Simulation of sedimentary Ore-Forming processes: Concentration of Pb and Zn from brines into organic and Fe-bearing carbonate sediments

An experimental sedimentary system comprising a tank of 4 m³ capacity equipped for monitoring chemical, mineralogical, and biological changes has been used to investigate the mechanisms by which Pb and Zn may be removed from solution in sulphide-deficient brines and concentrated in sediments. In the experimental system, Pb and Zn together with ferric hydroxides (probably lepidocrosite), organic matter, and a variety of calcium and magnesium carbonate phases, were deposited from an aerobic, highly saline, Pb and Zn-rich brine supporting a vigorous growth of the green alga Chlorococcus sp. The resultant organic and Febearing carbonate sediments contained Pb up to 0.5% and Zn up to 1.0%. Overall concentration factors compared with the overlying brine were in the range 200 to 300. Pb was removed from solution mainly by coprecipitation with carbonate phases; the Pb content of the two major carbonate phases decreasing in the order aragonite to monohydrocalcite. Zn was deposited in association with the Fe-bearing minerals. Complexing of Pb and Zn by organic matter, and the direct precipitation of Pb and Zn carbonates and/or hydroxides made, at most, a secondary contribution to the overall concentration process.     

Geochemical history of a Lower Miocene lake,the Cypris Formation,Sokolov Basin,Czech Republic

The intracontinental Lower Miocene Cypris paleo-lake originated during progressive subsidence in the Sokolov Basin, part of the Cenozoic Oh?e Rift, after the deposition of coal seams. The Cypris Fm. consists almost entirely of lacustrine clays with variable mineral composition and organic matter, where this succession is 70–120 m thick. The main objective of this study was to interpret the geochemical history of the Lower Miocene Cypris Fm. using high-resolution, down-core geochemical records and study of the organic matter. This work revealed that the lower part of the lacustrine sediment sequence was deposited in a freshwater lake, in an open hydrological system. An increase in the K/Zr and K/Ti ratios towards the upper part of the Cypris Fm. indicates a gradual increase in the pelitic fraction of the local sediments and/or a decline in input of volcanic material. Simultaneously, increasing Ca/K and Sr/K ratios indicate the precipitation of carbonates, predominantly dolomite and siderite. In the upper part of the Cypris Fm., there is a significant increase in Na/K, Na/Zr, and Na/Ti ratios, suggesting increasing salinity (alkalinity) of the paleoenvironment in a closed hydrological system. Reaction between the Na-rich water and clastic components of the sediment in an alkaline medium gave rise to the formation of zeolites, mixed-layer clay minerals and smectite. Abundant remains of aquatic organisms, especially algae, increased with greater salinity in the upper part of the Cypris Fm. This is reflected in the greater hydrogen index (HI_{Rock Eval}), and the growing proportion of liptinite group macerals of aquatic origin in the bulk organic matter. During the entire history of sedimentation in the Miocene lake, repetitive changes in the sediment geochemistry occurred at both micro- and macroscales, and fluctuations of K/Ti, K/Zr, and Sr/Ca ratios over meters to tens of meters are observed. These changes probably reflect either long-term climate fluctuations during the Lower Miocene or oscillations caused by changes in the rate of subsidence of the basin floor. Variations in the elemental composition of sediments can be used to correlate individual boreholes across the entire sedimentary basin.     

Species diversity and emergence patterns of nematocerous flies (Insecta: Diptera) from three coastal salt marshes in prince Edward Island, Canada

Emerging insects were monitored every 10 days between early May and late August 1993, from tidal pools in three coastal salt marshes on Prince Edward Island, Canada. The salt marsh pools ranged from about 1 m² to > 1,000 m² in surface area, and had salinities ranging from 11–27‰ Water temperatures through the study period ranged from 4–46°C. Most of the emerging insects were flies (Diptera; 85%), and two-thirds of these were in the sub-Order Nematocera, mainly Chironomidae, Ceratopogonidae, and Culicidae. Forty-three species of Nematocera were identified, although most of these were rare occurrences, and twelve of the species are undescribed. No consistent relationships were found between abundance or diversity and pool size or marsh for Nematocera species overall, although some species showed a statistical preference for a particular marsh or pool size. Emergence patterns were consistent between marshes for species found in different marshes, but overall patterns were highly variable, depending upon species.     

