Molecular modelling of rare earth element complexation in subduction zone fluids     

Jelle van Sijl  Neil L. Allan  Wim van Westrenen 《Geochimica et cosmochimica acta》2009,73(13):3934-3947

Complexation of (trace) elements in fluids plays a critical role in determining element mobility in subduction zones, but to date, the atomic-scale processes controlling elemental solubilities are poorly understood. As a first step towards computer simulation of element complexation in subduction zone fluids, a thermodynamic cycle was developed to investigate the hydration environment and energetics of lanthanide complexes using density functional theory. The first solvation shell is explicitly defined and the remaining part of the aqueous fluid is modelled using a polarisable continuum model, which allows extrapolation to a broad pressure and temperature range.We illustrate our method by comparing solvation of lanthanide series elements in H₂O in the presence of fluoride or chloride for conditions relevant to subduction zones. The energetics of lanthanide- and lanthanide-fluoride/chloride hydration complexes were determined computationally. Calculated hydration free energies for trivalent lanthanides with explicit eight- and nine-fold coordinated first hydration shells show good agreement with literature data at room pressure and temperature. The hydration free energy is more negative for smaller complexes (heavy lanthanides) relative to larger complexes (light lanthanides), with the difference between La and Lu in water amounting to 361 kJ mol⁻¹. The hydration free energy of all lanthanide ions becomes less negative with increasing pressure (p) and temperature (T) up to 2.5 GPa and 1000 K (typical conditions in the upper part of subducting slabs). The free energy difference between light- and heavy-lanthanides remains essentially unchanged at elevated (p, T) conditions. There are minor geometrical differences in local hydration environment between light lanthanide-chloride (La-Nd) and heavy lanthanide-chloride (Pm-Lu) hydrated complexes, without a distinguishable energy difference. Complexation with fluoride is energetically more favourable than with chloride by 206 ± 4 kJ mol⁻¹ across the entire lanthanide series. The association of fluoride-water and chloride-water fragments with lanthanide-water complexes is energetically more favourable for aqueous lanthanide complexes surrounded by fewer first hydration shell water molecules.The methods developed in this study, in conjunction with simulation of the energetics of trace element incorporation into minerals, open the possibility to use molecular modelling to constrain elemental behaviour in subduction zones.  相似文献   

Topographic control on distribution of modern microbially induced sedimentary structures (MISS): A case study from Texas coast     

Sushanta Bose  Henry S. Chafetz 《Sedimentary Geology》2009,213(3-4):136-149

Modern back-barrier tidal flats of Galveston Island, Follets Island, and Matagorda Peninsula of the Texas coast are dominated by mud- to fine sand-sized siliciclastic sediments and prolific microbial mats. These microbial mats modify sediment behavior and result in a variety of microbially induced sedimentary structures (MISS). Common structures include: knobby surfaces, reticulated surfaces, gas domes, mat-cracks, sieve-like surfaces, erosional pockets, wrinkles, and mat chips. In general, mat thicknesses increase from ～ 1 mm in the upper supratidal to ～ 3 cm (maximum) in the lower supratidal and then decrease to ～ 2 mm in the lower intertidal areas. This same wedge-shaped pattern is displayed by detailed measurements of mat thicknesses from the rims into the deeper centers of depressions (pools) on the supratidal flats. Measurements of 175 mat-cracks show that height of the curled edges of the mat-crack polygons increases with increase in mat thickness. Similarly, measurements of 150 gas domes reveal that the size of the gas domes also increases with increasing thickness of the associated mats. Because mat thickness varies with elevation on the tidal flat, curl height of the mat-cracks and size of the gas domes are also related to elevation.Six zones were identified based on the occurrence of MISS within the supratidal (zone-I) to upper subtidal (zone-VI) areas. At the highest elevation, knobby surfaces characterize zone-I whereas zone-II is defined by reticulated surfaces. Along with reticulated surfaces, gas domes and mat-cracks characterize zone-III and zone-IV, respectively. Association of sieve-like surfaces with mat-cracks typifies zone-V whereas mat deformation structures and sieve-like surfaces define zone-VI. Boundaries between the MISS-zones in general are parallel and related to tidal zones. The distribution patterns of the MISS-zones are strongly controlled by local topography of the sediment surface because the degree of inundation is the primary controlling factor for the mat growth and resultant MISS. Therefore, distribution of the microbially induced sedimentary structures in siliciclastics, along with the dimension of the mat-cracks and gas domes, can be potentially helpful in interpretation of topography of paleodepositional surfaces.  相似文献   

