ALBERT

Description: Highlights • Statistically different gas geochemistry was observed in two adjacent springs. • About 74% of helium was contributed by the mantle. • Excess N2 relative to Ar was attributed to subducted materials and seawater mixing. • Magmatic CO2 has been largely removed by calcite precipitation in the reaction zone. • The residual CO2 may also be supplied by microbial oxidation of alkanes. Gas emissions from hydrothermal systems can serve as indicators of subsurface activity. In addition to gas sources, hydrothermal gas geochemistry is strongly influenced by secondary processes that occur during/after hydrothermal circulation. Here, we observed statistically significant differences in the geochemical characteristics (except for helium isotopes) of bubbling gases discharged from two adjacent vents in the Northern Luzon Arc. Helium (3He/4He = 4.25–7.09 Ra) in both vents was controlled by mixing between mantle and crustal components, where about 74% of helium was contributed by the mantle. Differences in N2/Ar ratios (∼ 300–330) of the two neighboring springs are attributed to subducted materials and seawater mixing (contributing ∼2.5% N2 and Ar), rather than phase separation in the reaction zone. Specifically, Ar was mainly supplied by atmospheric components that dissolved in the percolated seawater with only 8%–9% contributed by the excess radiogenic 40Ar. Excess N2 relative to Ar was mainly supplied by the decomposition of subducted materials (83%–92%) of the South China Sea plate beneath the Philippine Sea Plate. The Lutao gases showed low CO2 concentrations (0.07–22.2 mmol/mol), despite the high 3He/4He ratios indicating a significant contribution of magmatic components. Magmatic CO2 may have been largely consumed by the high Ca Lutao vent fluids via carbonate precipitation in the reaction zone. Alternatively, stable carbon isotope compositions (δ13C) indicate that Lutao CO2 may be supplied by microbial oxidation of alkanes (e.g., CH4 with concentrations of 14.6–173 mmol/mol in the samples), with fractionation factor ΔCO2–CH4 ranging from −15‰ to −25‰ and conversion rates of 〈10%. Up to 65% of the CO2 in the 2016 samples experienced secondary calcite precipitation in the discharge zone. Our results indicate that recycled subducted materials could potentially affect the geochemical characteristics of gases discharged from arc-volcanic systems. In addition, the influence of secondary processes needs to be considered before tracing the sources of hydrothermal fluids and/or gases, especially in shallow-water hydrothermal systems.

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: 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: Highlights • δ13C and δ18O profiles increase from exterior to interior until reaching a plateau. • Primary Layer δ13C reflects the δ13C of the Dissolved Inorganic Carbon. • In high pCO2 experiments, δ13C and δ18O closer to equilibrium fields. • Brachiopods grow according to an incremental growth model. Abstract Brachiopod shells are ubiquitous since the Early Cambrian up to now. As they secrete a shell made of low-magnesium calcite, more resistant to diagenesis than biocarbonates richer in Mg, their geochemical signatures are generally considered a powerful tool for paleo-environmental and paleo-climatic reconstructions. However, gaps in knowledge still remain on the underlying controls of the shell chemistry, in particular at a high spatial resolution. In this study, in situ oxygen and carbon isotope measurements by SIMS (Secondary Ion Mass Spectrometry) were performed in brachiopod shells of the cold-temperate water species Magellania venosa, constituted of a primary and a secondary layer. The individual specimens studied here grew under controlled conditions mimicking the natural environment and in experiments under low-pH (high pCO2) and high-temperature conditions. Transversal carbon and oxygen profiles showed a “brachiopod pattern” typical of extant two-layered brachiopods, with the primary layer depleted in 18O and 13C relative to equilibrium and the secondary layer showing a gradual increasing trend until reaching a near-equilibrium plateau. Overall, shells cultured at low pH were found to have δ18O and δ13C values closer to equilibrium when compared to shells from the control experiment. These near-equilibrium values may reflect a decrease in shell precipitation rate, leading to less kinetic effects, and/or a more rapid kinetics for the equilibration between DIC species and water. By close pairing of seawater δ18O and δ13C to that of shell microstructure, our study enables us to derive layer-specific C and O enrichment factors, which show the extent of pH and temperature effects superimposed on the seawater δ18O and DIC δ13C signal inherited. Finally, we show that during brachiopod shell growth, newly precipitated calcite is added to the calcite already existing, thus empirically validating the conceptual accretionary growth model proposed by Ackerly (1989).

Description: The mesopelagic or ocean twilight zone (OTZ) in the ocean contains huge numbers of fish in a relatively pristine environment and may therefore attract interest as a commercial fishery. In this study we evaluate in economic terms, the likely trade-offs between the different services provided by the mesopelagic layer in the Bay of Biscay and the societal benefits of its commercial exploitation. Benefits arise mainly from the likely use of this group of species as raw material for producing fishmeal and fish oil. Costs are derived from the loss in climate regulating and cultural, services, but also from the loss in the provisioning service of other commercial species. To do so we compare the current non-exploited status with a situation in where mesopelagic fishes are harvested at levels capable of producing the Maximum Sustainable Yield. Results suggest that if mesopelagic fishes are harvested, a mean value of 1.2 million Euro loss in a year will be created in the Bay of Biscay, although in a range between 42 million Euro loss and 48 Euro million benefits. This uncertainty comes, mainly, from the limited existing knowledge of the mesopelagic fishes’ biomass but also from the uncertainty on the biomass of the rest of the species of the studied ecosystem. The large range indicates that a better understanding of the mesopelagic ecosystem is needed, however, results also show that ecosystem services under no exploitation provided by the OTZ could be more valuable than the fishmeal and fish oil that potentially could be obtained from the fishes harvested in this sea layer.

Description: The exchange of trace gases across the ocean/atmosphere interface, as well as the deposition of atmospheric pollutants and aerosols, are key processes linking the biogeochemical cycles and biological processes in the ocean with atmospheric chemistry and climate. Here we summarize our knowledge about the distributions of long-lived trace gases (CO2, CH4, N2O), short-lived trace gases, and pollutants (dimethyl sulfide (DMS), isoprene, halocarbons, NOx, SO2, O3, and others), and aerosols in the Indian Ocean. In general, dissolved trace gases show a pronounced temporal and spatial variability, which is caused by the variability of both physical processes (e.g., coastal upwelling) and biological productivity. The distributions of pollutants and aerosols and their depositions to the sea surface are mainly driven by the monsoon system and the variability of their land sources. Nitrogen and iron-containing aerosols can significantly affect biological production in the surface layer of the open Indian Ocean.