From nappe stacking to exhumation: Cretaceous tectonics in the Apuseni Mountains (Romania)

International Journal of Earth Sciences - New Ar–Ar muscovite and Rb–Sr biotite age data in combination with structural analyses from the Apuseni Mountains provide new constraints on...     

Paragenesis and geochemistry of ore minerals in the epizonal gold deposits of the Yangshan gold belt,West Qinling,China

Six epizonal gold deposits in the 30-km-long Yangshan gold belt, Gansu Province are estimated to contain more than 300 t of gold at an average grade of 4.76 g/t and thus define one of China's largest gold resources. Detailed paragenetic studies have recognized five stages of sulfide mineral precipitation in the deposits of the belt. Syngenetic/diagenetic pyrite (Py₀) has a framboidal or colloform texture and is disseminated in the metasedimentary host rocks. Early hydrothermal pyrite (Py₁) in quartz veins is disseminated in metasedimentary rocks and dikes and also occurs as semi-massive pyrite aggregates or bedding-parallel pyrite bands in phyllite. The main ore stage pyrite (Py₂) commonly overgrows Py₁ and is typically associated with main ore stage arsenopyrite (Apy₂). Late ore stage pyrite (Py₃), arsenopyrite (Apy₃), and stibnite occur in quartz ± calcite veins or are disseminated in country rocks. Post-ore stage pyrite (Py₄) occurs in quartz ± calcite veins that cut all earlier formed mineralization. Electron probe microanalyses and laser ablation-inductively coupled plasma mass spectrometry analyses reveal that different generations of sulfides have characteristic of major and trace element patterns, which can be used as a proxy for the distinct hydrothermal events. Syngenetic/diagenetic pyrite has high concentrations of As, Au, Bi, Co, Cu, Mn, Ni, Pb, Sb, and Zn. The Py₀ also retains a sedimentary Co/Ni ratio, which is distinct from hydrothermal ore-related pyrite. Early hydrothermal Py₁ has high contents of Ag, As, Au, Bi, Cu, Fe, Sb, and V, and it reflects elevated levels of these elements in the earliest mineralizing metamorphic fluids. The main ore stage Py₂ has a very high content of As (median value of 2.96 wt%) and Au (median value of 47.5 ppm) and slightly elevated Cu, but relatively low values for other trace elements. Arsenic in the main ore stage Py₂ occurs in solid solution. Late ore stage Py₃, formed coevally with stibnite, contains relatively high As (median value of 1.44 wt%), Au, Fe, Mn, Mo, Sb, and Zn and low Bi, Co, Ni, and Pb. The main ore stage Apy₂, compared to late ore stage arsenopyrite, is relatively enriched in As, whereas the later Apy₃ has high concentrations of S, Fe, and Sb, which is consistent with element patterns in associated main and late ore stage pyrite generations. Compared with pyrite from other stages, the post-ore stage Py₄ has relatively low concentrations of Fe and S, whereas As remains elevated (2.05～3.20 wt%), which could be interpreted by the substitution of As^? for S in the pyrite structure. These results suggest that syngenetic/diagenetic pyrite is the main metal source for the Yangshan gold deposits where such pyrite was metamorphosed at depth below presently exposed levels. The ore-forming elements were concentrated into the hydrothermal fluids during metamorphic devolatilization, and subsequently, during extensive fluid–rock interaction at shallower levels, these elements were precipitated via widespread sulfidation during the main ore stage.     

The carbon isotopic response of algae, (cyano)bacteria, archaea and higher plants to the late Cenomanian perturbation of the global carbon cycle: Insights from biomarkers in black shales from the Cape Verde Basin (DSDP Site 367)

The stable carbon isotopic compositions of free and sulfur (S)-bound biomarkers derived from algae, (cyano)bacteria, archaea and higher plants and total organic carbon (TOC) during the first phase of the late Cenomanian/Turonian oceanic anoxic event (OAE) were measured in black shales deposited in the southern proto-Atlantic Ocean in the Cape Verde basin (DSDP Site 367) to determine the response of these organisms to this major perturbation of the global carbon cycle resulting from widespread burial of marine organic matter. The average positive isotope excursions of TOC and biomarkers varied from 5.1‰ to 8.3‰. The δ¹³C values were cross correlated to infer potential common sources of biomarkers. This revealed common sources for C₃₁ and C₃₂ hopanes but no 1:1 relationship for pristane and phytane. The correlation of δ¹³C_TOC with the δ¹³C value of sulfur (S)-bound phytane is the strongest. This is because S-bound phytane is derived from phytol that originates from all marine primary producers (algae and cyanobacteria) and thus represents a weighted average of their carbon isotopic compositions. The δ¹³C values of S-bound phytane and C₃₅ hopane were also used to estimate pCO₂ levels. Before the OAE burial event, pCO₂ levels are estimated to be ca. 1300 ppmv using both biomarkers and the independent maximum Rubisco fractionation factors. At times of maximum organic carbon burial rates during the OAE, reconstructed pCO₂ levels are estimated to be ca. 700 ppmv. However, compared to other C/T OAE sections the positive isotope excursion of S-bound phytane is also affected by an increased production during the OAE. When we compensate for this, we arrive at pCO₂ levels around 1000 ppmv, a reduction of ca. 25%. This indicates that burial of organic matter can have a large effect on atmospheric CO₂ levels.     

