Structure of grain boundaries in wet,synthetic polycrystalline,statically recrystallizing halite – evidence from cryo‐SEM observations

It is well known from nature and experiments that the presence of brine strongly affects the microstructural evolution and the mechanical and transport properties of halite. Existing interpretations of the grain boundary structure in deformed, wet, salt samples annealed statically at room temperature are based on indirect evidence from reflected light microscopy and conventional scanning electron microscopy. This paper presents direct observations of fluid‐filled grain boundaries using the cryogenic‐scanning electron microscope (cryo‐SEM) in which the grain boundary fluids were frozen before breaking the samples. The rapid cooling transforms the brine into two phases, i.e. ice and hydrohalite, which are easily recognized from characteristic segregation patterns. We studied samples of wet, synthetic, polycrystalline halite annealed under static conditions at room temperature. In coarse‐grained samples, fine‐scale segregation patterns were observed at the boundaries of the primary recrystallizing grains. These points indicate the existence of fluid films with a thickness in the range of 30 nm, but the finer scale structure of the fluid remains unknown. In fine‐grained samples, the distribution and reorganization of fluids with annealing time is recorded by the combination of contact healing and successive accumulation of fluids in triple junction tubes. The contact healing is attributed to the small initial grain size, such that the fluid film necks down by accumulating the fluids into previously existing triple junctions via neck growth. Electron backscatter diffraction measurements of both primary and secondary recrystallized grains indicate that they are euhedral, i.e. the grain growth morphology is controlled by the anisotropy of the grain boundary energy of the growing grain, which results in planar growth faces.     

The effect of pore size on cementation in porous rocks

Halite cementation in porous sandstone from the Lower Triassic Bunter Formation in North‐West Germany has been studied using measurements of porosity and permeability, before and after salt extraction, as well as from petrographic observations. The results show that in cemented sandstones there is a clear tendency for the larger pores to be halite‐filled while the smaller pores, which are responsible for the residual porosity, are left empty. Observations on cemented ‘pin‐stripe’ aeolian sandstones, in which laminations of fine and coarser sand grains alternate on a millimetre scale, indicate that this selective cementation is not due to differences in the brine composition in the pores. The implication, which is also supported by other observations, is that fluids in small pores can maintain a higher supersaturation with respect to crystallization.     

Salt tectonics and shallow subseafloor fluid convection: models of coupled fluid‐heat‐salt transport

Thermohaline convection associated with salt domes has the potential to drive significant fluid flow and mass and heat transport in continental margins, but previous studies of fluid flow associated with salt structures have focused on continental settings or deep flow systems of importance to petroleum exploration. Motivated by recent geophysical and geochemical observations that suggest a convective pattern to near‐seafloor pore fluid flow in the northern Gulf of Mexico (GoMex), we devise numerical models that fully couple thermal and chemical processes to quantify the effects of salt geometry and seafloor relief on fluid flow beneath the seafloor. Steady‐state models that ignore halite dissolution demonstrate that seafloor relief plays an important role in the evolution of shallow geothermal convection cells and that salt at depth can contribute a thermal component to this convection. The inclusion of faults causes significant, but highly localized, increases in flow rates at seafloor discharge zones. Transient models that include halite dissolution show the evolution of flow during brine formation from early salt‐driven convection to later geothermal convection, characteristics of which are controlled by the interplay of seafloor relief and salt geometry. Predicted flow rates are on the order of a few millimeters per year or less for homogeneous sediments with a permeability of 10^?15 m², comparable to compaction‐driven flow rates. Sediment permeabilities likely fall below 10^?15 m² at depth in the GoMex basin, but such thermohaline convection can drive pervasive mass transport across the seafloor, affecting sediment diagenesis in shallow sediments. In more permeable settings, such flow could affect methane hydrate stability, seafloor chemosynthetic communities, and the longevity of fluid seeps.     

