Marine Chemistry最新文献

Biogeochemical transformations within highly saline subterranean estuaries (STE) dramatically affect solute cycling, resulting in submarine groundwater discharge (SGD) with distinct chemical signatures. The study hypothesizes that biogeochemical processes within hypersaline bay porewaters (PW) simultaneously affect nitrogen, carbon, and radium cycling. We measured radium isotopes (²²⁶Ra, ²²⁴Ra, and ²²³Ra), nutrients (dissolved inorganic nitrogen [DIN: NH₄⁺ + NO₂⁻ + NO₃⁻], HPO₄²⁻ [DIP], HSiO₃⁻ [DSi], dissolved organic carbon [DOC]), total alkalinity (TA), dissolved inorganic carbon (DIC), stable isotopes, and major cations in PW and surface water (SW) of Baffin Bay, a well-mixed, semi-enclosed estuary along the semiarid northwestern Gulf of Mexico coast, over three seasons in a characteristically dry year. This study's findings show a concurrent increase in NH₄⁺, DIP, DSi, and TA/DIC with reduced metal species (e.g., Mn and Fe) and Ra during the hot and dry seasons, particularly in PW, under increasingly reducing conditions. Principal component analyses (PCA) suggest these increases are primarily driven by dissimilatory nitrate/nitrite reduction to ammonium (DNRA) and dissolution of lithogenic particles and biogenic CaCO₃, modulated by organic matter degradation or remineralization. While more significant terrestrial groundwater inputs may contribute to solutes and Ra supply in the STE, the biogeochemically induced variability in solute concentrations in PW primarily drives larger SGD-derived fluxes, particularly notable in hot months. During a typically dry year, these fluxes, estimated as the average of ²²⁶Ra and ²²³Ra mass balance models (e.g., July/November fluxes in Mmol∙d⁻¹: 0.093/0.092 of NO₃⁻; 0.2/0.02 of NO₂⁻; 72/16 of NH₄⁺; 72.2/18 of DIN; 1.5/0.2 of HPO₄²⁻; 20/9 of HSiO₃⁻; 42/37 of DOC; 503/399 of TA; 582/431 of DIC) are orders of magnitude (∼4 for DIN and DIC, ∼3 for DIP, DSi, and DOC, and ∼2 for TA) greater than surface runoff inputs. These substantial SGD inputs likely sustain phytoplankton growth and potentially fuel harmful algal blooms while countering estuarine acidification.

Atmospheric deposition of trace metals of natural or anthropogenic origin is an important input of micronutrients to the surface ocean. However, understanding its direct impact on oceanic element cycles is challenging due to scarce data, coupled to diverse aerosol sources and variable solubilities. Here, we present a dataset that combines Ni, Zn and Pb isotopes for samples from the Moroccan and Senegalese coasts and in the high latitude North Atlantic Ocean. We combine the new with published data for other circum-North Atlantic sources to assess the processes that determine the isotope signatures in different types of aerosols. We then use open marine aerosol data to investigate the impact of these signatures in the open ocean. Isotope analyses were conducted on bulk aerosols (TSP), on their ultra-high-purity water leachates, and on rainwaters. Aerosols characterized by crustal elemental abundances have isotope compositions similar to Saharan mineral dust. Mixing with anthropogenic aerosols from Europe/North Africa results in lower ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb values for the Eastern North Atlantic region. Higher ²⁰⁶Pb/²⁰⁷Pb at a given ²⁰⁸Pb/²⁰⁷Pb, observed near the Canadian margin and occasionally at the Senegalese coast, points to anthropogenic inputs from North America. Based on trends in the aerosol data (e.g., δ⁶⁶Zn_JMC-Lyon versus ²⁰⁶Pb/²⁰⁷Pb, δ⁶⁰Ni_SRM986 versus Ni/V), we identify several anthropogenic sources of Zn and Ni. The δ⁶⁶Zn_JMC-Lyon of low-temperature pollution (e.g., non-exhaust traffic emission) appears to be around −0.1‰ to 0.2‰, while leachate δ⁶⁶Zn_JMC-Lyon as low as −0.21‰ indicates contributions from high-temperature combustion or smelting processes. Among aerosols with good correlations between Ni and V, δ⁶⁰Ni_SRM986 > 0.40‰ traces Ni contributions from oil combustion. Other Ni-enriched sources, possibly originating from laterite or sulfide, show relatively low δ⁶⁰Ni_SRM986 (as low as −0.85‰) and low V/Ni. Generally, aerosol sources for Zn are consistent throughout the North Atlantic, while Ni can be highly heterogenous. Combining the new data with literature elemental data, ratios of soluble Zn/Pb in anthropogenic aerosols are 1–100 times surface ocean ratios, suggesting that the low δ⁶⁶Zn_JMC-Lyon observed in anthropogenic aerosol can be key in controlling the upper ocean Zn isotope composition. These aerosols have, however, much less significance for surface ocean Ni.

