A groundwater isoscape (δD, δO) for Mexico

Numerous studies have shown that precipitation isocapes drive δD and δ¹⁸O patterns in surficial waters and in terrestrial food webs. While the GNIP (Global Network for Isotopes in Precipitation) dataset provided a key foundation for linking precipitation-terrestrial isoscapes globally, it has insufficient spatial coverage in many countries like Mexico. To overcome this limitation, we hypothesized that shallow phreatic groundwaters in Mexico could be used as an isotopic integrator of long-term seasonally weighted precipitation inputs to the landscape to aid in calibrating spatial H and O isotope datasets for terrestrial, biological and hydrological research. Groundwater was sampled from 234 sites in Mexico at ~ 50 km latitudinal spacing to obtain high spatial resolution and country-wide coverage for the construction of a groundwater isoscape. Our data revealed that shallow groundwater infiltration in Mexico appears largely unaffected by evaporation and reflects seasonally weighted precipitation inputs. These precipitation inputs are primarily biased to summertime when highest rainfall occurs, but a small degree of post-precipitation evaporation revealed a lower d-excess zone that corresponded to the interior semi-arid ecozone. We developed a predictive general linear model (GLM) for hydrogen and oxygen isotopic spatial patterns in Mexican groundwater and then compared the results to a validation subset of our field data, as well external data reported in the literature. The GLM used elevation, latitude, drainage basin (Atlantic vs. Pacific), and rainfall as the most relevant predictive variables. The GLM explained 81% of the overall isotopic variance observed in groundwater, 68% of the variance within our validation subset, and 77% of the variance in the external data set. Our predictive GLM is sufficiently accurate to allow for future ecological, hydrological and forensic isoscape applications in Mexico, and may be an approach that is applicable to other countries and regions where GNIP stations are lacking.     

Early generation of 20S-5α(H),14α(H),17α(H)- and 5α(H),14β(H),17β(H)-steranes in low salinity lacustrine shales

A quantitative sterane biomarker study was conducted on a series of paralic freshwater lacustrine shale samples ranging in maturity from immature to near oil window maturity taken from Section 3 of the Shahejie Formation (Es3) in the Liaohe Basin, N.E. China. Concentrations of 5α(H),14α(H),17α(H)-20S and 5α(H),14β(H),17β(H)-steranes remain nearly constant throughout the sample suite. However, the decrease in the absolute concentrations of the 20R-5α(H),14α(H),17α(H)-C₂₉ steranes with increasing maturity results in an increase in the conventionally defined maturity parameters, 20S/(20S + 20R)-ααα and αββ/(ααα + αββ) sterane ratios. In addition, the data suggest that relatively early generation of 5α(H),14α(H),17α(H)-20S and 5α(H),14β(H),17β(H)-steranes has occurred in lacustrine sediments with a vitrinate reflectance 0.3% (R_o). The data provide strong support for the major importance of relative thermal stability of epimers, but do not exclude the possibility of isomerization as a viable mechanism for production.     

α- and β-diversity Change of Late Ordovician Hirnantia Fauna of Changning, Sichuan, Southwest China

A continuous Ordovician-Silurian boundary section from the upper Wufeng Formation through the Kuanyinchiao Formation to the lower Lungmachi Formation has been carefully measured and collected at Shuanghe of Changning, southern Sichuan Province. For the first time, the temporal changes of α- and β-diversities of the Hirnantia fauna have been discussed in great detail. The general trend of brachiopod diversity change, increasing upward, is consistent with the regional trend of the Yangtze Platform, which had been controlled by both intrinsic and extrinsic factors. However, the sudden drop of diversity for a short period in the upper Kuanyinchiao Formation might have been controlled by environmental factors rather than normal faunal turnover. Synecological analysis using numerical methods recognizes two brachiopod-dominated associations of the Hirnantia fauna, the Dalmanella-Kinnella Association and the Mirorthis Association, both living in an offshore, deeper water environment corresponding to BA3-upper BA4, particularly lower BA3.     