Relationship of brines in the Kinnarot Basin,Jordan‐Dead Sea Rift Valley

Element ratios and water stable isotopes reveal the presence of only two independent deep brines in the Kinnarot Basin, Israel: the evaporite dissolution brine of Zemah‐1 and the inferred Ha’on mother brine (HMB) with low and high Br/Cl ratios, respectively. HMB is considered to be a representative of the Late Pliocene evaporated Sedom Sea. The freshwater‐diluted evaporation brine emerges as Ha’on brine on the eastern shore of Lake Tiberias and is also identified in the pore water of lake sediments. HMB is converted into Tiberias mother brine (TMB) by dolomitization of limestones and alteration of abundant volcanic rocks occurring along the western side of the lake. The Ha’on and Tiberias brines, both characterized by high δD and δ¹⁸O values, are similar in Na/Cl and Br/Cl ratios but are dissimilar in Br/K ratios because these brines were subjected to different degrees of interactions with rocks and sediments. Excepting the brine from KIN 8, all brines from the Tabigha area including the nearby off‐shore Barbutim brine are related to the TMB. The brine KIN 8 and all brines from the Fuliya and Hammat Gader areas are related to the HMB. The brine encountered in wildcat borehole Zemah‐1 is generated by halite‐anhydrite/gypsum dissolution and is independent from the HMB system.     

The connectivity of pore space in mudstones: insights from high‐pressure Wood's metal injection,BIB‐SEM imaging,and mercury intrusion porosimetry

Study of the pore space in mudstones by mercury intrusion porosimetry is a common but indirect technique and it is not clear which part of the pore space is actually filled with mercury. We studied samples from the Opalinus Clay, Boom Clay, Haynesville Shale, and Bossier Shale Formations using Wood's metal injection at 316 MPa, followed by novel ion beam polishing and high‐resolution scanning electron microscopy. This method allowed us to analyze at high resolution which parts of a rock are intruded by the liquid alloy at mm to cm scale. Results from the Opalinus Clay and Haynesville Shale show Wood's Metal in cracks, but the majority of the pore space is not filled although mercury intrusion data suggests that this is the case. In the silt‐rich Boom Clay sample, the majority of the pore space was filled Wood's metal, with unfilled islands of smaller pores. Bossier Shale shows heterogeneous impregnation with local filling of pores as small as 10 nm. We infer that mercury intrusion data from these samples is partly due to crack filling and compression of the sample. This compaction is caused by effective stress developed by mercury pressure and capillary resistance; it can close small pore throats, prevent injection of the liquid metal, and indicate an apparent porosity. Our results suggest that many published MIP data on mudstones could contain serious artifacts and reliable metal intrusion porosimetry requires a demonstration that the metal has entered the pores, for example by Wood's metal injection, broad ion beam polishing, and scanning electron microscopy.     

Long‐term chemical evolution and modification of continental basement brines – a field study from the Schwarzwald,SW Germany

Highly saline, deep‐seated basement brines are of major importance for ore‐forming processes, but their genesis is controversial. Based on studies of fluid inclusions from hydrothermal veins of various ages, we reconstruct the temporal evolution of continental basement fluids from the Variscan Schwarzwald (Germany). During the Carboniferous (vein type i), quartz–tourmaline veins precipitated from low‐salinity (<4.5wt% NaCl + CaCl₂), high‐temperature (≤390°C) H₂O‐NaCl‐(CO₂‐CH₄) fluids with Cl/Br mass ratios = 50–146. In the Permian (vein type ii), cooling of H₂O‐NaCl‐(KCl‐CaCl₂) metamorphic fluids (T ≤ 310°C, 2–4.5wt% NaCl + CaCl₂, Cl/Br mass ratios = 90) leads to the precipitation of quartz‐Sb‐Au veins. Around the Triassic–Jurassic boundary (vein type iii), quartz–haematite veins formed from two distinct fluids: a low‐salinity fluid (similar to (ii)) and a high‐salinity fluid (T = 100–320°C, >20wt% NaCl + CaCl₂, Cl/Br mass ratios = 60–110). Both fluids types were present during vein formation but did not mix with each other (because of hydrogeological reasons). Jurassic–Cretaceous veins (vein type iv) record fluid mixing between an older bittern brine (Cl/Br mass ratios ~80) and a younger halite dissolution brine (Cl/Br mass ratios >1000) of similar salinity, resulting in a mixed H₂O‐NaCl‐CaCl₂ brine (50–140°C, 23–26wt% NaCl + CaCl₂, Cl/Br mass ratios = 80–520). During post‐Cretaceous times (vein type v), the opening of the Upper Rhine Graben and the concomitant juxtaposition of various aquifers, which enabled mixing of high‐ and low‐salinity fluids and resulted in vein formation (multicomponent fluid H₂O‐NaCl‐CaCl₂‐(SO₄‐HCO₃), 70–190°C, 5–25wt% NaCl‐CaCl₂ and Cl/Br mass ratios = 2–140). The first occurrence of highly saline brines is recorded in veins that formed shortly after deposition of halite in the Muschelkalk Ocean above the basement, suggesting an external source of the brine's salinity. Hence, today's brines in the European basement probably developed from inherited evaporitic bittern brines. These were afterwards extensively modified by fluid–rock interaction on their migration paths through the crystalline basement and later by mixing with younger meteoric fluids and halite dissolution brines.     

