Accurate measurement of silver isotopic compositions in geological materials including low Pd/Ag meteorites

Very precise silver (Ag) isotopic compositions have been determined for a number of terrestrial rocks, and high and low Pd/Ag meteorites by utilizing multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). The meteorites include primitive chondrites, the Group IAB iron meteorites Canyon Diablo and Toluca, and the Group IIIAB iron meteorite Grant. Silver isotopic measurements are primarily of interest because ¹⁰⁷Ag was produced by decay of the short-lived radionuclide ¹⁰⁷Pd during the formation of the solar system and hence the Pd-Ag chronometer has set constraints on the timing of early planetesimal formation. A 2σ precision of ±0.05‰ can be obtained for analyses of standard solutions when Ag isotopic ratios are normalized to Pd, to correct for instrumental mass discrimination, and to bracketing standards. Caution must be exercised when making Ag isotopic measurements because isotopic artifacts can be generated in the laboratory and during mass spectrometry. The external reproducibility for geological samples based on replicate analyses of rocks is ±0.2‰ (2σ).All chondrites analyzed have similar Ag isotopic compositions that do not differ significantly (>0.3‰) from the ‘terrestrial’ value of the NIST SRM 978a Ag isotope standard. Hence, they show no evidence of excess ¹⁰⁷Ag derived from ¹⁰⁷Pd decay or, of stable Ag isotope fractionation associated with volatile element depletion within the accretion disk or from parent body metamorphism. The Group IAB iron meteorite samples analyzed show evidence of complex behavior and disturbance of Ag isotope systematics. Therefore, care must be taken when using this group of iron meteorites to obtain chronological information based on the Pd-Ag decay scheme.     

Chemical weathering in the Upper Huang He (Yellow River) draining the eastern Qinghai-Tibet Plateau

We examined the fluvial geochemistry of the Huang He (Yellow River) in its headwaters to determine natural chemical weathering rates on the northeastern Qinghai-Tibet Plateau, where anthropogenic impact is considered small. Qualitative treatment of the major element composition demonstrates the dominance of carbonate and evaporite dissolution. Most samples are supersaturated with respect to calcite, dolomite, and atmospheric CO₂ with moderate (0.710-0.715) ⁸⁷Sr/⁸⁶Sr ratios, while six out of 21 total samples have especially high concentrations of Na, Ca, Mg, Cl, and SO₄ from weathering of evaporites. We used inversion model calculations to apportion the total dissolved cations to rain-, evaporite-, carbonate-, and silicate-origin. The samples are either carbonate- or evaporite-dominated, but the relative contributions of the four sources vary widely among samples. Net CO₂ consumption rates by silicate weathering (6-120 × 10³ mol/km²/yr) are low and have a relative uncertainty of ∼40%. We extended the inversion model calculation to literature data for rivers draining orogenic zones worldwide. The Ganges-Brahmaputra draining the Himalayan front has higher CO₂ consumption rates (110-570 × 10³ mol/km²/yr) and more radiogenic ⁸⁷Sr/⁸⁶Sr (0.715-1.24) than the Upper Huang He, but the rivers at higher latitudes are similar to or lower than the Upper Huang He in CO₂ uptake by silicate weathering. In these orogenic zones, silicate weathering rates are only weakly coupled with temperature and become independent of runoff above ∼800 mm/yr.     

Assessing storm surge impacts on coastal inundation due to climate change: case studies of Baltimore and Dorchester County in Maryland

Natural Hazards - Hurricane Isabel (2003) generated record flooding around Chesapeake Bay and caused extensive damage in rural Eastern Shore of Maryland and metropolitan cities like Baltimore....     

The influence of coupled physical swelling and chemical reactions on deformable geomaterials

Coupled thermo‐hydro‐mechanical‐chemical modelling has attracted attention in past decades due to many contemporary geotechnical engineering applications (e.g., waste disposal, carbon capture and storage). However, molecular‐scale interactions within geomaterials (e.g., swelling and dissolution/precipitation) have a significant influence on the mechanical behaviour, yet are rarely incorporated into existing Thermal‐Hydro‐Mechanical‐Chemical (THMC) frameworks. This paper presents a new coupled hydro‐mechanical‐chemical constitutive model to bridge molecular‐scale interactions with macro‐physical deformation by combining the swelling and dissolution/precipitation through an extension of the new mixture‐coupling theory. Entropy analysis of the geomaterial system provides dissipation energy, and Helmholtz free energy gives the relationship between solids and fluids. Numerical simulation is used to compare with the selected recognized models, which demonstrates that the swelling and dissolution/precipitation processes may have a significant influence on the mechanical deformation of the geomaterials.     

Modeling the 2D behavior of dry‐stone retaining walls by a fully discrete element method

The dry‐stone retaining walls (DSRW) have been tipped as a promising solution for sustainable development. However, before recently, their behavior is relatively obscure. In this study, discrete element method (DEM) approach was applied to simulate the plane strain failure of these walls. A commercial DEM package (PFC2D™) was used throughout this study. The authors used a fully discrete approach; thus, both the wall and the backfill were modeled as discrete elements. The methodology for obtaining the micromechanical parameters was discussed in detail; this includes the three mechanical sub‐systems of DSRWs: wall, backfill and interface. The models were loaded progressively until failure, and then the results were compared with the full‐scale experimental results where the walls were loaded, respectively, with hydrostatic load and backfill. Despite its complexity and its intensive calculation time, DEM model can then be used to validate a more simplified approach. Copyright © 2015 John Wiley & Sons, Ltd.     

