Description: The low surface nitrate concentration and high atmospheric iron input in the tropical eastern North Atlantic provide beneficial conditions for N-2 fixation. Varying abundances of diazotrophs have been observed and an Fe- and P-colimitation of N-2 fixation was reported in this ocean region. It is however unclear, how different limiting factors control the temporal variability of N-2 fixation and what the role of Fe-limitation is in a region with high fluxes of dust deposition. To study the environmental controls on N-2 fixation, an one-dimensional ecosystem model is coupled with a physical model for the Tropical Eastern North Atlantic Times-series Station (TENATSO), north of the Cape Verde Islands. The model describes diazotrophy according to the physiology of Trichodesmium, taking into account a growth dependence on light, temperature, iron, dissolved inorganic (DIP) and organic phosphorus (DOP). The modelled total Chl a is compared with satellitederived total Chl a and modelled Trichodesmium (Tri) compared with satellite-derived cyanobacterial Chl a as well as with High Performance Liquid Chromatography data. Model results show a complex pattern of competitive as well as mutually beneficial interactions between diazotrophs and non-diazotrophic phytoplankton. High DOP availability after spring blooms of non-diazotrophic phytoplankton and the ability of Trichodesmium to take up DOP are crucial for allowing a maximal abundance of Tri in autumn. Part of the reactive nitrogen newly fixed by diazotrophs is directly excreted or released through mortality, significantly fuelling the growth of non-diazotrophic phytoplankton in autumn and winter. Fe consumption by non-diazotrophic phytoplankton earlier in the year makes Fe limitation of Tri in late summer more acute, whereas Tri growth in surface waters reduces phytoplankton abundance deeper in the water column by light limitation. Overall, the atmospheric iron input at the TENATSO site is required to enable diazotrophic growth and to support the observed abundance of non-diazotrophic phytoplankton

Description: Highlights • The vent fluids discharged from the Lutao hydrothermal field experienced low-degree subcritical phase separation. • The temperature and chemical compositions of the vent fluids were modulated by tides. • The time delay between tides and the response of hydrothermal system was about 3 h. • The typhoon “Fung-wong” cooled the reaction zone and decreased the degree of phase separation. • The hydrothermal system began to recover after the typhoon passed by. Abstract The Lutao hydrothermal field is an intertidal arc-volcanic system located offshore southeast Taiwan, hosting a Zhudanqu (ZDQ) vent and a Huwaichi (HWC) spring with strongly contrasting fluid chemistry. Low Mg, moderately enriched Cl, and H+ with respect to seawater indicate that the ZDQ endmember was derived from the brine phase that was formed during low-degree subcritical phase separation. In contrast, the endmember for the HWC vent fluids is related to the vapor phase. Temperature and pressure of the phase separation were estimated as ~150 °C and ~7 bar, respectively. The water/rock ratio was roughly calculated as about 2. The Lutao hydrothermal system was slightly affected by semi-diurnal tides, by some combination of tidal loading and tidal currents. The time delay between tides and the response of the hydrothermal system was about 3 h. While freshwater was almost absent in the HWC vent fluids at normal conditions, the typhoon “Fung-wong” on Sep 21st, 2014, led to intrusions of freshwater into the vent fluids with a percentage of ~16%. Both the ZDQ and the HWC endmember compositions showed some changes after the typhoon event, suggesting a cooling of the reaction zone. After the typhoon passed by, the hydrothermal system began to recover, evidenced by increasing percentages of the HWC endmember and decreasing freshwater contributions. The flux of the HWC endmember was estimated as 460–560 L h−1 based on these observations. This study, for the first time, reports a shallow-depth tidal-influenced hydrothermal system that was temporarily cooled by a tropical storm.

Description: Highlights • Aerobic oxidation of alkanes was observed in hydrothermal fluids during storage. • The residual CH4 shows the highest ever reported δ13C of up to +243‰. • The εC for C1, C2, and C3 oxidation were −37.1‰, −14.8‰ and −4.7‰, respectively. • The εH for methane was −281 ± 187‰, while the Λ value was 8.4 ± 4.6. • Aerobic oxidation could produce carbon isotope reversal of the residual alkanes. Aerobic oxidation of short-chain alkanes was observed in gas samples from the Lutao intertidal hydrothermal vents in Taiwan, during storage at 20 °C for up to 29 months without adding bacterial strains and replenishing substrates. The carbon isotope fractionation factors (εC) of methane (C1), ethane (C2), and propane (C3), were calculated using the Rayleigh fractionation equation to be −37.1 ± 7.5‰, −14.8 ± 4.8‰, and −4.7 ± 5.2‰, respectively. The hydrogen isotope fractionation factor (εH) of methane was determined to be −281 ± 187‰. DNA sequencing of the 16S rRNA gene in the vent fluids suggests that aerobic oxidation is dominated by methanotrophs of the genera Methylomicrobium and Methylophaga, which use the ribulose monophosphate pathway (RuMP). The degrees of isotope fractionation (εC and εH values) herein are larger than previously reported values, possibly due to the limited O2 supply and low abundance of aerobic methane-oxidizing bacteria in the experiments. Since the fractionation factor of methane is higher than those of ethane and propane, the aerobic oxidation of thermogenic or microbial alkanes could produce a carbon isotope reversal, which is frequently noted as a trait of abiotic hydrocarbons. This work demonstrates that in addition to anaerobic microbial oxidation, aerobic oxidation with a low cell density can also produce significant isotope fractionation of alkanes in geological closed/semi-closed environments and open flow reaction systems that are characterized by moderate temperatures and a limited supply of substrates and O2; these environments include cold seeps, mud volcanoes, and low-temperature hydrothermal plumes/aquifers/reservoirs.