Basin‐scale fluid movement patterns revealed by veins: Wessex Basin,UK

Calcite veins at outcrop in the Mesozoic, oil‐bearing Wessex Basin, UK, have been studied using field characterization, petrography, fluid inclusions and stable isotopes to help address the extent, timing and spatial and stratigraphic variability of basin‐scale fluid flow. The absence of quartz shows that veins formed at low temperature without an influence of hydrothermal fluids. Carbon isotopes suggest that the majority of vein calcite was derived locally from the host rock but up to one quarter of the carbon in the vein calcite came from CO₂ from petroleum source rocks. Veins become progressively enriched in source‐rock‐derived CO₂ from the outer margin towards the middle, indicating a growing influence of external CO₂. The carbon isotope data suggest large‐scale migration of substantial amounts of CO₂ around the whole basin. Fluid inclusion salinity data and interpreted water‐δ¹⁸O data show that meteoric water penetrated deep into the western part of the basin after interacting with halite‐rich evaporites in the Triassic section before entering fractured Lower and Middle Jurassic rocks. This large‐scale meteoric invasion of the basin probably happened during early Cenozoic uplift. A similar approach was used to reveal that, in the eastern part of the basin close to the area that underwent most uplift, uppermost Jurassic and Cretaceous rocks underwent vein formation in the presence of marine connate water suggesting a closed system. Stratigraphically underlying Upper Jurassic mudstone and Lower Cretaceous sandstone, in the most uplifted part of the basin, contain veins that resulted from intermediate behaviour with input from saline meteoric water and marine connate waters. Thus, while source‐rock‐derived CO₂ seems to have permeated the entire section, water movement has been more restricted. Oil‐filled inclusions in vein calcite have been found within dominant E‐W trending normal faults, suggesting that these may have facilitated oil migration.     

Topography‐driven flow versus buoyancy‐driven flow in the U.S. midcontinent: implications for the residence time of brines

Topography‐driven flow is normally considered to be the dominant groundwater flow system in uplifted sedimentary basins. In the U.S. midcontinent region east of the Rocky Mountains, the presence of brines derived from dissolution of halite suggests that significant topography‐driven flushing has occurred to remove older brines that presumably formed concurrently with Permian evaporites in the basin. However, the presence of evaporites and brines in the modern basin suggests that buoyancy‐driven flow could limit topography‐driven flushing significantly. Here we used numerical models of variable‐density fluid flow, halite dissolution, solute transport, and heat transport to quantify flow patterns and brine migration. Results indicate the coexistence of large‐scale topography‐ and buoyancy‐driven flow. Buoyancy‐driven flow and low permeability evaporites act to isolate brines, and the residence time of the brines was found to be quite long, at least 50 Myr. The modern distribution of salinity appears to reflect near‐steady‐state conditions. Results suggest that flushing of original evaporatively‐concentrated brines occurred tens of millions of years ago, possibly concurrent with maximum uplift ca. 60 Ma. Simulations also suggest that buoyancy‐driven convection could drive chemical exchange with crystalline basement rocks, which could supply significant Ca²⁺, Sr²⁺, and metals to brines.     

Geographic information system‐based edge effect correction for Ripley's K‐function under irregular boundaries

Ripley's K‐function is a test to detect geographically distributed patterns occurring across spatial scales. Initially, it assumed infinitely continuous planar space, but in reality, any geographic distribution occurs in a bounded region. Hence, the edge problem must be solved in the application of Ripley's K‐function. Traditionally, three basic edge correction methods were designed for regular study plots because of simplified geometric computation: the Ripley circumference, buffer zone, and toroidal methods. For an irregular‐shaped study region, a geographic information system (GIS) is needed to support geometric calculation of complex shapes. The Ripley circumference method was originally implemented by Haase and has been modified into a Python program in a GIS environment via Monte Carlo simulation (hereafter, the Ripley–Haase and Ripley–GIS methods). The results show that in terms of the statistical powers of clustering detection for irregular boundaries, the Ripley–GIS method is the most stable, followed by the buffer zone, toroidal, and Ripley–Haase methods. After edge effects of irregular boundaries have been eliminated, Ripley's K‐function is used to estimate the degree of spatial clustering of cities in a given territory, and in this paper, we demonstrate that by reference to the relationship between urban spatial structure and economic growth in China.     

