. Water column analyses show that the system is iron-rich compared to sulfide. Total Fe(II) concentrations in the hypolimnion are typically at least twice the total sulfide levels. In situ voltammetric analyses show that free Fe(II) as [Fe(H₂O)₆]²⁺ or free H₂S as H₂S/HS^- are either not present or at trace levels and that iron-rich sulfide complexes are present. From the in situ data and total Fe(II) and H₂S measurements, we infer that these iron-rich sulfide complexes may have stoichiometries such as Fe₂SH³⁺ (or polymeric forms of this and other stoichiometries). These iron-rich sulfide complexes appear related to dissolution of the iron-rich FeS mineral, mackinawite, because IAP calculations on data from discrete bottle samples obtained from bottom waters are similar to the pK_sp of mackinawite. Soluble iron-sulfide species are stable in the absence of O₂ (both in lake waters and the pipeline) and transported several miles during power generation. However, iron-sulfide complexes can react with O₂ to oxidize sulfide and can also dissociate releasing volatile H₂S when the waters containing them are exposed to the atmosphere downstream of the powerplant. Sediment analyses show that the lake is rich in oxidized iron solids (both crystalline and amorphous). Fe concentrations in FeS solids are low (<5 μmole/gr_{dry wt}) and the pyrite concentration ranges from about equal to the solid FeS to 30 times the solid FeS concentration. The degree of pyritization is below 0.12 indicating that pyrite formation is limited by free sulfide, which can react with the iron-rich sulfide complexes.     

The Global Paleomonsoon as seen through speleothem records from Asia and the Americas

The regional monsoons of the world have long been viewed as seasonal atmospheric circulation reversal—analogous to a thermally-driven land-sea breeze on a continental scale. This conventional view of monsoons is now being integrated at a global scale and accordingly, a new paradigm has emerged which considers regional monsoons to be manifestations of global-scale seasonal changes in response to overturning of atmospheric circulation in the tropics and subtropics, and henceforth, interactive components of a singular Global Monsoon (GM) system. The paleoclimate community, however, tends to view ‘paleomonsoon’ (PM), largely in terms of regional circulation phenomena. In the past decade, many high-quality speleothem oxygen isotope (δ¹⁸O) records have been established from the Asian Monsoon and the South American Monsoon regions that primarily reflect changes in the integrated intensities of monsoons on orbital-to-decadal timescales. With the emergence of these high-resolution and absolute-dated records from both sides of the Equator, it is now possible to test a concept of the ‘Global-Paleo-Monsoon’ (GPM) on a wide-range of timescales. Here we present a comprehensive synthesis of globally-distributed speleothem δ¹⁸O records and highlight three aspects of the GPM that are comparable to the modern GM: (1) the GPM intensity swings on different timescales; (2) their global extent; and (3) an anti-phased inter-hemispheric relationship between the Asian and South American monsoon systems on a wide range of timescales.     

Large bio-geographical shifts in the north-eastern Atlantic Ocean: From the subpolar gyre, via plankton, to blue whiting and pilot whales

Pronounced changes in fauna, extending from the English Channel in the south to the Barents Sea in the north-east and off Greenland in the north-west, have occurred in the late 1920s, the late 1960s and again in the late 1990s. We attribute these events to exchanges of subarctic and subtropical water masses in the north-eastern North Atlantic Ocean, associated with changes in the strength and extent of the subpolar gyre. These exchanges lead to variations in the influence exerted by the subarctic or Lusitanian biomes on the intermediate faunistic zone in the north-eastern Atlantic. This strong and persistent bottom-up bio-physical link is demonstrated using a numerical ocean general circulation model and data on four trophically connected levels in the food chain – phytoplankton, zooplankton, blue whiting, and pilot whales. The plankton data give a unique basin-scale depiction of these changes, and a long pilot whale record from the Faroe Islands offers an exceptional temporal perspective over three centuries. Recent advances in simulating the dynamics of the subpolar gyre suggests a potential for predicting the distribution of the main faunistic zones in the north-eastern Atlantic a few years into the future, which might facilitate a more rational management of the commercially important fisheries in this region.     

Major Cretaceous volcanic province in southern Rockall Trough

A group of three large curvilinear ridges, called the Barra Volcanic Ridge System, has been mapped in the acoustic basement of southern Rockall Trough. Typically, each ridge is about 2 km high and 20 km wide at its base. A crudely-layered acoustic character, moderate density but high strength of magnetisation point to a volcanic-sedimentary (ash?) composition for the ridges. Seismic continuity with the acoustic basement of the rest of Rockall Trough suggests that the trough basement is of similar composition. An age for the ridges of Lower Cretaceous is indicated by well ties and consideration of regional geology. Volumetrically, the ridges are on the scale of hot spot features such as the Wyville-Thomson Ridge.     