Description: The chemical and isotopic characteristics of calcium (Ca) in subduction zones are closely related to the budget of Ca and carbon cycles. Here we investigate the ultra-high Ca concentrations that characterize the hydrothermal fluids discharged from two types of vents, named the Zhudanqu brine vent (ZDQ) and the Huwaichi vapor spring (HWC), in the Lutao hydrothermal system at the north Luzon arc. The Ca concentrations of up to 159 mM and Ca/Cl ratio of up to 0.26 in the ZDQ vent fluids are possibly the highest ever reported for Ca enrichment in global seawater-circulated hydrothermal/geothermal systems. The differences in chemical compositions between the ZDQ and the HWC vent fluids are primary controlled by subcritical phase separation. The brine phase constitutes the ZDQ vent fluids, while the HWC vent fluids represent mixtures of the vapor phase and seawater. Both the vapor and the brine phases exhibit similar δ44/40Ca values (0.72 ± 0.05‰), suggesting no significant Ca isotope fractionation has occurred during phase separation. The hydrothermal endmember before phase separation (the “Lutao endmember”) presents depletions of 213 ± 15 mM of Na, 24.4 ± 0.4 mM of SO42−, and 10.2 mM of K, and enrichment of 130.2 ± 5.5 mM of Ca with respect to the percolated seawater. The total gained Ca is 154.6 ± 5.9 mM with a δ44/40Ca value of 0.67‰ – 0.77‰ (0.72 ± 0.05‰), considering anhydrite precipitation during hydrothermal circulation. The Holocene raised coral reef is unlikely to contribute substantial Ca into the Lutao system. Much of the gained Ca (111.6 ± 7.5 mM) is produced by high-degree albitization of the Lutao host rock, which is promoted by the low water/rock ratio (~ 2), slightly alkaline conditions, and relatively lower temperature of the Lutao system with respect to most mid-ocean ridge hydrothermal systems. Ca derived from this process inherits the Ca isotopes of plagioclase in the Lutao host rocks (δ44/40Ca = 0.82 ± 0.06‰). According to mass and isotopic balances, the recycled marine carbonate is proposed to contribute 43 ± 13.4 mM Ca with a δ44/40Ca value of 0.46−0.63+0.35‰ into the Lutao system. Such isotopically lighter Ca is derived from either pore fluids expulsed from underlying Philippine Sea sediments, or more probably, carbonate-bearing subduction fluids from the subducting South China Sea sediments and slab. The carbonate solubility in the subduction fluids could maintain at 600 mM near the reaction zone. The carbonate-rich fluids were subsequently migrated into the Lutao reaction zone and released an additional 43 ± 13.4 mM Ca via dolomitization. A small amount (~ 9%) addition of carbonate-rich fluids would not significantly change the budgets of Na, Mg, and Cl but could generate substantial Ca enrichment and Ca isotopic variations.

Description: Among mechanisms accounting for atmospheric pCO2 drawdown during glacial periods, processes operating in the North Atlantic (NA) and Southern Ocean (SO) have been proposed to be critical. Their individual and synergic effects during a course of glaciation, however, remain enigmatic. We conducted simulations to examine these effects at idealized glacial stages. Under early-glacial-like conditions, cooling in the SO can trigger an initial pCO2 drawdown while the associated sea ice expansion has little impact on air-sea gas exchange. Under later glacial-like conditions, further cooling in the NA enhances ocean carbon uptake due to a stronger solubility pump, and the SO-induced stronger deep stratification prevents carbon exchange between the deep and upper ocean. Meanwhile, strengthened dust deposition increases the SO contribution to the global biological pump, and CO2 outgassing is suppressed by fully extended sea ice cover. More carbon is then stored in the deep Pacific, acting as a passive reservoir.

Description: In this paper we describe the implementation of the carbon isotopes 13C and 14C (radiocarbon) into the marine biogeochemistry model REcoM3. The implementation is tested in long-term equilibrium simulations where REcoM3 is coupled with the ocean general circulation model FESOM2.1, applying a low-resolution configuration and idealized climate forcing. Focusing on the carbon-isotopic composition of dissolved inorganic carbon (δ13CDIC and Δ14CDIC), our model results are largely consistent with reconstructions for the pre-anthropogenic period. Our simulations also exhibit discrepancies, e.g. in upwelling regions and the interior of the North Pacific. Some of these differences are due to the limitations of our ocean circulation model setup, which results in a rather shallow meridional overturning circulation. We additionally study the accuracy of two simplified modelling approaches for dissolved inorganic 14C, which are faster (15 % and about a factor of five, respectively) than the complete consideration of the marine radiocarbon cycle. The accuracy of both simplified approaches is better than 5 %, which should be sufficient for most studies of Δ14CDIC.

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.