Stress‐dependent transport properties of fractured arkosic sandstone

We measure the fluid transport properties of microfractures and macrofractures in low‐porosity polyphase sandstone and investigate the controls of in situ stress state on fluid flow conduits in fractured rock. For this study, the permeability and porosity of the Punchbowl Formation sandstone, a hydrothermally altered arkosic sandstone, were measured and mapped in stress space under intact, microfractured, and macrofractured deformation states. In contrast to crystalline and other sedimentary rocks, the distributed intragranular and grain‐boundary microfracturing that precedes macroscopic fracture formation has little effect on the fluid transport properties. The permeability and porosity of microfractured and intact sandstone depend strongly on mean stress and are relatively insensitive to differential stress and proximity to the frictional sliding envelope. Porosity variations occur by elastic pore closure with intergranular sliding and pore collapse caused by microfracturing along weakly cemented grain contacts. The macroscopic fractured samples are best described as a two‐component system consisting (i) a tabular fracture with a 0.5‐mm‐thick gouge zone bounded by 1 mm thick zones of concentrated transgranular and intragranular microfractures and (ii) damaged sandstone. Using bulk porosity and permeability measurements and finite element methods models, we show that the tabular fracture is at least two orders of magnitude more permeable than the host rock at mean stresses up to 90 MPa. Further, we show that the tabular fracture zone dilates as the stress state approaches the friction envelope resulting in up to a three order of magnitude increase in fracture permeability. These results indicate that the enhanced and stress‐sensitive permeability in fault damage zones and sedimentary basins composed of arkosic sandstones will be controlled by the distribution of macroscopic fractures rather than microfractures.     

Apatite grain boundary morphology and its response to low-temperature fluid infiltration in crystalline basement

Apatite grain boundaries on fractured rock surfaces have been examined in an amphibolite facies regional metamorphic granite gneiss from the central Swiss Alps. The morphology of apatite has been characterized using a scanning electron microscope and matched to surface textures in adjoining silicates. Apatites show a wide variety of different surface features ranging from planar crystal faces, to small-scale ridges and dimples, to extensive irregular pitting. Many of these features form in response to the periodic infiltration of fluids along open grain boundaries during the cooling history of the gneiss. Apatite shows evidence of both dissolution and re-precipitation that is controlled by the nature of the grain boundary, the structure of the adjoining silicate phase and the alteration of the host rock. Fracturing occurs in a range of retrograde conditions and is common both within the apatite and along grain boundaries. This coupled to the evidence of fluid interaction with mineral surfaces suggests that extensive permeable networks may be typical of cooling crystalline basement rocks. Grain boundary textures have the potential to reveal a unique record of fluid infiltration in the crust that would be very difficult to decipher using traditional petrographic methods.     

Phase‐field modeling of epitaxial growth of polycrystalline quartz veins in hydrothermal experiments

Mineral precipitation in an open fracture plays a crucial role in the evolution of fracture permeability in rocks, and the microstructural development and precipitation rates are closely linked to fluid composition, the kind of host rock as well as temperature and pressure. In this study, we develop a continuum thermodynamic model to understand polycrystalline growth of quartz aggregates from the rock surface. The adapted multiphase‐field model takes into consideration both the absolute growth rate as a function of the driving force of the reaction (free energy differences between solid and liquid phases), and the equilibrium crystal shape (Wulff shape). In addition, we realize the anisotropic shape of the quartz crystal by introducing relative growth rates of the facets. The missing parameters of the model, including surface energy and relative growth rates, are determined by detailed analysis of the crystal shapes and crystallographic orientation of polycrystalline quartz aggregates in veins synthesized in previous hydrothermal experiments. The growth simulations were carried out for a single crystal and for grain aggregates from a rock surface. The single crystal simulation reveals the importance of crystal facetting on the growth rate; for example, growth velocity in the c‐axis direction drops by a factor of ~9 when the faceting is complete. The textures produced by the polycrystal simulations are similar to those observed in the hydrothermal experiments, including the number of surviving grains and crystallographic preferred orientations as a function of the distance from the rock wall. Our model and the methods to define its parameters provide a basis for further investigation of fracture sealing under varying conditions.     

