Time-series of δ26Mg values in a headwater catchment reveal decreasing magnesium isotope variability from precipitation to runoff

Data on temporal variability in Mg isotope ratios of atmospheric deposition and runoff are critical for decreasing the uncertainty associated with construction of isotope mass balances in headwater catchments, and statistical evaluation of isotope differences among Mg pools and fluxes. Such evaluations, in turn, are needed to distinguish between biotic and abiotic contributions to Mg²⁺ in catchment runoff. We report the first annual time-series of δ²⁶Mg values simultaneously determined for rainfall, canopy throughfall, soil water and runoff. The studied 55-ha catchment, situated in western Czech Republic, is underlain by Mg-rich amphibolite and covered by mature spruce stands. Between 1970 and 1996, the site received extremely high amounts of acid deposition and fly ash form nearby coal-burning power plants. The δ²⁶Mg values of open-area precipitation (median of −0.79‰) at our study site were statistically indistinguishable from the δ²⁶Mg values of throughfall (−0.73‰), but significantly different from the δ²⁶Mg values of soil water (−0.55‰) and runoff (−0.55‰). The range of δ²⁶Mg values during the observation period decreased in the order: open-area precipitation (0.57‰) > throughfall (0.27‰) > runoff (0.21‰) > soil water (0.16‰). The decreasing variability in δ²⁶Mg values of Mg²⁺ from precipitation to soil water and runoff reflected an increasing homogenization of atmospheric Mg in the catchment and its mixing with geogenic Mg. In addition to atmospheric Mg, runoff also contained Mg mobilized from the three major solid Mg pools, bedrock (δ²⁶Mg of −0.32‰), soil (−0.28‰), and vegetation (−0.31‰). The drought of summer 2019 did not affect the nearly constant δ²⁶Mg value of runoff. Collectively, our data show that within-catchment processes buffer the Mg isotope variability of the atmospheric input.     

Metamorphic record of collision and collapse in the Ediacaran‐Cambrian Araçuaí orogen,SE‐Brazil: Insights from P–T pseudosections and monazite dating

The Araçuaí orogen is the Brazilian counterpart of the Araçuaí‐West Congo orogenic system (AWCO), a component of the Ediacaran‐Cambrian orogenic network formed during the amalgamation of West Gondwana. The northwestern portion of the Araçuaí orogen is dominated by a succession of metasedimentary rocks made up of Meso‐ to Neoproterozoic rift, passive margin and syn‐orogenic sequences, locally intruded by post‐collisional granites. These sequences are involved in three distinct tectonic units, which from west to east are: the southern Espinhaço fold‐thrust system (SE‐thrust system), the normal‐sense Chapada Acauã shear zone (CASZ) and the Salinas synclinorium. Three deformation phases were documented in the region. The first two phases (D₁ and D₂) are characterized by contractional structures and represent the collisional development stage of the orogen. The third phase (D₃) is extensional and currently viewed as a manifestation of orogenic collapse of the system. The distribution of the metamorphic mineral assemblages in the region characterizes two metamorphic domains. The M‐Domain I on the west, encompassing the SE‐thrust system and the CASZ, is marked by a syn‐collisional (syn‐D₁) Barrovian‐type metamorphism with P–T conditions increasing eastwards and reaching ~8.5 kbar at ~650°C between 575 and 565 Ma. The M‐Domain II comprises the Salinas synclinorium in the hangingwall of the CASZ, and besides the greenschist facies syn‐collisional metamorphism, records mainly a Buchan‐type metamorphic event, which took place under 3–5.5 kbar and up to 640°C at c. 530 Ma. The northwestern Araçuaí orogen exhibits, thus, a paired metamorphic pattern, in which the Barrovian and Buchan‐type metamorphic domains are juxtaposed by a normal‐sense shear zone. Lithospheric thinning during the extensional collapse of the orogen promoted ascent of the geotherms and melt generation. A large volume of granites was emplaced in the high grade and anatectic core of the orogen during this stage, and heat advected from these intrusions caused the development of Buchan facies series over a relatively large area. Renewed granite plutonism, hydrothermal activities followed by progressive cooling affected the system between 530 and 490 Ma.     

