Sources of Inaccuracy in Boron Isotope Measurement Using LA-MC-ICP-MS

Laser ablation multi-collector-inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) has become a valuable tool for the in situ measurement of the boron isotope composition of geological samples at high (tens to hundreds of μm) spatial resolution. That said, this application suffers from significant analytical challenges. We focus in this study on the underlying processes of two of the main causes for inaccuracies using this technique. We provide empirical evidence that not only Ca ions (Sadekov et al. 2019, Standish et al. 2019, Evans et al. 2021) but also Ar ions, that are reflected within the flight tube of the mass spectrometer, are the source for previously reported issues with spectral baselines. We also address the impact of plasma conditions on the instrumental mass fractionation as a source for matrix- and mass-load-related analytical biases. Comparing experimental data with the results of a dedicated release and diffusion model (RDM) we estimate that a close to complete (~ 97%) release of boron from the sample aerosol is needed to allow for consistently accurate LA boron isotope measurement results without the need for corrections.     

Computing derivative information of sequentially coupled subsurface models

A generic framework for the computation of derivative information required for gradient-based optimization using sequentially coupled subsurface simulation models is presented. The proposed approach allows for the computation of any derivative information with no modification of the mathematical framework. It only requires the forward model Jacobians and the objective function to be appropriately defined. The flexibility of the framework is demonstrated by its application in different reservoir management studies. The performance of the gradient computation strategy is demonstrated in a synthetic water-flooding model, where the forward model is constructed based on a sequentially coupled flow-transport system. The methodology is illustrated for a synthetic model, with different types of applications of data assimilation and life-cycle optimization. Results are compared with the classical fully coupled (FIM) forward simulation. Based on the presented numerical examples, it is demonstrated how, without any modifications of the basic framework, the solution of gradient-based optimization models can be obtained for any given set of coupled equations. The sequential derivative computation methods deliver similar results compared to FIM methods, while being computationally more efficient.     

A Spectral Analysis Based Methodology to Detect Climatological Influences on Daily Urban Water Demand

Urban water demand (UWD) is highly dependent on interacting natural and socio-economic factors, and thus a wide range of data analysis and forecasting methods are required to fully understand the issue. This study applies, for the first time, the continuous wavelet transform to determine changes in the temporal pattern of UWD and its potential meteorological drivers for three major Canadian cities: Calgary, Montreal, and Ottawa. This analysis is complemented by Fourier and cross-spectral analysis to determine inter-relationships and the significance of the patterns detected. The results show that the annual (365 days) cycle provides the most consistent and significant relationship between UWD and meteorological drivers. Wavelet analysis shows that UWD is only sensitive to air temperature in the summer months when mean daily temperatures are greater than 10 to 12 °C. For the three cities studied, the UWD increases by between 10 ML (Montreal) and 50 ML (Calgary) per day with every 1 °C increase in air temperature. In an area with low precipitation (Calgary), there is an inverse relationship between UWD and precipitation during summer months. Wavelet transform and Fourier analysis also detected a 7-day cycle in UWD, particularly in the more industrialized city of Montreal, which is related to the working week. In general, applying the season dependent linear relationships between UWD and temperature is suggested as perhaps being more appropriate and potentially successful for forecasting, rather than continuous complex nonlinear algorithms that are designed to explain variability in the entire UWD record.     

Compression Behaviour of Chlef Sand and Transition of Fines Content Using Pressure-Dependent Maximum Void Ratios of Sand

Geotechnical and Geological Engineering - This paper presents a study on Chlef sand to examine the effect of fines content (Fc), relative density (RD) and initial conditions on the compressibility...     

Lithospheric Electrical Structure across the Eastern Segment of the Altyn Tagh Fault on the Northern Margin of the Tibetan Plateau

Project INDEPTH (InterNational DEep Profiling of Tibet and the Himalaya) is an interdisciplinary program designed to develop a better understanding of deep structures and mechanics of the Tibetan Plateau. As a component of magnetotelluric (MT) work in the 4th phase of the project, MT data were collected along a profile that crosses the eastern segment of the Altyn Tagh fault on the northern margin of the plateau. Time series data processing used robust algorithms to give high quality responses. Dimensionality analysis showed that 2D approach is only valid for the northern section of the profile. Consequently, 2D inversions were only conducted for the northern section, and 3D inversions were conducted on MT data from the whole profile. From the 2D inversion model, the eastern segment of the Altyn Tagh fault only appears as a crustal structure, which suggests accommodation of strike slip motion along the Altyn Tagh fault by thrusting within the Qilian block. A large-scale off-profile conductor within the mid-lower crust of the Qilian block was revealed from the 3D inversion model, which is probably correlated with the North Qaidam thrust belt. Furthermore, the unconnected conductors from the 3D inversion model indicate that deformations in the study area are generally localized.     