North African climate variability. Part 2: Tropical circulation systems

Summary Tropical North African climate variability is investigated using a Sahel rainfall index and streamflow of the Nile River in the 20^th century. The mechanisms that govern tropical North Africa climate are diagnosed from NCEP reanalysis data in the period 1958–1998: spatially – using composite and correlation analysis, and temporally – using wavelet co-spectral analysis. The Sahelian climate is characterised by a decadal rhythm, whilst the mountainous eastern and equatorial regions exhibit interannual cycles. ENSO-modulated zonal circulations over the Atlantic/Pacific sector are important for decadal variations, and create a climatic polarity between South America and tropical North Africa as revealed through upper-level velocity potential and convection patterns. A more localised N–S shift in convection between the Sahel and Guinea coast is associated with the African Easterly Jet.     

Using Statistical Downscaling to Quantify the GCM-Related Uncertainty in Regional Climate Change Scenarios： A Case Study of Swedish Precipitation

There are a number of sources of uncertainty in regional climate change scenarios. When statistical downscaling is used to obtain regional climate change scenarios, the uncertainty may originate from the uncertainties in the global climate models used, the skill of the statistical model, and the forcing scenarios applied to the global climate model. The uncertainty associated with global climate models can be evaluated by examining the differences in the predictors and in the downscaled climate change scenarios based on a set of different global climate models. When standardized global climate model simulations such as the second phase of the Coupled Model Intercomparison Project （CMIP2） are used, the difference in the downscaled variables mainly reflects differences in the climate models and the natural variability in the simulated climates. It is proposed that the spread of the estimates can be taken as a measure of the uncertainty associated with global climate models. The proposed method is applied to the estimation of global-climate-model-related uncertainty in regional precipitation change scenarios in Sweden. Results from statistical downscaling based on 17 global climate models show that there is an overall increase in annual precipitation all over Sweden although a considerable spread of the changes in the precipitation exists. The general increase can be attributed to the increased large-scale precipitation and the enhanced westerly wind. The estimated uncertainty is nearly independent of region. However, there is a seasonal dependence. The estimates for winter show the highest level of confidence, while the estimates for summer show the least.     

Postglacial history of alpine vegetation,fire, and climate from Laguna de Río Seco,Sierra Nevada,southern Spain

The Sierra Nevada of southern Spain is a landscape with a rich biological and cultural heritage. The range was extensively glaciated during the late Pleistocene. However, the postglacial paleoecologic history of the highest range in southern Europe is nearly completely unknown. Here we use sediments from a small lake above present treeline – Laguna de Río Seco at 3020 m elevation – in a paleoecological study documenting over 11,500 calendar years of vegetation, fire and climate change, addressing ecological and paleoclimatic issues unique to this area through comparison with regional paleoecological sequences. The early record is dominated by Pinus pollen, with Betula, deciduous Quercus, and grasses, with an understory of shrubs. It is unlikely that pine trees grew around the lake, and fire was relatively unimportant at this site during this period. Aquatic microfossils indicate that the wettest conditions and highest lake levels at Laguna de Río Seco occurred before 7800 cal yr BP. This is in contrast to lower elevation sites, where wettest conditions occurred after ca 7800. Greater differences in early Holocene seasonal insolation may have translated to greater snowpack and subsequently higher lake levels at higher elevations, but not necessarily at lower elevations, where higher evaporation rates prevailed. With declining seasonality after ca 8000 cal yr BP, but continuing summer precipitation, lake levels at the highest elevation site remained high, but lake levels at lower elevation sites increased as evaporation rates declined. Drier conditions commenced regionally after ca 5700 cal yr BP, shown at Laguna de Río Seco by declines in wetland pollen, and increases in high elevation steppe shrubs common today (Juniperus, Artemisia, and others). The disappearance or decline of mesophytes, such as Betula from ca 4000 cal yr BP is part of a regional depletion in Mediterranean Spain and elsewhere in Europe from the mid to late Holocene. On the other hand, Castanea sativa increased in Laguna de Río Seco record after ca 4000 cal yr BP, and especially in post-Roman times, probably due to arboriculture. Though not as important at high than at low elevations, fire occurrence was elevated, particularly after ca 3700 years ago, in response to regional human population expansion. The local and regional impact of humans increased substantially after ca 2700 years ago, with the loss of Pinus forest within the mountain range, increases in evidence of pasturing herbivores around the lake, and Olea cultivation at lower elevations. Though human impact was not as extensive at high elevation as at lower elevation sites in southern Iberia, this record confirms that even remote sites were not free of direct human influence during the Holocene.     

