ALBERT

Description: Since the initial discovery of the non-exponential mass fractionation (non-EMF) of Nd isotopes analysis in 2002, similar deviations from an EMF pattern have been reported for measurements of a number of isotope systems (e.g., Si, Ge, Sr, Sn, Ba, Yb, W, Os, Hg and Pb) with MC-ICP-MS. However, the previous controversial reports on the magnitude of the deviations from EMF suggest that instrumental mass bias behaviour of MC-ICP-MS is neither fully understood nor well-characterised. Consequently, the standard approach of using a mass dependent fractionation (MDF) correction model (e.g., exponential law) may lead to both inaccurate and imprecise results. In this study, we systematically characterise the instrumental mass fractionation of MC-ICP-MS using Nd isotope measurements carried out under different plasma conditions, quantified using the normalised argon index (NAI) as an estimate of plasma temperature. Our results indicate that the mass bias of MC-ICP-MS is not always a simple exponential function of mass but shows systematic deviations from an EMF behaviour, which are closely associated with decreased NAIs. As a result, the conventional exponential correction yields a 143Nd/144Nd value of 0.512257 for the reference material BHVO-2 when the NAI is low, which is 722 ppm lower than the reported value of 0.512979. By tuning the plasma to higher NAIs (higher plasma temperatures), the deviations from the EMF array are systematically attenuated and the exponential correction is able to correct for the instrumental mass bias under high NAIs. In contrast, a regression correction model for Nd isotopes is developed to account for the observed mass fractionation behaviour that does not follow EMF under low NAIs, given that the regression correction relies on the observed loglinear fractionation of different isotope pairs and does not require both isotope ratios to undergo EMF. We expect that the analytical protocol and fundamental insights gained in this study are applicable to a wide range of other isotope measurements with MC-ICP-MS.

Description: This chapter provides an overview of near-surface geochemical processes operating on Earth, with special emphasis placed on (i) marine weathering such as alteration and dissolution of silicates, carbonates and terrigenous riverine particles in the ocean, complemented by (ii) reverse weathering reactions leading to marine authigenic clay formation, and the impact of these phenomena on ocean alkalinity budget and the chemical and isotope composition of seawater. Model simulations of the above processes provide estimates of the global marine fluxes of major cations (Na+, K+, Mg2+, Ca2+) and alkalinity in the ocean induced by silicate weathering and dissolution of terrigenous material in seawater. Additional constraints on silicate vs. carbonate weathering, oceanic/coastal CaCO3 cycling, and paleo-seawater reconstructions are provided via the stable and radiogenic isotope systems of alkali and alkaline earth metals (Li, K, Mg, Ca, and Sr isotopes) that are discussed within the context of marine and reverse weathering in the present and past ocean. Key points • Impact of weathering processes on marine elemental cycles and the ocean alkalinity budget. • Alteration and dissolution of silicate minerals and riverine particles in the ocean quantified via thermodynamic equilibrium (PHREEQC) calculations, in seawater and top sediment settings. • Estimates of global ocean fluxes of dissolved cations (Na+ , K+ , Mg 2+ , Ca2+ ) and alkalinity induced by alteration and dissolution of terrigenous material in seawater and marine sediments. • Principles and mechanisms of isotope variability in nature (mass-dependent and radiogenic isotope effects) observed for alkali and alkaline earth metals. • Silicate vs. carbonate weathering and coastal carbon/carbonate cycling constrained via stable and radiogenic Ca and Sr, and Li isotopes. • Oceanic processes, marine carbonate chemistry (alkalinization vs. acidification), and paleo-seawater reconstructions constrained via d44 Ca, d88 Sr, d26 Mg proxies and numerical (MATLAB) modeling. • Emerging metal isotope proxies (d41 K) for silicate and reverse weathering in the ocean.

Description: Highlights • a high-fidelity RANS CFD method is used to simulate the flow through netting panels. • The influence of netting solidity, twine diameter, mesh opening angle and incident angle is examined. • Mesh opening angle, solidity and angle of incidence greatly influence the hydrodynamic force coefficients and efficiency. To ensure the economic and environmental sustainability of the fisheries and aquaculture industries, it is necessary to address issues related to fuel consumption, environmental degradation, and fish welfare. Hence, we need a thorough understanding of the filtration efficiency and the hydrodynamic forces acting on towed fishing gears and netting structures. Here we apply a Reynolds-averaged Navier-Stokes (RANS) CFD method to model the flow through netting panels, where we vary the operational and design parameters of flow speed, netting solidity, twine diameter, mesh opening angle and the incidence angle of the flow to the panel. Thus, we create a simulated data set which we analyze to provide a fundamental understanding of the functional relationships for the pressure drop and tangential drag coefficients, and the flow deflection in terms of these parameters. We pay particular attention to the effect of mesh opening angle, a parameter that has not received much attention in the literature. We demonstrate that it has a large influence on the drag and lift coefficients and consequently on the hydrodynamic efficiency of netting panels. These results will be particularly useful for reducing the hydrodynamic forces on netting structures and improving the fuel efficiency of towed fishing gear operations.