Microlaboratory study on magnetic,gravity and high-tension separation of hercynite and pleonaste from low-grade ilmenite concentrates

Some ilmenite concentrates obtained from oleate flotation of ilmenite ores from NE Poland contain less than the required 45% TiO₂ due to the presence of green spinels (hercynite and pleonaste). Such concentrates were further upgraded by different separation techniques. It was established at microlaboratory scale that magnetic, gravity and high-tension separations can provide qualified ilmenite concentrates with TiO₂ recovery in the order of 50 to 80%.     

Magmatic evolution of the Karmøy Ophiolite Complex,SW Norway: relationships between MORB-IAT-boninitic-calc-alkaline and alkaline magmatism

The polyphasal magmatic evolution of the Caledonian Karmøy Ophiolite Complex includes: (1) formation of an axis sequence from island-arc tholeiitic (IAT) and more MORB-like magmas (493+7/-4 Ma); (2) intrusion of magmas of boninitic affinity (485±2 Ma); (3) intrusion of MORB- and IAT-like magmas; (4) intrusion and extrusion of calc-alkaline magmas (470+9/-5 Ma); (5) intrusion and extrusion of basalts with alkaline trace-element affinity. Repeated intrusion of MORB and IAT-like magmas may be explained by intermittent magmatism involving magma-chamber solidification and remelting of a source characterized by initial _Nd of approximately +6.5. The boninitic rocks may have formed from two LREE-depleted sources: the primary source of the axis-sequence magmas and the residual source left after extraction of these magmas. These sources have been enriched in LREE, Th and Zr from subducted material exhibiting a continental Nd-isotope signature with initial _Nd less than-8. Covariation between _Nd and Th, Zr, Nd, Y and Yb may be explained by metasomatic enrichment of a LREE-depleted mantle source by a LREE-enriched subduction component, followed by partial melting during which the degree of melting of the metasomatized mantle source increased linearly with the amount of subduction component added to the mantle source. The calc-alkaline magmas may have formed by remelting of a highly depleted source, which became enriched in some trace elements derived from the source of the subsequent alkaline magmatism. The geology and geochemistry of the Karmøy Ophiolite Complex suggest growth of an island-arc upon newly-formed oceanic crust, followed by arc-splitting and the development of a new basin.     

Sedimentary and faunal events revealed by a revised correlation of post‐glacial Hirnantian (Late Ordovician) strata in the Welsh Basin,UK

The discovery of a previously unrecognized unconformity and of new faunas in the type Llandovery area underpins a revised correlation of Hirnantian strata in mid Wales. This has revealed the sedimentary and faunal events which affected the Lower Palaeozoic Welsh Basin during the global rise in sea level that followed the end‐Ordovician glacial maximum and has allowed their interpretation in the context of local and global influences. In peri‐basinal shelfal settings the onset of post‐glacial deepening is recorded by an unfossiliferous, transgressive shoreface sequence (Cwm Clyd Sandstone and Garth House formations) which rests unconformably on Rawtheyan rocks, deformed during an episode of pre‐Hirnantian tectonism. In the deep water facies of the basin centre, this same sequence boundary is now recognized as the contact between fine‐grained, re‐sedimented mudstones and an underlying regressive sequence of turbidite sandstones and conglomerates; it is at a level lower than previously cited and calls into question the established lithostratigraphy. In younger Hirnantian strata, graptolites associated with the newly recognized Ystradwalter Member (Chwefri Formation) demonstrate that this distal shelf unit correlates with the persculptus graptolite‐bearing Mottled Mudstone Member of the basinal succession. Together these members record an important macrofaunal recolonization of the Welsh Basin and mark a key event in the post‐glacial transgression. Further deepening saw the establishment of a stratified water column and the imposition of anoxic bottom water conditions across the basin floor. These post‐glacial Hirnantian events are consistent with the re‐establishment of connections between a silled Welsh Basin and the open Iapetus Ocean. However, a comparison with other areas suggests that each event records a separate deepening episode within a pulsed glacio‐eustatic transgression, while also reflecting changes in post‐glacial climate and patterns of oceanic circulation and associated biotic flux. British Geological Survey © NERC 2009. All rights reserved.     