Rare earth elements (REEs) including Yttrium (Y) are commonly used as tracers of estuarine and oceanic mixing. The lanthanide series and yttrium are usually referred to as REYs. The geochemical behavior of REYs in estuarine environments is generally described as being non-conservative, with large-scale removal by particle scavenging. During mixing, partitioning of these elements occurs according to their source function and the stability of natural complexes, with heavy REEs typically forming more stable complexes than light REEs in solution. In this study, we compare the concentrations and partitioning of the 0.7 μm-filtered and 0.05 μm-filtered fractions of the dissolved REYs collected during the summers of 2017 and 2021 in the surface waters (< 3 m) of the St. Lawrence estuarine system (river, estuary and gulf) with those of the Saguenay Fjord, a tributary of the latter that drains the Mesoproterozoic rocks of the Canadian Shield. Whereas REYs do not mix conservatively in the St. Lawrence Estuary (SLE) in the summer, they nearly do so in the Saguenay Fjord (SF). REY concentrations are 2.5 to 6 times greater in the surface waters of the SF than those of the SLE at the same salinity and, in contrast to most estuaries including the SLE, the fjord waters are enriched in LREEs. The 0.05 μm-filtered REY concentrations are positively correlated with dissolved organic carbon (DOC) and chromophoric dissolved organic matter (CDOM) concentrations in the SF but independent of both DOC and CDOM concentrations in the SLE. The CDOM in the fjord differs from that of the estuary as it is more aromatic and has a higher molecular weight. The formation of strong REE-humate complexes stabilizes REY ions in the SF surface waters and impedes their adsorption to and scavenging by solid surfaces during estuarine mixing. The LREE enrichment in the SF surface waters most likely reflects the geology of the fjord's drainage basin, more specifically the exposed Mesoproterozoic granites and gneisses of the Canadian Shield that are enriched in LREE relative to the younger Paleozoic sedimentary rocks exposed along the St. Lawrence Lowlands.

The Amundsen Sea, located in West Antarctica, is experiencing rapid melting due to the intrusion of Circumpolar Deep Water, which is causing ice sheet thinning and basal melting. The resulting changes can affect the biogeochemical cycle of dissolved organic matter (DOM) by supplying iron from sea ice and/or glacier, thereby influencing primary production and ocean circulation. Therefore, it is crucial to understand the dynamics of the DOM in this region. In this study, our primary focus was to examine the optical properties of DOM in the oceanic regions adjacent to the West Getz Ice Shelf (WGIS) and the Dotson Ice Shelf (DIS). Significant differences in DOM optical properties, including the chromophoric DOM (CDOM) absorption coefficient at 350 nm (a₃₅₀), spectral slope coefficient (S_275–295), and specific UV absorbance at 254 nm (SUVA₂₅₄), were observed between the WGIS and DIS regions (t-test, p < 0.05). Notably, the WGIS regions exhibited high a₃₅₀ values. Additionally, the S_275–295 and SUVA₂₅₄ values, which serve as indices of molecular weight, indicated that the DOM pool in the WGIS regions was dominated by high molecular weight compounds with a substantial proportion of aromatic compounds. In contrast, the low values of a₃₅₀ and SUVA₂₅₄ along with the high S_275–295 values in the DIS region suggested the dominance of low molecular weight CDOM associated with compounds of lower aromaticity. Furthermore, significant negative correlations were found between biomass of Phaeocystis antarctica (P. antarctica) and phosphate (PO₄) in the WGIS regions (r² = 0.82, p < 0.01 for WGIS 1 and r² = 0.73, p < 0.01 for WGIS 2). However, no significant relationship was observed in the DIS region. These findings suggest that the high value and molecular weight of a₃₅₀, extending from the surface layer to the deep layer, in the WGIS regions were associated with autochthonous sources, primarily driven by the colony-forming bloom of P. antarctica. These findings demonstrate that the quantity and quality of DOM in the Amundsen Sea are strongly affected by bloom conditions. The results emphasize that a combination of physical and biological processes interacts in complex ways to determine the characteristics of DOM in the Amundsen Sea.