Theoretical Prediction of Gibbs Free Energies of Formation for Crystalline α-MOOH and α-M2O3 Based on a Linear Free-Energy Relationship

In the present study, the modified Sverjensky–Molling equation, derived from a linear-free energy relationship, is used to predict the Gibbs free energies of formation of crystalline phases of α-MOOH (with a goethite structure) and α-M2O3 (with a hematite structure) from the known thermodynamic properties of the corresponding aqueous trivalent cations (M3+). The modified equation is expressed as ΔG0f,MVX=aMVXΔG0n,M3++bMVX+βMVXγM3+, where the coefficients aMVX, bMVX, and βMVX characterize a particular structural family of MvX (M is a trivalent cation [M3+] and X represents the remainder of the composition of solid); γ3+ is the ionic radius of trivalent cations (M3+); ΔG0f,MVX is the standard Gibbs free energy of formation of MvX; and ΔG0n,M3+ is the non-solvation energy of trivalent cations (M3+). By fitting the equation to the known experimental thermodynamic data, the coefficients for the goethite family (α-MOOH) are aMVX=0.8838, bMVX=?424.4431 (kcal/mol), and βMVX=115 (kcal/mol.?), while the coefficients for the hematite family (α-M2O3) are aMVX=1.7468, bMVX=?814.9573 (kcal/mol), and βMVX=278 (kcal/mol.?). The constrained relationship can be used to predict the standard Gibbs free energies of formation of crystalline phases and fictive phases (i.e. phases that are thermodynamically unstable and do not occur at standard conditions) within the isostructural families of goethite (α-MOOH) and hematite (α-M2O3) if the standard Gibbs free energies of formation of the trivalent cations are known.     

Spectral analysis of nonlocal regularization in two‐dimensional finite element models

Strain‐softening in geomaterials often leads to ill‐posed boundary‐valued problems (BVP), which cannot be solved with finite element methods without introducing some kind of regularization such as nonlocal plasticity. Hereafter we propose to apply spectral analysis for testing the performance of nonlocal plasticity in regularizing ill‐posed BVP and producing mesh‐independent solutions when local plasticity usually fails. The spectral analysis consists of examining the eigenvalues and eigenvectors of the global tangential stiffness matrix of the incremental equilibrium equations. Based on spectral analysis, we propose a criterion for passing or failing the test of constitutive regularization in the context of BVP. If the eigenvalues of the tangential operator are all positive then the regularization succeeds, otherwise it fails and may not prevent artificial mesh‐dependent solutions from appearing. The approach is illustrated in the particular case of a biaxial compression with strain‐softening plasticity. In this particular case, local softening plasticity is found to produce negative eigenvalues in the tangential stiffness matrix, which indicates ill‐posed BVP. In contrast, nonlocal softening plasticity always produces positive eigenvalues, which regularizes ill‐posed BVP. The dominant eigenvectors, which generate localized deformation patterns, have a bandwidth independent of mesh size, provided that the mesh is fine enough to capture localization. These mesh‐independent eigenmodes explain why nonlocal plasticity produces numerical solutions that are mesh‐independent. Copyright © 2011 John Wiley & Sons, Ltd.     

Lower Triassic δC isotope curve from shallow-marine carbonates in Japan, Panthalassa realm: Confirmation of the Tethys δC curve

δ¹³C data from Tethyan sections provide evidence of profound changes in the carbon cycle during the Lower Triassic. Sections from the Panthalassa realm were investigated to establish whether these variations are also present there. In the Jurassic accretionary wedges in Japan, exotic blocks having a Panthalassan affinity, have been incorporated. The majority of the blocks are pelagic cherts but rare shallow-water carbonates are also present. We present a δ¹³C study on the Lower Triassic of a shallow-water carbonate succession deposited on a mid-oceanic seamount and accreted to the Chichibu Belt, Japan. Two sections have been measured at Kamura, central Kyushu Island. The carbon isotope curve shows depleted values across the Permian–Triassic boundary (PTB), subsequently followed by an increase to heavier values into the Dienerian, culminating in a maximum of almost +4‰ V-PDB, before a steep drop at a stratigraphic gap. Low values are recorded in the Smithian, but rise to enriched δ¹³C values > +3.5‰ near the Smithian–Spathian boundary. The observed trend of the stable carbon isotope curve from Japanese sediments mirrors the curves derived from sections in the Tethys (e.g. Italy, Iran, Turkey, Oman and the South China Nanpanjing Basin). Our results support the interpretation of this curve as representing a global trend across the PTB and in the Lower Triassic, although some distinct features are absent around the Dienerian/Smithian boundary. Profound variations of the carbon isotope curve in the Lower Triassic are presented for the first time from a marine section outside of the Tethys. They indicate severe, global changes in the Lower Triassic carbon cycle, and the causative processes must have significantly contributed to the delayed biotic recovery after the PTB. Large amounts of carbon were shifted between carbon reservoirs, most probably between shallow- and deep-ocean waters, and/or ocean and sediment. Anoxia followed by overturn of the ocean water masses may have been the mechanism which quickly altered ecological conditions in the ocean leading to variable availability of nutrients and oxygen, and changes in isotope composition of the available carbon in the surface waters that was incorporated in the precipitated carbonate.     