Description: Gypsum makes up about one fifth of giant salt deposits formed by evaporation of seawater throughout Earth’s history. Although thermodynamic calculations and precipitation experiments predict that gypsum precipitates when the salinity of evaporating seawater attains about 110 g kg-1, gypsum deposits of the Mediterranean Salt Giant often bear the geochemical signature of precipitation from less saline water masses. Addressing this geochemical riddle is important because marine gypsum deposition and continental gypsum erosion affect the global carbon cycle. We investigated gypsum deposits formed in the marginal basins of the Mediterranean Sea during the Messinian Salinity Crisis (about 6 million years ago). These often bear low-salinity fluid inclusions and isotopically light crystallization water, confirming previous published reports that the Mediterranean Salt Giant harbors low-salinity gypsum deposits. A geochemical model constrained by fluid inclusion salinity and isotope (87Sr/86Sr, δ34SSO4, δ18OH2O, δDH2O) measurements excludes that Ca2+- and SO42--enriched continental runoff alone provides the trigger for gypsum precipitation at low salinity. We propose that, concurrent with the prevalent evaporative conditions and with Ca2+- and SO42--bearing runoff, the biogeochemical sulfur cycle is capable of producing a spatially-restricted and temporally-transient increase of Ca2+ and SO42- within benthic microbial mats, creating local chemical conditions conductive to gypsum precipitation. This hypothesis is supported by the presence of dense packages of fossils of colorless sulfur bacteria within gypsum in several Mediterranean marginal basins, together with independent geochemical and petrographic evidence for an active biogeochemical sulfur cycle in the same basins. Should this scenario be confirmed, it would expand the range of environments that promote marine gypsum deposition; it would also imply that an additional, biological coupling between the calcium, sulfur and carbon cycles exists.

Description: The dynamic processes associated with subducting tectonic plates and rising plumes of hot material are typically treated separately in dynamical models and seismological studies. However, various types of observations and related models indicate these processes overlap spatially. Here we use precursors to PP and SS reflecting off mantle transition zone discontinuities to map deflections of these discontinuities near three subduction zones surrounding the Caribbean Plate: 1) Lesser Antilles, 2) Middle America and 3) northern South American subduction zones. In all three regions slow seismic anomalies are present behind the sinking slab within the transition zone in tomographic images. Using array methods, we identify precursors and verify their in-plane propagation for MW ≥ 5.8 events occurring between the years 2000 and 2020 by generating a large number of source receiver combinations with reflection points in the area, including crossing ray paths. The measured time lag between PP/SS arrivals and their corresponding precursors on robust stacks are used to measure the depth of the mantle transition zone discontinuities. In all three areas we find evidence for upward deflection of the 660 discontinuity behind the sinking slab, consistent with the presence of hot plume material (average temperature anomalies of 180 to 620 K), while there is not a corresponding downward deflection of the 410 km discontinuity. One interpretation of these disparate observations is suggested based on comparison to existing models of mantle convection and subduction: plume material rising across 660 km discontinuity could be entrained by lateral flow in the transition zone induced by the nearby sinking slab, and thus delaying the rise of hot material across the 410 km discontinuity.

Description: Observations of spatio-temporal variability of the deep ocean are rare and little is known about occurrence of deep ocean mesoscale dynamics. Here, we make use of 2.5 years of time series data from three distributed sensor arrays, which acquired high-resolution temperature, pressure and sound speed data of the bottom layer offshore northern Chile. Estimating salinity and density from the direct observations enable access to the full spectrum of hydrographic variability from a multi-hourly to annual time scale and with average inter-station distances of less than 1 km. Analyses revealed interannual warming over the continental slope of 0.002 °C yr−1–0.003 °C yr−1, and could trace periodic hydrographic anomalies, likely related to coastal-trapped waves, as far as to the lower continental slope. A concurrent change in the shape of the warm anomalies and the rate of deep-sea warming that occurs with the crossing of the deep-sea trench suggests that the abyssal part of the eastern boundary current system off Chile does not extend past the deep sea trench. Furthermore, the comparison of anomaly timing and shape in between stations implies southwards flow over the mid to lower continental slope, centred closer to the trench.