The deposition of volcanic ash into the ocean initiates a range of chemical and biological reactions. During diagenesis, these reactions may enhance the preservation of organic carbon (OC) in marine sediments, which ultimately promotes CO₂ sequestration from the ocean-atmosphere system. However, this interpretation is reliant on a small number of studies that make a link between tephra and OC burial. Here, we compare organic and inorganic geochemical data from tephra-bearing marine sediments from three sites that differ widely in their location, age, and composition. We show that OC is buried in, and proximal to, tephra layers, in proportions higher than would be expected via simple admixture of surrounding sediment. Our data indicate that this OC is preserved primarily through interactions with reactive iron phases, which act to physically protect the carbon from oxidation. Analysis of the composition of the OC associated with reactive iron indicates it is isotopically (consistently more negative δ¹³C than sediment) and chemically (comprised of compounds not found in the sediment) distinct from OC in the background sediments. We interpret this signal as indicating a microbial source of OC, with autochthonous OC production resulting from autotrophic microbial exploitation of nutrients supplied from tephra. This finding has implications for our understanding of carbon cycling on Earth, and possibly for the emergence of life in terrestrial and perhaps even extra-terrestrial environments.

This study examined the factors controlling the intra- and inter-seasonal variations of dissolved methane (CH₄) and nitrous oxide (N₂O) in the southeastern Arabian Sea (SEAS). Time-series measurements of CH₄, N₂O and allied biogeochemical parameters were carried out during the monthly campaigns in the coastal waters and a seasonal campaign in the shelf waters of the SEAS. The southwest monsoon period (SWM) brought drastic changes in the regional hydrography through the incursion of hypoxic waters due to coastal upwelling, which increased N₂O concentrations substantially but reduced CH₄ levels. The ranges of N₂O and CH₄ during the upwelling period were 8–89 nM and 9–165 nM, respectively, and the non-upwelling period was 2–27 nM and 5–271 nM, respectively. The significant positive correlations of N₂O with apparent oxygen utilisation (AOU), the sum of dissolved nitrate and nitrite (NO₂⁻ + NO₃⁻) and excess N₂O (ΔN₂O), as well as a negative correlation with dissolved oxygen indicates that nitrification is the major process in this region during the non-upwelling period. In contrast, during SWM, N₂O did not correlate with NO₂⁻ + NO₃⁻; however, it exhibited a significant negative correlation with dissolved nitrite (under hypoxia), suggesting the possibility of nitrifier-denitrification as an active process during hypoxia. The high (low) levels of CH₄ recorded during the oxic spring inter-monsoon (hypoxic during the SWM) period showed a direct dependency on the changes in the benthic community. The high abundance of the adult macrofauna and active bioturbation resulted in high sedimentary CH₄ release, which led to enhanced water column CH₄ concentrations (17–271 nM) during the spring inter-monsoon period. In addition, the breakdown of methylated organic compounds under nutrient-limited conditions may also support the elevated CH₄ levels in surface waters. A low macrofaunal abundance and reduced bioturbation led to a considerable reduction of subsurface CH₄ concentrations during hypoxia. Overall, the SEAS is found to be a net source of CH₄ and N₂O to the atmosphere, with its sea-to-air fluxes ranging from 1.7 to 85.8 μM m⁻² d⁻¹ (19.88 ± 22.20 μM m⁻² d⁻¹) for N₂O and 4–756 μM m⁻² d⁻¹(133 ± 158 μM m⁻² d⁻¹) for CH_4.

Total alkalinity (TA) is a variable that reflects the acid buffering capacity of seawater, and is key to studies of the global carbon cycle. Daily and seasonal TA variations are poorly constrained due to limitations in observational techniques, and this hampers our understanding of the carbonate system. High quality and high temporal resolution TA observations are required to constrain the controlling factors on TA. Estuarine and coastal waters usually have low TA values and may experience enhanced remineralization of organic matter in response to processes such as eutrophication and terrestrial organic matter input. Therefore, these waters are considered vulnerable to acidification as a consequence of ongoing atmospheric anthropogenic carbon dioxide uptake. An In Situ Analyzer for seawater Total Alkalinity (ISA-TA) was deployed for the first time in low salinity, dynamic estuarine waters (Kiel Fjord, southwestern Baltic Sea). The ISA-TA and a range of additional sensors (for pH, pCO₂, nitrate and temperature, salinity, dissolved oxygen) used to obtain ancillary data to interpret the TA variability, were deployed on a pontoon in the inner Kiel Fjord for approximately four months. Discrete samples (for TA, nutrients including NO₃⁻, soluble reactive phosphorus (SRP) and H₄SiO₄, chlorophyll a) were collected regularly to validate the ISA-TA and to interpret the TA data. The effects on TA in the study area of nitrate uptake and of other processes such as precipitation, run-off and mixing of different waters were observed. The difference between the TA values measured with the ISA-TA and TA of discretely collected samples measured with the Gran titration method was −2.6 ± 0.9 μmol kg⁻¹ (n = 106), demonstrating that the ISA-TA provides stable and accurate TA measurements in dynamic, low salinity (13.2–20.8), estuarine waters. The TA and ancillary data recorded by the sensor suite revealed that physical mixing was the main factor determining the variability in TA in Kiel Fjord during the study period.