Climatic and non-climatic effects on the δO and δC compositions of Lake Awassa, Ethiopia, during the last 6.5 ka

A comparison of a 6450 ¹⁴C yr δ¹⁸O and δ¹³C record of authigenic calcite from Lake Awassa, Ethiopia, with other proxy climate records in the area suggests that the lake records long-term regional climate changes. Co-varying and increasing δ¹⁸O and δ¹³C values from 4800 BP suggest an aridification of climate after the early Holocene insolation maximum. After 4000 BP, humid conditions return until after 2800 BP when δ¹⁸O increases again, reflecting more arid conditions recorded elsewhere in Ethiopia. In addition to these long-term changes, there are abrupt decreases in both δ¹⁸O_calcite and δ¹³C_calcite immediately after tephra layers. The likeliest explanation for these abrupt decreases in isotopes is the effect of tephra on the lake's catchment vegetation. δ¹⁸O, δ¹³C and lake-level measurements from Lake Awassa since the 1970s suggest that the lake is currently isotopically sensitive to short-term (annual–decadal) climate change. However, during this period, the catchment has undergone progressive deforestation that may have caused an increase in runoff. Caution is therefore required when reconstructing palaeoclimates as a contemporary lake may not always be a good analogue for lake hydrology in the past.     

Mercury mobilization by oxidative dissolution of cinnabar (α-HgS) and metacinnabar (β-HgS)

Cinnabar (α-HgS) and metacinnabar (β-HgS) dissolved at environmentally significant rates in oxygenated slurry experiments simulating a low-flow fluvial system. Based on SO₄²⁻ production, cinnabar dissolution rates were 2.64 to 6.16 μmol (SO₄²⁻) m^− 2 day^− 1, and metacinnabar dissolution rates were 1.20 to 1.90 μmol (SO₄²⁻) m^− 2 day^− 1. Monodentate-bound thiosulfate (S₂O₃²⁻) was identified as an oxidation product on the HgS surface by ATR-IR spectroscopy based on strong infrared absorption bands in the 1140–1145 cm^− 1 and 1006–1014 cm^− 1 regions. The presence of sulfide oxidation intermediates on the HgS surface indicates that SO₄²⁻ concentration underestimates α-HgS and β-HgS dissolution in this setting. Mercury release rates during dissolution were more than two orders of magnitude less than SO₄²⁻ production, but were significant: 0.47 mg (Hg) m^− 2 y^− 1 from cinnabar [6.45 nmol (Hg) m^− 2 day^− 1], and 0.17 mg (Hg) m^− 2 y^− 1 from metacinnabar [2.29 nmol (Hg) m^− 2 day^− 1]. The Hg mobilized during α-HgS and β-HgS dissolution is sufficient to form natural Au–Hg amalgam in downstream placer settings. The proportion of mercury that is not remobilized during α-HgS and β-HgS dissolution likely adsorbs to the dissolving mercuric sulfide. Adsorption of Hg²⁺ to cinnabar was detected in situ by anodic stripping voltammetry using a cinnabar-modified carbon paste electrode following accumulation of Hg²⁺ on the electrode at open circuit potential.     

‘Infinite domain’ elements in finite element analysis of underground excavations

The Finite Element Method is frequently used to analyse problems involving an ‘infinite domain’. A typical problem is an underground excavation in prestressed infinite medium in either tunnelling or mining operations or a foundation in an infinite half space. This paper examines the implications of mesh truncation on the accuracy of the accuracy of the solution. At the same time, a more economical and accurate method of analysing these problems using special ‘infinite domain’ Finite Elements is presented.     