High-P (P = 1.5–1.8 GPa) blueschist from Elba: Implications for underthrusting and exhumation of continental units in the Northern Apennines

The Acquadolce Subunit on the Island of Elba, Italy, records blueschist facies metamorphism related to the Oligocene–early Miocene stages of continental collision in the Northern Apennines. The blueschist facies metamorphism is represented by glaucophane- and lawsonite-bearing metabasite associated with marble and calcschist. These rock types occur as lenses in a schistose complex representing foredeep deposits of early Oligocene age. Detailed petrological analyses on metabasic and metapelitic protoliths, involving mineral and bulk-rock chemistry coupled with P–T and P–T–X(Fe₂O₃) pseudosection modelling using PERPLE_X, show that the Acquadolce Subunit recorded nearly isothermal exhumation from peak pressure–temperature conditions of 1.5–1.8 GPa and 320–370°C. During exhumation, peak lawsonite- and possibly carpholite- or stilpnomelane-bearing assemblages were overprinted and partially obliterated by epidote-blueschist and, subsequently, albite-greenschist facies metamorphic assemblages. This study sheds new light on the tectonic evolution of Adria-derived metamorphic units in the Northern Apennines, by showing (a) the deep underthrusting of continental crust during continental collision and (b) rapid exhumation along ‘cold’ and nearly isothermal paths, compatible with syn-orogenic extrusion.     

The groundwater recharge regime of some slightly metamorphosed neoproterozoic sedimentary rocks: an application of natural environmental tracers

Isotope data of precipitation and groundwater in parts of the Voltaian Basin in Northern Ghana were used to explain the groundwater recharge regime in the area. Groundwater recharge is an important parameter in the development of a decision support system for the management and efficient utilization of groundwater resources in the area. It is therefore important to establish the processes and sources of groundwater recharge. δ¹⁸O and δ²H data for local precipitation suggest enrichment relative to the Global Meteoric Water Line (GMWL) and indicate that precipitation takes place at a relative humidity less than 100%. The groundwater data plot on an evaporation line with a slope of 5, suggesting a high degree of evaporative enrichment of the precipitation in the process of vertical infiltration and percolation through the unsaturated zone into the saturated zone. This finding is consistent with the observation of high evapotranspiration rates in the area and ties in with the fact that significant clay fraction in the unsaturated zone limits vertical percolation and thus exposes the percolating rainwater to the effects of high temperatures and low humidities resulting in high evapotranspiration rates. Groundwater recharge estimates from the chloride mass balance, CMB, method suggest recharge in the range of 1.8–32% of the annual average precipitation in the form of rainfall. The highest rates are associated with areas where open wells encourage significant amount of groundwater recharge from precipitation in the area. In the northern parts of the study area, groundwater recharge is lower than 12%. The recharge so computed through the application of the CMB methodology takes on a spatial distribution akin to the converse of the spatial pattern of both δ¹⁸O and δ²H in the area. As such, the locations of the highest recharge are associated with the most depleted values of the two isotopes. This observation is consistent with the assertion that low vertical hydraulic conductivities slow down vertical percolation of precipitation down to the groundwater water. The percolating precipitation water thus gets enriched in the heavier isotopes through high evapotranspiration rates. At the same time, the amount of water that finally reaches the water table is considerably reduced. Copyright © 2013 John Wiley & Sons, Ltd.     

Water source dynamics of high Arctic river basins

Arctic river basins are amongst the most vulnerable to climate change. However, there is currently limited knowledge of the hydrological processes that govern flow dynamics in Arctic river basins. We address this research gap using natural hydrochemical and isotopic tracers to identify water sources that contributed to runoff in river basins spanning a gradient of glacierization (0–61%) in Svalbard during summer 2010 and 2011. Spatially distinct hydrological processes operating over diurnal, weekly and seasonal timescales were characterized by river hydrochemistry and isotopic composition. Two conceptual water sources (‘meltwater’ and ‘groundwater’) were identified and used as a basis for end‐member mixing analyses to assess seasonal and year‐to‐year variability in water source dynamics. In glacier‐fed rivers, meltwater dominated flows at all sites (typically >80%) with the highest contributions observed at the beginning of each study period in early July when snow cover was most extensive. Rivers in non‐glacierized basins were sourced initially from snowmelt but became increasingly dependent on groundwater inputs (up to 100% of total flow volume) by late summer. These hydrological changes were attributed to the depletion of snowpacks and enhanced soil water storage capacity as the active layer expanded throughout each melt season. These findings provide insight into the processes that underpin water source dynamics in Arctic river systems and potential future changes in Arctic hydrology that might be expected under a changing climate. Copyright © 2013 John Wiley & Sons, Ltd.