Muscovite dehydration melting: Reaction mechanisms,microstructures, and implications for anatexis

Dehydration melting of muscovite in metasedimentary sequences is the initially dominant mechanism of granitic melt generation in orogenic hinterlands. In dry (vapour-absent) crust, muscovite reacts with quartz to produce K-feldspar, sillimanite, and monzogranitic melt. When water vapour is present in excess, sillimanite and melt are the primary products of muscovite breakdown, and any K-feldspar produced is due to melt crystallization. Here we document the reaction mechanisms that control nucleation and growth of K-feldspar, sillimanite, and silicate melt in the metamorphic core of the Himalaya, and outline the microstructural criteria used to distinguish peritectic K-feldspar from K-feldspar grains formed during melt crystallization. We have characterized four stages of microstructural evolution in selected psammitic and pelitic samples from the Langtang and Everest regions: (a) K-feldspar nucleates epitaxially on plagioclase while intergrowths of fibrolitic sillimanite and the remaining hydrous melt components replace muscovite. (b) In quartzofeldspathic domains, K-feldspar replaces plagioclase by K⁺–Na⁺ cation exchange, while melt and intergrowths of sillimanite+quartz form in the aluminous domains. (c) At 7–8 vol.% melt generation, the system evolves from a closed to open system and all phases coarsen by up to two orders of magnitude, resulting in large K-feldspar porphyroblasts. (d) Preferential crystallization of residual melt on K-feldspar porphyroblasts and coarsened quartz forms an augen gneiss texture with a monzogranitic-tonalitic matrix that contains intergrowths of sillimanite+tourmaline+muscovite+apatite. Initial poikiloblasts of peritectic K-feldspar trap fine-grained inclusions of quartz and biotite by replacement growth of matrix plagioclase. During subsequent coarsening, peritectic K-feldspar grains overgrow and trap fabric-aligned biotite, resulting in a core to rim coarsening of inclusion size. These microstructural criteria enable a mass balance of peritectic K-feldspar and sillimanite to constrain the amount of free H₂O present during muscovite dehydration. The resulting modal proportion of K-feldspar in the Himalayan metamorphic core requires vapour-absent conditions during muscovite dehydration melting and leucogranite formation, indicating that the generation of large volumes of granitic melts in orogenic belts is not necessarily contingent on an external source of fluids.     

Behaviour of radiogenic Pb in zircon during ultrahigh-temperature metamorphism: an ion imaging and ion tomography case study from the Kerala Khondalite Belt,southern India

Zircon crystals from a locally charnockitized Paleoproterozoic high-K metagranite from the Kerala Khondalite Belt (KKB) of southern India have been investigated by high-spatial resolution secondary ion mass spectrometry analysis of U–Th–Pb and rare earth elements (REE), together with scanning ion imaging and scanning ion tomography (depth-profiled ion imaging). The spot analyses constrain the magmatic crystallization age of the metagranite to ca. 1,850 Ma, with ultrahigh-temperature (UHT) metamorphism occurring at ca. 570 Ma and superimposed charnockite formation at ca. 520–510 Ma, while the ion imaging reveals a patchy distribution of radiogenic Pb throughout the zircon cores. Middle- to heavy-REE depletion in ca. 570 Ma zircon rims suggests that these grew in equilibrium with garnet and therefore date the UHT metamorphism in the KKB. The maximum apparent ²⁰⁷Pb/²⁰⁶Pb age obtained from the unsupported radiogenic Pb concentrations is also consistent with formation of the Pb patches during this event. The superimposed charnockitization event appears to have caused additional Pb-loss in the cores and recrystallization of the rims. The results of depth-profiling of the scanning ion tomography image stack show that the Pb-rich domains range in size from <5 nm to several 10 nm (diameter if assumed to be spherical). The occurrence of such patchy Pb has previously been documented only from UHT metamorphic zircon, where it likely results from annealing of radiation-damaged zircon. The formation of a discrete, heterogeneously distributed and subsequently immobile Pb phase effectively arrests the normal Pb-loss process seen at lower grades of metamorphism.     

Seismic velocity-ratio in the crust and uppermost mantle in southeast Wellington province,New Zealand

The regional variation of the seismic velocity-ratio () over a 200 km long traverse has been studied by means of microearthquake surveys. The Wadati-plot method is used with a minimum of four P and S arrivals for each of 49 earthquakes. The area as a whole is found to be characterized by a value of 1.74–1.76 for earthquakes of depth 12–40 km, except in a 50 km long section near Wellington, where is low at 1.60. This low has been attributed to the fault zones in the region. A small change of is observed between the upper crust (5 km) and lower crust (12 km), but there is no change of between the lower crust and uppermost mantle.