Numerical performance of projection methods in finite element consolidation models

Projection, or conjugate gradient like, methods are becoming increasingly popular for the efficient solution of large sparse sets of unsymmetric indefinite equations arising from the numerical integration of (initial) boundary value problems. One such problem is soil consolidation coupling a flow and a structural model, typically solved by finite elements (FE) in space and a marching scheme in time (e.g. the Crank–Nicolson scheme). The attraction of a projection method stems from a number of factors, including the ease of implementation, the requirement of limited core memory and the low computational cost if a cheap and effective matrix preconditioner is available. In the present paper, biconjugate gradient stabilized (Bi‐ CGSTAB) is used to solve FE consolidation equations in 2‐D and 3‐D settings with variable time integration steps. Three different nodal orderings are selected along with the preconditioner ILUT based on incomplete triangular factorization and variable fill‐in. The overall cost of the solver is made up of the preconditioning cost plus the cost to converge which is in turn related to the number of iterations and the elementary operations required by each iteration. The results show that nodal ordering affects the perfor mance of Bi‐CGSTAB. For normally conditioned consolidation problems Bi‐CGSTAB with the best ILUT preconditioner may converge in a number of iterations up to two order of magnitude smaller than the size of the FE model and proves an accurate, cost‐effective and robust alternative to direct methods. Copyright © 2001 John Wiley & Sons, Ltd.     

Implementation of the finite element method in the three‐dimensional discontinuous deformation analysis (3D‐DDA)

A modified three‐dimensional discontinuous deformation analysis (3D‐DDA) method is derived using four‐noded tetrahedral elements to improve the accuracy of current 3D‐DDA algorithm in practical applications. The analysis program for the modified 3D‐DDA method is developed in a C++ environment and its accuracy is illustrated through comparisons with several analytical solutions that are available for selected problems. The predicted solutions for these problems using the modified 3D‐DDA approach all show satisfactory agreement with the corresponding analytical results. Results presented in this paper demonstrate that the modified 3D‐DDA method with discontinuous modeling capabilities offers a useful computational tool to determine stresses and deformations in practical problems involving fissured elastic media with reasonable accuracy. Copyright © 2008 John Wiley & Sons, Ltd.     

Paleoclimate reconstruction derived from speleothem strontium and δC in Central Florida

Variability of strontium and carbon isotopes are reported from a speleothem from Central Florida, USA. Thermal ionization mass spectrometry of uranium–thorium isotopes indicate the speleothem was precipitated during the last 4000 years. Sr concentrations are negatively correlated with δ¹³C, a relationship inferred to record changes in soil productivity. Coeval changes in the Sr content and δ¹³C signals, as induced by soil productivity, are explained by changing precipitation above the cave. Both proxies record a 170–180-year solar cycle that has also been found in the Gulf of Mexico marine records and elsewhere. Consequently, this result provides evidence of an extraterrestrially driven modulator of precipitation in Central Florida.     

Tree-Ring δD as an Indicator of Asian Monsoon Intensity

Oxygen and hydrogen isotopic compositions of meteoric water are known to correlate with surface air temperature, except in tropical areas. This relationship has been described using a number of terms corresponding to specific observations, such as latitude, altitude and seasonal effects. However, these temperature effects do not seem to apply to precipitation in monsoonal areas of Asia. Questions have been raised as to whether the isotopic composition of meteoric water can be used to reconstruct paleomonsoon intensity. Tree rings of two modern spruce trees (Picea meyeri) and a 10,000-yr-old timber (Picea jezoensis) were analyzed for hydrogen isotopic composition. On average, the older tree is depleted in deuterium by 45‰ compared to the modern trees. We attribute this isotopic depletion to the strength of summer monsoons, which were more intense in the early Holocene than at present. Although this study is not definitive, it suggests that paleomonsoon intensity can be reconstructed by direct or proxy methods that yield the oxygen or hydrogen isotopic composition of meteoric water.     

Thermodynamic stability of various alkylated, dealkylated and rearranged 17α- and 17β-hopane isomers using molecular mechanics calculations

The thermodynamic stability of selected alkylated, dealkylated and rearranged 17α- and 17β-hopane isomers in the C₂₇, C₂₈, C₂₉, C₃₀ and C₃₁ families were calculated using molecular mechanics (MM2) methods and, where possible, calculated equilibrium ratios of certain isomers were compared with observed ratios of isomers in thermally mature crude oil samples. Those calculated and observed ratios having similar values include: (1) the relative distributions among 17β(H)/17α(H) and 21β(H)/21α(H)-hopanes including the absence of the 17β(H),21β(H)- and 17α(H),21α(H)-hopanes; (2) the 22R/22S ratios in 30-methyl-17α-hopane and 30-methyl-17β-moretane; (3) the relative distributions among 17α(H)/17β(H)- and 21α(H)/21β(H)-28,30-bisnorhopanes and among 25,28,30-trisnorhopanes, including the relatively greater stability of 17β(H) isomers in contrast to the regular hopane series; and (4) the ratios of 28(18−17S)abeo hopanes with respect to their unrearranged counterparts including the C₂₇ compounds, Ts/Tm.     