The cycling of oceanic dissolved organic carbon (DOC) is a crucial component of the global carbon cycle, yet the identification of sources and the mechanisms of its molecular transformation remain poorly understood. This study compared the isotopic and molecular composition of DOC between the oligotrophic South China Sea (SCS) and the adjacent North Pacific Ocean (NPO), and traced both its allochthonous and autochthonous sources as well as its dynamic cycling processes. DOC was collected through solid-phase extraction (SPE) from water samples of both the SCS and NPO. Carbon content, isotopic ratios, and high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) measurements revealed that SPE-DOC contained both labile and refractory fractions. According to our mass balance model, the labile fraction of SPE-DOC exhibited a decline from 11.5 to 12.6 μM in surface waters to a negligible concentration below 1000 m. Conversely, the refractory fraction of SPE-RDOC maintained a relatively consistent value, ranging from 12.7 to 19.0 μM across the entire water column. The vertical distribution patterns of the molecular composition and carbon isotopic ratios jointly indicated that the DOC distributions are shaped by distinct biological and physical processes within different biogeochemical realms of the water column. The production and transformation of the relatively labile DOC fractions were the dominant processes in the epipelagic and mesopelagic zones (upper 1000 m). The extent of diapycnal mixing between the SCS and NPO explained the different vertical distributions of refractory DOC molecules in the bathypelagic oceans. The molecular indices of polyphenol compounds, aromaticity, double bond saturation state, terrestrial mass peaks, and δ¹³C ratios of SPE-DOC indicated contributions from terrestrial sources, likely riverine input, in the SCS. This study sheds light on the molecular evidence of DOC sources, as well as their transformation and conservative mixing processes along the overturning circulation in marginal seas.

We studied the impact of iron limitation on zinc uptake and the zinc isotope (δ⁶⁶Zn) composition for Southern Ocean phytoplankton. We undertook laboratory culture and field incubation experiments, and linked these to in situ depth profiles of dissolved (dZn) and particulate (pZn) zinc collected from three sites in the Southern Ocean. For the laboratory experiments, diatom growth rates, cellular zinc accumulation, and δ⁶⁶Zn all responded to changes in iron and zinc bioavailability. A significant increase in the cellular quota for zinc (expressed as zinc:phosphorous (Zn:P)) occurred upon iron limitation and zinc enrichment. At the same time, δ⁶⁶Zn for organic tissues became isotopically light under high zinc and low iron concentrations. The opposite occurred for frustule δ⁶⁶Zn values. Here δ⁶⁶Zn_{frustule-organic} for cultured phytoplankton became isotopically heavier under high zinc and low iron concentrations. For senescing and dead cells, Zn:P declined and δ⁶⁶Zn increased, indicating a loss of isotopically light zinc from organic matter. For field incubation experiments, δ⁶⁶Zn_frustule was isotopically heavier than seawater, except for added zinc treatments. The percentage of zinc associated with frustule material for laboratory and field incubations encompassed a wide range with values between 1 and 57%. Depth profiles of δ⁶⁶Zn for dZn and pZn varied, with dZn being isotopically lighter than pZn in low dZn concentration subantarctic waters, whereas the opposite occurred in polar waters where dZn was isotopically heavier than pZn at higher dZn concentrations. Our results show that iron and zinc availability regulates the zinc content of phytoplankton and the δ⁶⁶Zn composition of the Southern Ocean, which is propagated to other parts of the world ocean.

Dissolved organic carbon (DOC) is the largest organic carbon pool in the ocean, and is the most active component in respect to the ocean carbon cycling. However, its study in Antarctica has been limited due to challenges associated with sample collection. In this study, we conduct an investigation on the chromophoric dissolved organic matter (CDOM) in a highly productive Amundsen Sea Polynya (ASP), where phytoplankton blooms occur annually during the austral summer, serving as the primary source of DOC and CDOM. The relative abundances of CDOM, as indicated by the absorption coefficient at 254 nm (a₂₅₄), exhibit significant variability, reaching up to 6.34 m⁻¹. Four fluorescent components, including two humic-like components (C1 and C4) and two protein-like components (C2 and C3), are identified by excitation emission matrix coupled with parallel factor analysis (EEM-PARAFAC). Our findings suggest that heterotrophic metabolism primarily contributes to the formation of humic-like fluorescent components and DOC removal. Water mass, solar radiation, primary productivity as well as microbial degradation are identified as the main factors influencing CDOM dynamics in ASP. This study bears significant implications for advancing our understandings of the CDOM and DOC dynamics in the coastal polynyas of Antarctica, thus facilitating improved evaluation of carbon cycle in the Antarctica.