Dissolved and labile concentrations of Cd, Cu, Pb, and Zn in the South Fork Coeur d’Alene River, Idaho: Comparisons among chemical equilibrium models and implications for biotic ligand models

In order to evaluate thermodynamic speciation calculations inherent in biotic ligand models, the speciation of dissolved Cd, Cu, Pb, and Zn in aquatic systems influenced by historical mining activities is examined using equilibrium computer models and the diffusive gradients in thin films (DGT) technique. Several metal/organic-matter complexation models, including WHAM VI, NICA-Donnan, and Stockholm Humic model (SHM), are used in combination with inorganic speciation models to calculate the thermodynamic speciation of dissolved metals and concentrations of metal associated with biotic ligands (e.g., fish gills). Maximum dynamic metal concentrations, determined from total dissolved metal concentrations and thermodynamic speciation calculations, are compared with labile metal concentrations measured by DGT to assess which metal/organic-matter complexation model best describes metal speciation and, thereby, biotic ligand speciation, in the studied systems. Results indicate that the choice of model that defines metal/organic-matter interactions does not affect calculated concentrations of Cd and Zn associated with biotic ligands for geochemical conditions in the study area, whereas concentrations of Cu and Pb associated with biotic ligands depend on whether the speciation calculations use WHAM VI, NICA-Donnan, or SHM. Agreement between labile metal concentrations and dynamic metal concentrations occurs when WHAM VI is used to calculate Cu speciation and SHM is used to calculate Pb speciation. Additional work in systems that contain wide ranges in concentrations of multiple metals should incorporate analytical speciation methods, such as DGT, to constrain the speciation component of biotic ligand models.     

Supercritical gas sorption on moist coals

The effect of moisture on the CO₂ and CH₄ sorption capacity of three bituminous coals from Australia and China was investigated at 55 °C and at pressures up to 20 MPa. A gravimetric apparatus was used to measure the gas adsorption isotherms of coal with moisture contents ranging from 0 to about 8%. A modified Dubinin–Radushkevich (DR) adsorption model was found to fit the experimental data under all conditions. Moisture adsorption isotherms of these coals were measured at 21 °C. The Guggenheim–Anderson–de Boer (GAB) model was capable of accurately representing the moisture isotherms over the full range of relative pressures.Moist coal had a significantly lower maximum sorption capacity for both CO₂ and CH₄ than dry coal. However, the extent to which the capacity was reduced was dependent upon the rank of the coal. Higher rank coals were less affected by the presence of moisture than low rank coals. All coals exhibited a certain moisture content beyond which further moisture did not affect the sorption capacity. This limiting moisture content was dependent on the rank of the coal and the sorbate gas and, for these coals, corresponded approximately to the equilibrium moisture content that would be attained by exposing the coal to about 40–80% relative humidity. The experimental results indicate that the loss of sorption capacity by the coal in the presence of water can be simply explained by volumetric displacement of the CO₂ and CH₄ by the water. Below the limiting moisture content, the CO₂ sorption capacity reduced by about 7.3 kg t^− 1 for each 1% increase in moisture. For CH₄, sorption capacity was reduced by about 1.8 kg t^− 1 for each 1% increase in moisture.The heat of sorption calculated from the DR model decreased slightly on addition of moisture. One explanation is that water is preferentially attracted to high energy adsorption sites (that have high energy by virtue of their electrostatic nature), expelling CO₂ and CH₄ molecules.     