Three-year assessment of particulate organic carbon fluxes in Amundsen Gulf (Beaufort Sea): Satellite observations and sediment trap measurements

Surface concentrations and vertical fluxes of particulate organic carbon (POC) were assessed in the Amundsen Gulf (southeastern Beaufort Sea, Arctic Ocean) over the years 2004 to 2006 by using ocean color remote-sensing imagery and sequential sediment traps moored over the ca. 400 m isobath. Environmental conditions (sea ice, wind) and oceanographic variables (temperature, salinity, fluorescence and currents) were investigated to explain the variability of POC data. Annual downward POC fluxes in 2004, 2005 and 2006 cumulated, respectively, to 3.3, 4.2 and 6.0 g C m^?2 yr^?1 at ～100 m depth, and to 1.3, 2.2 and 3.3 g C m^?2 yr^?1 at ～210 m depth. The fraction of settling POC attributable to autochthonous processes occurring at or next to ice break-up was estimated to be 75–84% of the 100 m annual fluxes and to be 61–75% of the 210 m fluxes. Over the three ice-reduced seasons, distinct scenarios between ice conditions, surface POC pools and vertical POC export at 100 m were identified: (1) in 2004, despite a normal ice break-up, a weak primary production was measured and low vertical fluxes were collected as old ice moved across the region; (2) in 2005, a lengthened ice-free period allowed an extended season of surface POC production near-shore, while an intermediate increase of vertical fluxes was recorded offshore; and (3) in 2006, a late ice melt gave rise to a pulsed ice edge bloom and to large vertical fluxes also associated with extra ice-flushed material. Linear regressions of vertical POC fluxes against satellite-derived surface POC concentrations suggested that the pelagic POC retention in the upper 100 m of the Amundsen Gulf ranged from ca. 70% to 90% depending on the timing of ice cover melt. Regardless of the inter-annual variability, the estimated fraction of the surface POC reservoir reaching the 210 m water depth was reduced to ～5%. Therefore, as the Arctic Ocean warms up, our results support the expectation that the increasing extent of the seasonal ice zone will promote the POC pathways that benefit pelagic webs rather than benthic communities.     

History matching time-lapse seismic data using the ensemble Kalman filter with multiple data assimilations

The ensemble Kalman filter (EnKF) has become a popular method for history matching production and seismic data in petroleum reservoir models. However, it is known that EnKF may fail to give acceptable data matches especially for highly nonlinear problems. In this paper, we introduce a procedure to improve EnKF data matches based on assimilating the same data multiple times with the covariance matrix of the measurement errors multiplied by the number of data assimilations. We prove the equivalence between single and multiple data assimilations for the linear-Gaussian case and present computational evidence that multiple data assimilations can improve EnKF estimates for the nonlinear case. The proposed procedure was tested by assimilating time-lapse seismic data in two synthetic reservoir problems, and the results show significant improvements compared to the standard EnKF. In addition, we review the inversion schemes used in the EnKF analysis and present a rescaling procedure to avoid loss of information during the truncation of small singular values.     

Downstream changes in antimony and arsenic speciation in sediments at a mesothermal gold deposit in British Columbia,Canada

This study investigates Sb speciation in sediments along the drainage of the Upper Peter adit at the Bralorne Au mine in southern British Columbia, Canada, and compares the behavior of Sb with that of As. The Upper Peter mineralization consists of native Au in quartz-carbonate veins with 1 wt.% sulfides dominated by pyrite and arsenopyrite although stibnite, the primary Sb-bearing sulfide mineral, can be locally significant. Dissolved Sb concentrations can reach up to 349 μg L⁻¹ in the mine pool. Sediments were collected for detailed geochemical and mineralogical characterization at locations along the 350-m flow path, which includes a 100-m shallow channel within the adit, a sediment settling pond about 45 m beyond the adit portal and an open wetland another 120 m farther downstream. From the mine pool to the wetland outlet, dissolved Sb in the drainage drops from 199 μg L⁻¹ to below the detection limit due to the combined effect of dilution and removal from solution. Speciation analyses using X-ray absorption near-edge structure (XANES) spectroscopy indicate that Sb(III)–S accounts for around 70% of total Sb in the sediments in the main pool at the far end of the adit. At a short distance (24 m) downstream of the main adit pool, however, Sb(III)–O and Sb(V)–O species represent ?50% of total Sb in the bulk sediments, indicating significant oxidation of the primary sulfides inside the adit. Although Sb appears largely oxidized in the bulk samples collected near the portal, Sb(III)–S species are nevertheless present in the <53-μm fraction, suggesting a higher oxidation rate for stibnite in the coarser grains, possibly due to galvanic interaction with pyrite. Secondary Sb species released from the sulfide oxidation are most likely sorbed/co-precipitated with Fe-, Mn-, and Al-oxyhydroxides along the flow channel in the adit and in the sediment settling pond, with the Fe phase being the dominant sink for Sb.     