Reactive transport and thermo‐hydro‐mechanical coupling in deep sedimentary basins affected by glaciation cycles: model development,verification, and illustrative example

Deep sedimentary basins are complex systems that over long time scales may be affected by numerous interacting processes including groundwater flow, heat and mass transport, water–rock interactions, and mechanical loads induced by ice sheets. Understanding the interactions among these processes is important for the evaluation of the hydrodynamic and geochemical stability of geological CO₂ disposal sites and is equally relevant to the safety evaluation of deep geologic repositories for nuclear waste. We present a reactive transport formulation coupled to thermo‐hydrodynamic and simplified mechanical processes. The formulation determines solution density and ion activities for ionic strengths ranging from freshwater to dense brines based on solution composition and simultaneously accounts for the hydro‐mechanical effects caused by long‐term surface loading during a glaciation cycle. The formulation was implemented into the existing MIN3P reactive transport code (MIN3P‐THCm) and was used to illustrate the processes occurring in a two‐dimensional cross section of a sedimentary basin subjected to a simplified glaciation scenario consisting of a single cycle of ice‐sheet advance and retreat over a time period of 32 500 years. Although the sedimentary basin simulation is illustrative in nature, it captures the key geological features of deep Paleozoic sedimentary basins in North America, including interbedded sandstones, shales, evaporites, and carbonates in the presence of dense brines. Simulated fluid pressures are shown to increase in low hydraulic conductivity units during ice‐sheet advance due to hydro‐mechanical coupling. During the period of deglaciation, Darcy velocities increase in the shallow aquifers and to a lesser extent in deeper high‐hydraulic conductivity units (e.g., sandstones) as a result of the infiltration of glacial meltwater below the warm‐based ice sheet. Dedolomitization is predicted to be the most widespread geochemical process, focused near the freshwater/brine interface. For the illustrative sedimentary basin, the results suggest a high degree of hydrodynamic and geochemical stability.     

Mathematical modeling of phase separation of seawater near an igneous dike

We provide a simplified treatment of phase separation of seawater near an igneous dike to obtain rough estimates of the thickness and duration of the two‐phase zone, the volume fractions of vapor and brine formed, and their distribution in the subsurface. Under the assumption that heat transfer occurs mainly by thermal conduction we show that, for a 2‐m wide dike, the maximum width of the two phase zone is approximately 20 cm and that a zone of halite is initially deposited near the dike wall. The two‐phase zone is mainly filled with vapor. For a value of thermal diffusivity of a = 10^?6 m² sec^?1, the two‐phase zone begins to disappear at the base of the system after 13 days, and disappears completely by 16 days. For a lower value of thermal diffusivity, the width of the two‐phase region does not change appreciably but its duration increases as a^?1. The width of the two‐phase zone determined by this simplified model agrees reasonably well with transient numerical solutions for the analogous two‐phase flow in a pure water system; however the duration of two‐phase flow is matched better using a smaller value of a. We compare the seafloor values of vapor salinity and temperature given by the model with vapor salinity data from the ‘A’ vent at 9–10°N on the East Pacific Rise (EPR) and argue that either non‐equilibrium thermodynamic behavior or near‐surface mixing of brine with vapor in the two‐phase region may explain the discrepancies between model predictions and data.     

Comparing closed system, flow-through and fluid infiltration geochemical modelling: examples from K-alteration in the Ernest Henry Fe-oxide–Cu–Au system