Sulfur biogeochemical cycling and novel Fe-S mineralization pathways in a tidally re-flooded wetland

Sulfur biogeochemical cycling and associated Fe-S mineralization processes exert a major influence over acidity dynamics, electron flow and contaminant mobility in wetlands, benthic sediments and groundwater systems. While S biogeochemical cycling has been studied intensively in many environmental settings, relatively little direct information exists on S cycling in formerly drained wetlands that have been remediated via tidal re-flooding. This study focuses on a tidal wetland that was drained in the 1970s (causing severe soil and water acidification), and subsequently remediated by controlled re-flooding in 2002. We examine reduction rates and Fe-S mineralization at the tidal fringe, 7 years after the commencement of re-flooding. The initial drainage of the wetland examined here caused in-situ pyrite (FeS₂) oxidation, resulting in the drained soil layers being highly acidic and rich in -bearing Fe(III) minerals, including jarosite (KFe₃(SO₄)₂(OH)₆). Tidal re-flooding has neutralized much of the previous acidity, with the pore-water pH now mostly spanning pH 5-7. The fastest rates of in-situ reduction (up to ∼300 nmol cm⁻³ day⁻¹) occur within the inter-tidal zone in the near-surface soil layers (to ∼60 cm below ground surface). The reduction rates correlate with pore-water dissolved organic C concentrations, thereby suggesting that electron donor supply was the predominant rate determining factor. Elemental S was a major short-term product of reduction, comprising up to 69% of reduced inorganic S in the near-surface soil layers. This enrichment in elemental S can be partly attributed to interactions between biogenic H₂S and jarosite - a process that also contributed to enrichment in pore-water Fe²⁺ (up to 55 mM) and (up to 50 mM). The iron sulfide thiospinel, greigite (Fe₃S₄), was abundant in near-surface soil layers within the inter- to sub-tidal zone where tidal water level fluctuations created oscillatory redox conditions. There was evidence for relatively rapid pyrite re-formation within the re-flooded soil layers. However, the results indicate that pyrite re-formation has occurred mainly in the lower formerly drained soil layers, whereas the accumulation of elemental S and greigite has been confined towards the soil surface. The discovery that pyrite formation was spatially decoupled from that of elemental S and greigite challenges the concept that greigite is an essential precursor required for sedimentary pyrite formation. In fact, the results suggest that greigite and pyrite may represent distinct end-points of divergent Fe-S mineralization pathways. Overall, this study highlights novel aspects of Fe-S mineralization within tidal wetlands that have been drained and re-flooded, in contrast to normal, undisturbed tidal wetlands. As such, the long-term biogeochemical trajectory of drained and acidified wetlands that are remediated by tidal re-flooding cannot be predicted from the well-studied behaviour of normal tidal wetlands.     

An agent-based model for risk-based flood incident management

Effective flood incident management (FIM) requires successful operation of complex, interacting human and technological systems. A dynamic agent-based model of FIM processes has been developed to provide new insights which can be used for policy analysis and other practical applications. The model integrates remotely sensed information on topography, buildings and road networks with empirical survey data to fit characteristics of specific communities. The multiagent simulation has been coupled with a hydrodynamic model to estimate the vulnerability of individuals to flooding under different storm surge conditions, defence breach scenarios, flood warning times and evacuation strategies. A case study in the coastal town of Towyn in the United Kingdom has demonstrated the capacity of the model to analyse the risks of flooding to people, support flood emergency planning and appraise the benefits of flood incident management measures.     

How many is enough? Determining optimal count totals for ecological and palaeoecological studies of testate amoebae

Testate amoebae are increasingly used in ecological and palaeoecological studies of wetlands. To characterise the amoeba community a certain number of individuals need to be counted under the microscope. To date, most studies have aimed for 150 individuals, but that sample size is not based on adequate evidence. When testate amoeba concentrations are low, it can be difficult or impossible to reach this total. The impacts of lower count totals have never been seriously scrutinised. We investigated the impact of count size on number of taxa identified, quantitative inferences of environmental variables and the strength of the links between amoebae and environmental data in the context of predicting depth to water table. Low counts were simulated by random selection of individuals from four existing datasets. Results show progressively diminishing returns by all criteria as count size increases from low numbers to counts of 150. A higher count is required to identify all taxa than to adequately characterise the community for transfer function inference. We suggest that in most cases, it will be a more efficient use of time to count a greater number of samples to a lower count. While a count of 50 individuals may be sufficient for some samples from some sites we recommend that counts of 100 individuals should be sufficient for most samples. Counts need only be increased to 150 or more where the aim is to identify relatively minor, but still potentially ecologically relevant community changes. This approach will help reduce lack of replication and low resolution, which are common limitations in testate amoeba-based palaeoecological and ecological studies.