Hydrothermal fluid source constrained by Co/Ni ratios in coexisting arsenopyrite and tourmaline: the auriferous lode of Passagem, Quadrilátero Ferrífero of Minas Gerais, Brazil

The auriferous lode of Passagem de Mariana is characterised by abundant tourmaline, which is intergrown with arsenopyrite. Spot measurements using laser ablation–inductively coupled plasma–mass spectrometry show that Co and Ni are the most abundant trace elements in the arsenopyrite (45–538?ppm Co, 246–828?ppm Ni), with Co/Ni ratios consistently <1. The coexisting tourmaline also has Co/Ni <1, with Co and Ni contents that are ~2 orders of magnitude lower than those in the arsenopyrite. The Co/Ni ratios of tourmaline and arsenopyrite are tightly distributed along a positive linear trend, the angular coefficient of which represents the Co/Ni of the hydrothermal fluid from which these minerals precipitated. The fluid Co/Ni ratio is close to the average Co/Ni value for the upper continental crust. In conjunction with the abundance of lode tourmaline and its B-isotope data (from the literature), the Co/Ni ratios of tourmaline and arsenopyrite fingerprint a continental evaporitic source of B.     

Hypersaline fluids generated by high-grade metamorphism of evaporites: fluid inclusion study of uranium occurrences in the Western Zambian Copperbelt

In the Pan-African Lufilian belt (Western Zambian Copperbelt), uranium mineralizations, preferentially scattered in kyanite ± talc micaschists (metamorphosed evaporitic sediments) or concentrated along transposed quartz veins provide an opportunity to (1) understand the time/space relationship between the ore minerals and the deformation of the host rocks, (2) identify the different fluid events associated with specific stages of quartz deformation and (3) characterize the ore fluid geochemistry in terms of fluid origin and fluid/rock interactions. In the U occurrences studied in Lolwa and Mitukuluku (Domes region, Western Zambian Copperbelt), two mineralizing stages are described. The first generation of ore fluids (53–59 wt% CaCl₂, 13–15 wt% NaCl; N₂–H₂ in the gas phase of fluid inclusions) circulated during the high-temperature quartz recrystallization, at 500–700 °C. This temperature is in agreement with the P–T conditions recorded during the crustal thickening related to continental collision at ca. 530 Ma. LA-ICPMS analyses show the presence of uranium within this fluid, with a concentration mode around 20 ppm. The second generation of ore fluid (21–32 wt% NaCl, 19–21 wt% CaCl₂; CO₂–CO in the gas phase of fluid inclusions) percolated at lower temperature conditions, at the brittle–ductile transition, between 200 and 300 °C. This temperature could be related to the exhumation of the high-grade metamorphic rocks at ca. 500 Ma. The formation of H₂ and CO is interpreted as the result of radiolysis in the presence of dissolved uranium in the aqueous phase of these fluid inclusions. Finally, a late fluid (14–16 wt% NaCl_equiv) circulated in the brittle domain but seems unrelated to U (re-)mobilization event.     

Simulation of Geological Contacts from Interpreted Geological Model Using Multiple-Point Statistics

Applications of multiple-point statistics (mps) algorithms to large non-repetitive geological objects such as those found in mining deposits are difficult because most mps algorithms rely on pattern repetition for simulation. In many cases, an interpreted geological model built from a computer-aided design system is readily available but suffers as a training image due to the lack of patterns repetitiveness. Porphyry copper deposits and iron ore formations are good examples of such mining deposits with non-repetitive patterns. This paper presents an algorithm called contactsim that focuses on reproducing the patterns of the contacts between geological types. The algorithm learns the shapes of the lithotype contacts as interpreted by the geologist, and simulates their patterns at a later stage. Defining a zone of uncertainty around the lithological contact is a critical step in contactsim, because it defines both the zones where the simulation is performed and where the algorithm should focus to learn the transitional patterns between lithotypes. A larger zone of uncertainty results in greater variation between realizations. The definition of the uncertainty zone must take into consideration the geological understanding of the deposit, and the reliability of the contact zones. The contactsim algorithm is demonstrated on an iron ore formation.     

Modification of fluid inclusions in quartz by deviatoric stress. II: experimentally induced changes in inclusion volume and composition

Fluid inclusions in quartz are known to modify their densities during shear deformation. Modifications of chemical composition are also suspected. However, such changes have not been experimentally demonstrated, their mechanisms remain unexplained, and no criteria are available to assess whether deformed inclusions preserve information on paleofluid properties. To address these issues, quartz crystals containing natural CO₂–H₂O–NaCl fluid inclusions have been experimentally subjected to compressive deviatoric stresses of 90–250 MPa at 700°C and ~600 MPa confining pressure. The resulting microcracking of the inclusions leads to expansion by up to 20%, producing low fluid densities that bear no relation to physical conditions outside the sample. Nevertheless, the chemical composition of the precursor inclusions is preserved. With time the microcracks heal and form swarms of tiny satellite inclusions with a wide range of densities, the highest reflecting the value of the maximum principle stress, σ ₁. These new inclusions lose H₂O via diffusion, thereby passively increasing their salt and gas contents, and triggering plastic deformation of the surrounding quartz via H₂O-weakening. Using microstructural criteria to identify the characteristic types of modified inclusions, both the pre-deformation fluid composition and syn-deformation maximum stress on the host mineral can be derived from microthermometric analysis and thermodynamic modelling.