Gamma-ray bursts and their links with supernovae and cosmology     

Peter Meszairos  Neil Gehrels 《天体物理学报》2012,(8):1139-1161

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Soil erosion and sediment transport in Tanzania: Part II – sedimentological evidence of phased land degradation     

Maarten Wynants  Aloyce Patrick  Linus Munishi  Kelvin Mtei  Samuel Bodé  Alex Taylor  Geoffrey Millward  Neil Roberts  David Gilvear  Patrick Ndakidemi  Pascal Boeckx  William H. Blake 《地球表面变化过程与地形》2021,46(15):3112-3126

Soil resources in parts of Tanzania are rapidly being depleted by increased rates of soil erosion and downstream sediment transport, threatening ecosystem health, water and livelihood security in the region. However, incomplete understanding to what effect the dynamics of soil erosion and sediment transport are responding to land-use changes and climatic variability are hindering the actions needed to future-proof Tanzanian land-use practices. Complementary environmental diagnostic tools were applied to reconstruct the rates and sources of sedimentation over time in three Tanzanian river systems that have experienced changing land use and climatic conditions. Detailed historical analysis of sediment deposits revealed drastic changes in sediment yield and source contributions. Quantitative sedimentation reconstruction using radionuclide dating showed a 20-fold increase in sediment yield over the past 120 years. The observed dramatic increase in sediment yield is most likely driven by increasing land-use pressures. Deforestation, cropland expansion and increasing grazing pressures resulted into accelerating rates of sheet erosion. A regime shift after years of progressive soil degradation and convergence of surface flows resulted into a highly incised landscape, where high amounts of eroded soil from throughout the catchment are rapidly transported downstream by strongly connected ephemeral drainage networks. By integrating complementary spatial and temporal evidence bases, this study demonstrated links between land-use change, increased soil erosion and downstream sedimentation. Such evidence can guide stakeholders and policy makers in the design of targeted management interventions to safeguard future soil health and water quality.  相似文献   

Deformation of a young salt giant: regional topography of the Red Sea Miocene evaporites   总被引：1，自引：0，他引：1       下载免费PDF全文

Neil C. Mitchell  Marco Ligi  Peter Feldens  Christian Hübscher 《Basin Research》2017,29(Z1):352-369

The deformational behaviour of ‘salt giants’ during and shortly after their deposition is difficult to decipher in ocean margin settings where the original evaporites have been deeply buried and strongly mobilized. Here, we examine seismic reflection data from the Red Sea, where evaporites deposited until the end of the Miocene (~5.3 Ma), are generally covered by only 200–300 m of low‐density sediments and where the presence of an axial spreading centre allows us to observe how they have responded to a varied configuration of underlying basement. The regional morphology of the S‐reflection, representing the evaporite surface, is mapped out from seismic data from 13 cruises. The S‐reflection is locally rugged and commonly angular. It is either underlain by layered reflectivity, suggestive of layered evaporite beds, or by more transparent seismic character, suggestive of massive halite. On average, the depth of the reflection on the flanks of the axial rift systematically declines from 700 to 1100 m below sea level (mbsl) going northwards from 16 to 23°N. In the central Red Sea, the S‐reflection has 100‐ to 200‐m‐deep depressions, extending towards the coasts in places. In the southern Red Sea, the S‐reflection forms a surface at 300–800 mbsl that appears less disrupted. We suggest that the evaporites originally had a flat, horizontal surface at the end of the Miocene and have subsequently been distorted by isostatic effects and axial rifting, which in turn promoted evaporite flowage. Off‐axis evaporite depressions correspond with flows identified with multibeam sonar. Furthermore, across‐rift lows in Bouguer gravity anomalies represent valleys in the underlying basement. The off‐axis evaporite depressions overlie those valleys, as would be expected if halokinetic movements were greatest where the evaporites are locally thick, leading to deflation of the evaporite surface. The thickness of post‐Miocene sediment, also mapped out as part of this procedure, confirms the generally pelagic nature of this interval and increases on average from ~250 to 300 m from the central to the southern Red Sea, mimicking the variation in pelagic productivity observed in the present water column.  相似文献   