Characterization and assessment of the devastating natural hazards across the Canadian Prairie Provinces from 2009 to 2011

From 2009 to 2011, the Canadian Prairies were subjected to exceptionally variable precipitation regimes, ranging between record drought and unprecedented flooding. Adjacent regions concurrently experienced droughts and floods, and individual areas transitioned rapidly from pluvial to drought conditions and vice versa. Such events had major impacts; for example, damages from floods in the Assiniboine River Basin (ARB) have exceeded $1 billion, and forest fires ravaged the town of Slave Lake, Alberta. This study first characterizes, and then assesses, these devastating natural hazards in terms of their physical processes (across multiple spatial and temporal scales) related to both the spatially contrasting precipitation states and rapid temporal transitions between these states. Subtle differences in large-scale atmospheric flow had marked impacts on precipitation. Primary factors controlling the distribution and amount of precipitation included the location and persistence of key surface and upper-air features, as well as their interaction. Additionally, multiple events—rather than individual extremes—were responsible for the flooding over the Saskatchewan River Basin and the ARB. Very heavy rainfall events (≥25 mm d^?1) accounted for up to 55 % of warm season rain at some locations, and the frequency of heavy rainfall events was critical for determining whether a region experienced drought or pluvial conditions. This study has increased our knowledge of the characteristics, impacts and mechanisms of rapidly transitioning disparate precipitation states on the Canadian Prairies and will aid in better understanding both past and projected future hydro-climatic extremes in the region.     

Discrimination of lithogenic and anthropogenic sources of metals and sulphur in soils of the central-northern part of the Zambian Copperbelt Mining District: A topsoil vs. subsurface soil concept

Samples of topsoil together with reference samples of subsurface soil from a depth of 80–90 cm were collected in the central-northern part of the Zambian Copperbelt to distinguish lithogenic sources of metals from anthropogenic contamination of soils caused by fallout of dust from mining operations, flotation ore treatment plants, tailings dams, smelters and slag dumping grounds. The total sulphur, Cu and Co contents were found to be significantly higher in topsoil relative to subsurface soil over a large part of the surveyed area, and Zn, Pb, As and Hg contents showed a definite increase in the close neighbourhood of smelters and in the direction of prevailing winds. This indicates that the increase of these elements in the topsoil is due to anthropogenic activities. The areal extent and degree of anthropogenic contamination of topsoil can be expressed by an enrichment index (EI) based on the average ratio of the actual and median concentrations of the given contaminants. Although the contamination of soil by dust fallout decreases progressively with depth in the soil profile, in areas strongly affected by mining and mineral processing the anthropogenic contamination by sulphur and copper can be traced to a depth of 80–90 cm. In contrast, the concentration of elements such as Cr, Ni, and V, that show a direct correlation with the content of iron in the soils, increases in the subsurface soil relative to the topsoil. This is particularly evident in areas underlain by rocks of the Katanga Supergroup.     

Microseismic Event Detection Kalman Filter: Derivation of the Noise Covariance Matrix and Automated First Break Determination for Accurate Source Location Estimation

Since 1972, Weir-Jones Engineering Consultants (WJEC) has been involved in the development and installation of microseismic monitoring systems for the mining, heavy construction and oil/gas industries. To be of practical value in an industrial environment, microseismic monitoring systems must produce information which is both reliable and timely. The most critical parameters obtained from a microseismic monitoring system are the real-time location and magnitude of the seismic events. Location and magnitude are derived using source location algorithms that typically utilize forward modeling and iterative optimal estimation techniques to determine the location of the global minimum of a predefined cost function in a three-dimensional solution space. Generally, this cost function is defined as the RMS difference between measured seismic time series information and synthetic measurements generated by assuming a velocity structure for the area under investigation (forward modeling). The seismic data typically used in the source location algorithm includes P- and S-wave arrival times, and raypath angles of incidence obtained from P-wave hodogram analysis and P-wave first break identification. In order to obtain accurate and timely source location estimates it is of paramount importance that the extraction of accurate P-wave and S-wave information from the recorded time series be automated—in this way consistent data can be made available with minimal delay. WJEC has invested considerable resources in the development of real-time digital filters to optimize extraction, and this paper outlines some of the enhancements made to existing Kalman Filter designs to facilitate the automation of P-wave first break identification.     

Tin–polymetallic sulfide deposits in the eastern part of the Dachang tin field (South China) and the role of black shales in their origin