Relative contributions of crust and mantle to generation of Campanian high-K calc-alkaline I-type granitoids in a subduction setting, with special reference to the Harşit Pluton, Eastern Turkey

We present elemental and Sr–Nd–Pb isotopic data for the magmatic suite (~79 Ma) of the Harşit pluton, from the Eastern Pontides (NE Turkey), with the aim of determining its magma source and geodynamic evolution. The pluton comprises granite, granodiorite, tonalite and minor diorite (SiO₂ = 59.43–76.95 wt%), with only minor gabbroic diorite mafic microgranular enclaves in composition (SiO₂ = 54.95–56.32 wt%), and exhibits low Mg# (<46). All samples show a high-K calc-alkaline differentiation trend and I-type features. The chondrite-normalized REE patterns are fractionated [(La/Yb) _n  = 2.40–12.44] and display weak Eu anomalies (Eu/Eu* = 0.30–0.76). The rocks are characterized by enrichment of LILE and depletion of HFSE. The Harşit host rocks have weak concave-upward REE patterns, suggesting that amphibole and garnet played a significant role in their generation during magma segregation. The host rocks and their enclaves are isotopically indistinguishable. Sr–Nd isotopic data for all of the samples display I _Sr = 0.70676–0.70708, ε _Nd(79 Ma) = −4.4 to −3.3, with T _DM = 1.09–1.36 Ga. The lead isotopic ratios are (²⁰⁶Pb/²⁰⁴Pb) = 18.79–18.87, (²⁰⁷Pb/²⁰⁴Pb) = 15.59–15.61 and (²⁰⁸Pb/²⁰⁴Pb) = 38.71–38.83. These geochemical data rule out pure crustal-derived magma genesis in a post-collision extensional stage and suggest mixed-origin magma generation in a subduction setting. The melting that generated these high-K granitoidic rocks may have resulted from the upper Cretaceous subduction of the Izmir–Ankara–Erzincan oceanic slab beneath the Eurasian block in the region. The back-arc extensional events would have caused melting of the enriched subcontinental lithospheric mantle and formed mafic magma. The underplating of the lower crust by mafic magmas would have played a significant role in the generation of high-K magma. Thus, a thermal anomaly induced by underplated basic magma into a hot crust would have caused partial melting in the lower part of the crust. In this scenario, the lithospheric mantle-derived basaltic melt first mixed with granitic magma of crustal origin at depth. Then, the melts, which subsequently underwent a fractional crystallization and crustal assimilation processes, could ascend to shallower crustal levels to generate a variety of rock types ranging from diorite to granite. Sr–Nd isotope modeling shows that the generation of these magmas involved ~65–75% of the lower crustal-derived melt and ~25–35% of subcontinental lithospheric mantle. Further, geochemical data and the Ar–Ar plateau age on hornblende, combined with regional studies, imply that the Harşit pluton formed in a subduction setting and that the back-arc extensional period started by least ~79 Ma in the Eastern Pontides.     

Climatic bisection of the last interglacial warm period in the Polar North Atlantic

New multiproxy marine data of the Eemian interglacial (MIS5e) from the Norwegian Sea manifest a cold event with near-glacial surface ocean summer temperatures (3–4 °C). This mid-Eemian cooling divided the otherwise relatively warm interglacial climate and was associated with widespread expansions of winter sea-ice and polar water masses due to changes in atmospheric circulation and ocean stability. While the data also verify a late rather than early last interglacial warm peak, which is in general disharmony with northern hemisphere insolation maximum and the regional climatic progression of the early Holocene, the cold event itself was likely instrumental for delaying the last interglacial climate development in the Polar North when compared with regions farther south. Such a ‘climatic decoupling’ of the Polar region may bear profound implications for the employment of Eemian conditions to help evaluate the present and future state of the Arctic cryosphere during a warming interglacial.