On low period sub-oceanic Rayleigh waves and their attenuation     

Sujit Kumar Bose M. Sc. 《Pure and Applied Geophysics》1961,49(1):15-35

Summary In most cases it is found that Rayleigh waves in the period range I to 12 secs fail to cross appreciable oceanic paths. Several explanations have been given, but none seem very much satisfactory. Here an attempt has been made to show that the attenuation of the Rayleigh waves in the low period range is due to their passage through a non-uniform earth's crust, the non-uniformity arising due to the ocean. The ocean has been taken to be an indentation in a flat earth's crust, with horizontal bottom and slant sides. Approximate numerical calculations hint that the vertical component of displacement is attenuated more than the horizontal component.  相似文献   

Geographic Patterns of Craft Breweries at the Intraurban Scale     

Isabelle Nilsson  Neil Reid  Matthew Lehnert 《The Professional geographer》2018,70(1):114-125

This article examines the intraurban geography of craft breweries in ten cities across the United States. First, through an exhaustive literature review, we outline both supply- and demand-side factors that might cause craft breweries to cluster. Second, we empirically test whether these establishments tend to cluster within cities using spatial statistical techniques. Many communities are attempting to support the establishment of more craft breweries as a way to boost tourism and economic development. The findings from this article aid in this discussion by providing insights into how craft brewers locate and the factors that could influence their location decision behavior. Our findings suggest that craft brewers do in fact cluster. There are both supply and demand factors responsible. On the supply side, the collaborative environment within the industry and the artisan nature of the industry's products allows for benefits of clustering to outweigh the costs associated with this behavior. On the demand side, the emergence of “brewery districts” allows individual brewers to enjoy the reputation benefits associated with the district in terms of increased foot traffic from locals and visitors looking to sample a variety of beers.  相似文献   

Ground-Based Observations of the Thermodynamic and Kinematic Properties of Lake-Breeze Fronts in Southern Manitoba,Canada     

Michelle Curry  John Hanesiak  Scott Kehler  David M.  L. Sills  Neil M. Taylor 《Boundary-Layer Meteorology》2017,162(1):143-169

The effects on the convective boundary layer (CBL) of shading due to shallow cumulus clouds are investigated. The main question is to see whether clouds are able to produce secondary circulations by shading of the surface (dynamic heterogeneities) and how these dynamic heterogeneities interact with static heterogeneities in terms of the production of secondary circulations. Also the effects of cloud shadows on cloud-field characteristics are analyzed. The effects are studied using large-eddy simulations of a cloud-topped CBL with an idealized surface. Over a homogeneous surface, shadows trigger secondary circulations with different strengths depending on the solar zenith angle \(\vartheta \), with large \(\vartheta \) favouring the development of secondary circulations. Over a static heterogeneous surface with a simple striped pattern, the strength of secondary circulations is effectively reduced by dynamic heterogeneities at small \(\vartheta \). At large \(\vartheta \), however, the effect on secondary circulations depends on the orientation of the striped static heterogeneities to the shadow-casting direction of the clouds. The influence of shadows is only small if they are cast perpendicular to the striped heterogeneity, but if stripes and the shadow-casting direction are parallel, secondary circulations are reduced in strength also for large \(\vartheta \). Shadow effects on the cloud-field characteristics vary with \(\vartheta \) as well. The results show that small \(\vartheta \) favours the development of small clouds with a reduced lifetime while large \(\vartheta \) promotes the development of larger clouds with an extended lifetime compared to non-shading clouds.  相似文献   

Quantifying system disturbance and recovery from historical mining-derived metal contamination at Brotherswater,northwest England     

Daniel N. Schillereff  Richard C. Chiverrell  Neil Macdonald  Janet M. Hooke  Katharine E. Welsh 《Journal of Paleolimnology》2016,56(2-3):205-221

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Recharge Estimation by Stage-Discharge Interpolation of Springflows from Cross-Correlated Well Measurements     

William H. Avery  Joseph J. Donovan  J. Neil Ketchum 《Ground water》1999,37(3):332-337

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