Potassic alteration of rocks adjacent to, and within the Ernest Henry Fe‐oxide–Cu–Au deposit is used here as a test case to investigate fluid–rock interactions using various equilibrium dynamic geochemical modelling approaches available in the HCh code. Reaction of a simple K–Fe–(Na,Ca) brine (constrained by published fluid inclusion analysis) with an albite‐bearing felsic volcanic rock, resulted in predicted assemblages defined by (i) K‐feldspar–muscovite–magnetite, (ii) biotite–K‐feldspar–magnetite, (iii) biotite–quartz–albite and (iv) albite–biotite–actinolite–pyroxene with increasing rock buffering (decreasing log w/r). Models for isothermal–isobaric conditions (450°C and 2500 bars) were compared with models run over a T–P gradient (450 to 200°C and 2500 to 500 bars). Three principal equilibrium dynamic simulation methods have been used: (i) static closed system, where individual steps are independent of all others, (ii) flow‐through and flush, where a part of the result is passed as input further along the flow line, and (iii) fluid infiltration models that simulate fluid moving through a rock column. Each type is best suited to a specific geological fluid–rock scenario, with increasing complexity, computation requirements and approximation to different parts of the natural system. Static closed system models can be used to quickly ascertain the broad alteration assemblages related to changes in the water/rock ratio, while flow‐through models are better suited to simulating outflow of reacted fluid into fresh rock. The fluid infiltration model can be used to simulate spatially controlled fluid metasomatism of rock, and we show that, given assumptions of porosity relationships and spatial dimensions, this model is a first‐order approximation to full reactive transport, without requiring significant computational time. This work presents an overview of the current state of equilibrium dynamic modelling technology using the HCh code with a view to applying these techniques to predictive modelling in exploration for mineral deposits. Application to the Ernest Henry Fe‐oxide–Cu–Au deposit demonstrates that isothermal fluid–rock reaction can account for some of the alteration zonation around the deposit.     

Basin‐Wide Sediment Grain‐Size Numerical Analysis and Paleo‐Climate Interpretation in the Shiyang River Drainage Basin

Basin‐wide sediment transport affects estimates of basin sediment yield, which is a fundamental scientific issue in drainage basin studies. Many studies have been conducted to examine erosion and deposition rates in drainage networks. In this study, we proposed a new approach using grain‐size standard deviation model of sedimentary samples from different geomorphological units for numerical analysis and paleo‐climate interpretation in the Shiyang River drainage basin, arid China. 1043 sedimentary samples were obtained from the upper reaches, the midstream alluvial plain and the terminal lake area; chronological frames were established based on 58 radiocarbon ages. Grain‐size standard deviation model was introduced to examine sediment components according to grain‐size and transport forces. In addition, transient paleo‐climate simulations, including the Community Climate System Model version 3 and the Kiel models, were synthesized, as well as the results from PMIP 3.0 project, to detect the long‐term climate backgrounds. Totally, we found four major common components, including fine particulates (<2 μm), fine silt (2–20 μm), sandy silt (20–200 μm), coarse sand (>200 μm), from basin‐wide sedimentary samples. The fine particulates and fine silt components exist in all the sedimentary facies, showing long‐term airborne aerosol changes and its transport by suspended load. There are some differences in ranges of sandy silt and coarse sand components, due to lake and river hydrodynamics, as well as the distance with the Gobi Desert. Paleo‐climate simulations have shown that the strong Asian summer monsoon during the transition of the Last Deglaciation and Holocene was conducive to erosion and transport of basin‐wide suspended load, also enhancing sediment sorting effects due to strong lake hydrodynamics. Our findings provide a new approach in research of long‐term basin‐wide sediment transport processes.     

TIEBOUT DYNAMICS: NEIGHBORHOOD RESPONSE TO A CENTRAL‐CITY/SUBURBAN HOUSE‐PRICE DIFFERENTIAL*

ABSTRACT We take advantage of an unusual natural experiment—a high‐quality 1920s subdivision split neatly in half by a central‐city/suburban boundary—to study the response over 30 years to the relative decline in the quality of central‐city services since the 1960s. As expected, a large sale price differential opens in the 1960s. Demographic characteristics are nevertheless similar across the boundary. Survey data indicate Tiebout sorting: the central city side attracts households who prefer alternatives to suburban public schools. Children attend parochial and public “magnet” schools. A neighborhood association supplements municipal services. Rigid service district boundaries inhibit closure of the house‐price differential.     