The Origin of Paleokarst in the Huanglong Formation of the Eastern Sichuan Basin: Evidence from δ13C, δ18O and 87Sr/86Sr

Karst rocks from the Huanglong Formation exposed at the margin of the Eastern Sichuan Basin can be divided into four types:slightly corroded, moderately corroded porous, intensely corroded brecciated and intensely corroded and replaced secondary calcic karstic rocks. The carbon, oxygen and strontium isotope compositions of the various karst rocks are analyzed systematically and compared to rocks without karst corrosion. The results indicate that(1) the Huanglong Formation in the eastern Sichuan Basin was a restricted bay supplied and controlled by freshwater in which mudmicrite and mud-dolomicrite exhibit low δ13C and δ18O values and high 87Sr/86 Sr ratios;(2) all types of karstic rocks in the paleokarst reservoirs of the Huanglong Formation in the research area are affected by atmospheric freshwater with the δ13C and δ18O values and 87Sr/86 Sr ratios in the original formation approaching those of atmospheric freshwater, which reflects ancient hydrological conditions, fluid properties, isotopic source and the fractionation effect;(3) the intensely corroded and replaced secondary limestone is affected by a variety of diagenetic fluids, often reflected by δ13C and δ18O values, while the 87Sr/86 Sr ratios exhibit the strong degree of the corrosion;(4) after comparing the 87Sr/86 Sr ratios of each type of karst rock, the diagenetic fluids are determined to be mainly atmospheric freshwater, and depending on the strength of corrosion, and the low 87Sr/86 Sr ratio fluids in the layer will participate in the karst process. The carbon, oxygen, and strontium isotopes of different karstic reservoirs can provide meaningful geochemical information for forecasting and evaluating the development and distribution rules of the Huanglong Formation at the margin of the eastern Sichuan Basin in time and space.     

Water ordering and surface relaxations at the hematite (1 1 0)-water interface

Structural characterization of iron oxide-water interfaces provides insight into the mechanisms through which these minerals control contaminant fate and element cycling in soil, sedimentary, and groundwater systems. Ordering of interfacial water and structural relaxations at the hematite (1 1 0) surface have been investigated in situ using high-resolution specular X-ray reflectivity. These measurements demonstrate that relaxations are constrained to primarily the top ∼5 Å of the surface. Near-surface iron atoms do not relax substantially, although the uppermost layer displays an increased distribution width, while the undercoordinated oxygens on the surface uniformly relaxed outward. Two sites of adsorbed water and additional layering of water farther from the surface were observed. Water fully covers the (1 1 0) surface and appears to form a continuous network extending into bulk solution, with positional order decreasing to that of a disordered bulk fluid within 1 nm. The arrangement of water is similar to that on the hematite (0 1 2) surface, which has a similar surface topography, although these surfaces display different vibrational amplitudes or positional disorder of adsorbed water molecules and average spacings of near-surface layered water. Comparison between these surfaces suggests that interfacial water ordering on hematite is controlled primarily by surface structure and steric constraints and that highly ordered water is likely common to most hematite-water interfaces.     

50 Myr recovery from the largest negative δ13C excursion in the Ediacaran ocean

Sedimentary rocks deposited during the Ediacaran period (～630–542 Ma) contain carbonates whose carbon isotopic ratios show a marked negative excursion consisting of a precipitous drop from +5‰ to ?12‰, followed by a sub‐linear recovery to positive δ¹³C values. Isotopic ages (U/Pb) and thermal subsidence modelling are combined to constrain the excursion in time and indicate an onset at ～600 Ma, and duration of recovery of approximately 50 Myr. The excursion is widely recognized in Oman and has potential correlatives in Ediacaran strata elsewhere, and may thus represent a characteristic feature of the Ediacaran period. The amplitude of this carbon isotope excursion far exceeds those of other Neoproterozoic anomalies. The isotopic trend of negative excursion and long‐term recovery spanned at least one short‐lived glacial episode (at 580 Ma), but appears unrelated to glaciation, which indicates that negative anomalies in the Neoproterozoic marine carbon isotope record are not directly or uniquely linked to ice ages.