Description: Highlights • Ankaramites are Ca-rich and Ni-poor porphyritic basalts that are common in oceanic arcs. • Melt inclusions from Kibblewhite Volcano show similar compositions to ankaramites. • Ankaramite is a primary magma component in oceanic arcs. • Interaction between melt and mantle can produce ankaramitic melts. • Harzburgite formed by melt-mantle interactions is the source of high-Mg andesites. Abstract Ankaramites, which are clinopyroxene-rich basalts with primitive whole-rock compositions (Mg# 〉65), are common in oceanic arcs and are characterized by high whole-rock CaO/Al2O3 (〉1.0) ratios and olivine crystals with anomalously low nickel contents (〈0.2 wt% NiO). These geochemical characteristics cannot be explained by the melting of ordinary mantle peridotite. However, their origin is critical for understanding the formation of primary magmas in oceanic arcs. Here, we investigated olivine-hosted melt inclusions (MIs) from ankaramites and magnesian andesites of the Kibblewhite Volcano in the Kermadec arc. The MIs from the ankaramites have similar major and trace element characteristics to the host rocks, indicating that the ankaramites did not result from an accumulation of mafic minerals but rather represent the primary magma in the Kibblewhite Volcano. The MIs from the magnesian andesites were hosted in forsteritic olivine xenocrysts with a wide range of NiO contents (Fo90–92; 0.13–0.39 wt% NiO) and have similar major element compositions to the ankaramites but exhibit a wide range of CaO/Al2O3 (0.85–1.54). The trace element characteristics of the MIs from the magnesian andesites do not match those of the host rocks, indicating that they are not primary melts of the magnesian andesites but primitive basaltic melts generated before the magnesian andesites formed. Interestingly, the CaO/Al2O3 ratio of MIs from the magnesian andesites was negatively correlated with the NiO content of their host olivines. This correlation suggests that the composition of the primary basaltic magmas of the Kibblewhite Volcano changed continuously from peridotite-derived to ankaramitic. This correlation could not be explained by grain-scale process, crustal anatexis, or contribution of slab-derived carbonate-rich fluids. Instead, we propose that this correlation can be explained by the interaction of the ascending primary basaltic melts with the lithospheric mantle. During melt-mantle interaction, the assimilation of clinopyroxene and fractionation of olivine and orthopyroxene caused the CaO/Al2O3 ratio to increase in the melt and the Ni content to decrease. Furthermore, because the magnesian andesites have low CaO/Al2O3 ratios and could be derived from a clinopyroxene-poor mantle lithology, the interaction between the melt and mantle may also be closely related to the origin of the magnesian andesites at Kibblewhite Volcano. This interpretation provides a new perspective on the origin of the oceanic arc ankaramites and why primary andesitic and basaltic magmas coexist in the Kibblewhite Volcano.

Description: Detection of small plastic particles in environmental water samples has been a topic of increasing interest in recent years. A multitude of techniques, such as variants of Raman spectroscopy, have been employed to facilitate their analysis in such complex sample matrices. However, these studies are often conducted for a limited number of plastic types in matrices with relatively little additional materials. Thus, much remains unknown about what parameters influence the detection limits of Raman spectroscopy for more environmentally relevant samples. To address this, this study utilizes Raman spectroscopy to detect six plastic particle types; 161 and 33 nm polystyrene, 〈 450 nm and 36 nm poly(ethylene terephthalate), 121 nm polypropylene, and 126 nm polyethylene; spiked into artificial saltwater, artificial freshwater, North Sea, Thames River, and Elbe River water. Overall, factors such as plastic particle properties, water matrix composition, and experimental setup were shown to influence the final limits of detection.

Description: Accurate reconstruction of seasonal atmospheric patterns of the past is essential for reliable prediction of how climate will evolve due to anthropogenic CO2 forcing. The Eocene ‘hot house’ climate, as the warmest epoch during the Cenozoic, is considered as a potential analogue for ‘high-CO2’ future climate scenarios. In this context, the reconstruction of variations in seasonality are as important as changes in mean annual conditions. Here we combine stable oxygen (δ18O) and dual clumped isotope (Δ47 + Δ48) measurements of a bivalve shell to determine sub-annual variations in sea surface temperatures and oceanic freshening in the Paris Basin during the Mid-Eocene Climate Optimum, 40 million years ago. Our reconstruction indicates to high mean annual temperatures with a small seasonal amplitude (33.3 °C ± 4.4 °C) and an enhanced fresh water input during the summer period. Our results implying a substantially warmer climate state with different hydrological conditions for Western Europe during the Eocene than previously suggested by proxy data or climate modelling.