Eighteenth‐Century Meissen Porcelain Reference Data Obtained By Proton‐Beam Analysis (PIXE–PIGE)

Prior to their restoration, the porcelain bodies of broken pieces from 31 authentic Meissen objects of the early 18th century were investigated by proton‐beam analysis. Attention was paid so that the proton beam probed only the bare porcelain paste areas of fractures. Thus, contributions to the measured X‐ray and γ‐ray spectra from adjacent surface glaze were prevented. The chemical compositions, obtained by simultaneous detection of elements with Z ≥ 13 (X‐rays) and lighter elements Z ≤ 14 (γ‐rays), represent rather consistent mixtures of paste ingredients. This result highlights the durable recipes and raw materials used in early Meissen porcelain production in the years 1725–50. Mean concentration values of element oxides, deduced from the detailed measurements, prove suitable for use as a database for Meissen porcelain paste identification. Material authentication of intact objects, without access to the bare porcelain body, is demonstrated by inspection of the white glaze. Unique museum objects are examined in atmosphere and without sampling. A low proton‐beam intensity and a short irradiation time ensure non‐destructive analysis. Simultaneous radiation and backscattered particle detection allow complete composition analysis, using the established ion beam techniques of particle‐induced X‐ray emission (PIXE), particle‐induced gamma‐ray emission (PIGE) and Rutherford backscattering spectrometry (RBS).     

Hydrothermal,multiphase convection of H2O‐NaCl fluids from ambient to magmatic temperatures: a new numerical scheme and benchmarks for code comparison

Thermohaline convection of subsurface fluids strongly influences heat and mass fluxes within the Earth's crust. The most effective hydrothermal systems develop in the vicinity of magmatic activity and can be important for geothermal energy production and ore formation. As most parts of these systems are inaccessible to direct observations, numerical simulations are necessary to understand and characterize fluid flow. Here, we present a new numerical scheme for thermohaline convection based on the control volume finite element method (CVFEM), allowing for unstructured meshes, the representation of sharp thermal and solute fronts in advection‐dominated systems and phase separation of variably miscible, compressible fluids. The model is an implementation of the Complex Systems Modelling Platform CSMP++ and includes an accurate thermodynamic representation of strongly nonlinear fluid properties of salt water for magmatic‐hydrothermal conditions (up to 1000°C, 500 MPa and 100 wt% NaCl). The method ensures that all fluid properties are taken as calculated on the respective node using a fully upstream‐weighted approach, which greatly increases the stability of the numerical scheme. We compare results from our model with two well‐established codes, HYDROTHERM and TOUGH2, by conducting benchmarks of different complexity and find good to excellent agreement in the temporal and spatial evolution of the hydrothermal systems. In a simulation with high‐temperature, high‐salinity conditions currently outside of the range of both HYDROTHERM and TOUGH2, we show the significance of the formation of a solid halite phase, which introduces heterogeneity. Results suggest that salt added by magmatic degassing is not easily vented or accommodated within the crust and can result in dynamic, complex hydrologies.     

Ecohydrology and Environmental Change to Lake Albacutya and Wyperfeld Park in North‐Western Victoria,Australia

Lake Albacutya is a well‐known intermittent lake in north‐western Victoria. The lake is near the termination of the Wimmera River. From time‐to‐time the lake fills and flow passes down Outlet Creek into Wyperfeld National Park. The wetlands associated with the lake have a high biodiversity value and are named in international treaties. This paper examines the hydrologic factors associated with lake filling and flow into Wyperfeld. The lake has filled approximately six times since 1880 and has partially filled on other occasions. Examination of rainfall data from 1875 at Horsham gave no indication of long term rainfall decline, and showed that rainfall at Horsham can be viewed as representative of rainfall in the Wimmera River catchment. However a double‐mass analysis showed that the relationship between the Wimmera River flow and rainfall has varied from 1890 to the present. Examination of data associated with six fillings of Lake Albacutya suggested that filling is a two‐year event requiring at least 550 GL of flow passing Horsham over the two years immediately associated with the flood. A simple model based on rainfall and this threshold reproduced observed characteristics of the data reasonably well. This suggested that the flooding frequency of Lake Albacutya has dropped from about one in 25 years in the natural state to a substantially lower frequency under current river conditions. The results also suggested that because of changes in the Wimmera River the last filling and flood into Wyperfeld in 1976 was far smaller than it would otherwise have been. This is consistent with field mapping of the flood in relation to River Red Gum (Eucalyptus camaldulensis Dehnh.) stands. Analysis of the health of these stands showed major dieback with the severity of this being roughly proportional to the distance from the 1976 flood boundaries. An examination of values associated with the lake and adjoining Wyperfeld National Park suggested that biodiversity and economic values are and will be compromised by the reduction in flooding. In particular, an internationally‐known provenance of Red Gum is at risk, and bird‐breeding opportunities have diminished.