The Dafulou and Huile vein and stratabound cassiterite-sulfide deposits and sheeted ore veins at the Kangma cassiterite-sulfide deposit are located in the eastern part of the Dachang tin field. These deposits are hosted in a sedimentary sequence containing significant concentrations of organic matter in the form of Lower Devonian calcareous black shales and hornfels. These rocks together with the younger intrusion of Longxianggai granite (91DŽ Ma) actively participated in the formation of Sn-polymetallic deposits. The following three major stages have been distinguished in stratiform and vein-type orebodies at Dafulou, Huile and Kangma: stage I (cassiterite, pyrrhotite, arsenopyrite, tourmaline, carbonate), stage II - main sulfide stage (quartz, cassiterite, arsenopyrite, pyrrhotite, sphalerite, stannite, pyrite, carbonates) and stage III (native Bi, galena, electrum, sulfosalts). Stage IV (post-ore), recognized at Huile is represented by barren carbonates and zeolites. Whole rock geochemistry has revealed that at Dafulou, Bi and Cu correlate strongly with S, whereas V and Pb correlate well with C_org (organic carbon). The similar distribution patterns of selected elements in average slightly mineralized low-Ca black shales indicate a fluid composition similar for all deposits studied. Studies of graphitization of the organic matter in black shales adjacent to orebodies indicate that d₍₀₀₂₎ and FWHM (full width in half maximum)/peak height values gradually decrease in the following sequence: Dafulou deposit M Kangma deposit M Huile deposit. The pyrolysate of wall rocks at the Dafulou deposit is relatively enriched in asphaltenes and maltenes (55.6-72.0% of the pyrolysate) comparable with pyrolysate obtained from more distal black shales (19.2-28.5%). Typical GC-MS spectra of pyrolysate from distal black shales are dominated by alkanes in the n-C15 to n-C25 range, aromatic molecules being represented mostly by alkyl-naphthalenes. In contrast, only traces of aliphatic hydrocarbons in the n-C14 to n-C18 range and elemental sulfur were identified in pyrolysates from pyrrhotitized wall rocks. The earliest fluid inclusions of the studied system occur in the quartz-tourmaline-cassiterite assemblage of stage I at Dafulou. These inclusions are H₂O-CO₂-CH₄-rich, with 10 to 20 vol% of aqueous phase. P-T conditions of the trapping of inclusions are estimated to be up to 400 °C and 1.3 to 2.0 kbar (between 5.0 and 7.5 km under lithostatic pressure). In contrast, the presence of a low density gaseous CO₂-CH₄ phase indicates relatively low pressures during the formation of the breccia-type quartz-calcite-cassiterite-sulfide mineralization (stage II), when P-T conditions probably reached approx. 380 to 400 °C and 0.6 kbar (up to 6 km under hydrostatic pressure). Fluid inclusion data and oxygen isotope thermometry indicate that cassiterite-sulfide ores of the main sulfide stage (stage II) formed from aqueous-carbonic fluid (CO₂/CH₄ =ᄺ) at temperatures of up to 390 °C at Dafulou and in a temperature range of 250 to 360 °C at Huile and 260 to 370 °C at Kangma. The '³⁴S values of sulfides from Dafulou range mostly between -1 and -6‰, whereas sulfides from the Kangma and Huile deposits are characterized by more negative '³⁴S values (between -8 and -11‰, and between -9 and -12‰, respectively). These data suggest that bacteriogenic sulfides of black shales were a dominant source of reduced sulfur for epigenetic (vein and replacement) mineralization. Oxygen isotopic compositions of five quartz-cassiterite pairs from Dafulou and Huile show a relatively narrow range of calculated oxygen isotope temperatures (250-320 °C, using the equation of Alderton 1989) and high '¹⁸O_fluid values between +8 and +10‰ (SMOW), which are in agreement with fluid derivation from and/or high temperature equilibration with the Longxianggai granite. The carbon and oxygen isotope composition of carbonates reflects variable carbon sources. Stage I calcite is characterized by narrow ranges of '¹³C (-7.0 to -9.5‰ PDB) and '¹⁸O (+15.0 to +17.5‰ SMOW). This calcite shows ubiquitous deformation, evidenced by intense development of twins. Fluid compositions calculated at 330 °C for the Dafulou and Huile deposits and at 270-300 °C for the Kangma deposit ('¹⁸O_fluid between +10.0 and +11.5‰ SMOW, '¹³C_fluid between -5.5 and -7.5‰ PDB), agree with fluid derivation from and/or equilibration with the peraluminous, high-'¹⁸O Longxianggai granite and suggest a significant influence of contact metasedimentary sequences (carbon derived from decomposition and/or alteration of organic matter of calcareous black shales). The '¹³ C values of organic matter from the Lower to Upper Devonian host rocks at the Dafulou deposit (-24.0 and -28.0‰) fit with a marine origin from algae. However, organic matter adjacent to the host rock-ore contact displays a slight enrichment in ¹³C. The organic carbon from the Huile and Kangma deposits is even more ¹³C enriched (-24.6 to -23.5‰). The most heavy '¹³ C values (-16.5‰) were detected in hornfels sampled at the contact of the Upper Devonian sediments with the Longxianggai granite. The '¹³C data broadly correlate with the degree of structural ordering (degree of graphitization) of organic matter, which indicates that both variables are related to thermal overprint.     

The stability constant of the UO22+ -humic acid complex

Between pH 3.5 and 7, humic acids form a water-soluble uranyl-humic acid complex with the uranyl ion, UO₂²⁺ (log β₁ = 7.8 ± 0.4 at μ = 0.1). The stability constant of the complex is practically independent of the ionic strength (μ). Experimental results can be explained by the formation of a complex in which every uranyl ion is simultaneously bonded to one phenolic oxygen and one dissociated carboxyl group. The bonding through the phenolic group is considerably stronger than that through carboxylic groups.