Marine Biogeochemical Cycles Research Articles

Comparison of sedimentary iron speciation obtained by sequential extraction and X-ray absorption spectroscopy

Iron (Fe) speciation in marine sediments and suspended particulate matter (SPM) are widely used to investigate the role of Fe minerals in marine biogeochemical cycling and to reconstruct paleo-redox conditions. A traditional method for the determination of Fe speciation are sequential extractions, in which operationally defined Fe pools are dissolved by specific extraction solutions. More recently, many studies make use of synchrotron radiation-based X-ray absorption near edge spectroscopy (XANES), especially if little sample material is available or a high spatial resolution is required. However, few studies have systematically compared Fe speciation obtained by the two methods. Here, we report Fe speciation for marine sediments (both wet and freeze-dried) and SPM from contrasting marine environments (western Baltic Sea and Amazon shelf) obtained by sequential extraction and XANES. The two methods yield comparable results regarding the approximate proportion of reactive Fe ((oxyhydr)oxide, carbonate and sulfide minerals) in the total Fe pool and the extent to which reactive Fe minerals have been converted to pyrite. However, methodological issues associated with both approaches complicate a direct comparison of specific mineral groups. Pyrite concentrations obtained by XANES are lower than those obtained by extraction, which is attributed to an underestimation by XANES due to self-absorption effects and an overestimation by the chromium reduction method due to dissolution of reduced sulfur phases that are not associated with Fe. As substantial amounts of pyrite are oxidized during freeze-drying and sample storage, we recommend to analyze wet sediments in modern marine environments. The XANES spectra of Fe (oxyhydr)oxide and Fe(III)-containing (ferric) clay minerals are similar, which is why these components cannot be differentiated by XANES. Similarly, sequential extraction schemes are known to dissolve a variable proportion of ferric clay minerals along with Fe carbonates and Fe (oxyhydr)oxides. Further investigating the role of ferric clay minerals in the low-temperature marine Fe cycle may therefore require the use of additional methods. Our findings may help to assess the transferability of XANES-based Fe speciation for small sediment and SPM samples to those reported in more traditional studies on Fe biogeochemical cycling and paleo-redox conditions.

Ocean circulation and biological processes drive seasonal variations of dissolved Al, Cd, Ni, Cu, and Zn on the Northeast Atlantic continental margin

Nutrients and nutrient-like dissolved trace metals (dTMs) are essential for the functioning of marine organisms and therefore form an important part of ocean biogeochemical cycles. Here, we report on the seasonal distributions of dissolved zinc (dZn), nickel (dNi), copper (dCu), cadmium (dCd), aluminum (dAl), and nutrients on the Northeast Atlantic continental margin (Celtic Sea), which is representative for temperate shelf seas globally. Variations in surface water dTM and nutrient concentrations were mainly regulated by seasonal changes in biological processes. The stoichiometry of dTMs (especially for dCu and dZn) and nutrients on the continental shelf was additionally affected by fluvial inputs. Nutrients and dTMs at depth on the continental slope were determined by water mass mixing driven by ocean circulation, without an important role for local remineralization processes. The Mediterranean Outflow Waters are especially important for delivering Mediterranean-sourced dTMs to the Northeast Atlantic Ocean and drive dTM:nutrient kinks at a depth of ~1000 m. These results highlight the importance of riverine inputs, seasonality of primary production and ocean circulation on the distributions of nutrients and nutrient-like dTMs in temperate continental margin seas. Future climate related changes in the forcing factors may impact the availability of nutrients and dTMs to marine organisms in highly productive continental shelf regions and consequently the regional carbon cycle.

Bacterial catabolism of membrane phospholipids links marine biogeochemical cycles.

In marine systems, the availability of inorganic phosphate can limit primary production leading to bacterial and phytoplankton utilization of the plethora of organic forms available. Among these are phospholipids that form the lipid bilayer of all cells as well as released extracellular vesicles. However, information on phospholipid degradation is almost nonexistent despite their relevance for biogeochemical cycling. Here, we identify complete catabolic pathways for the degradation of the common phospholipid headgroups phosphocholine (PC) and phosphorylethanolamine (PE) in marine bacteria. Using Phaeobacter sp. MED193 as a model, we provide genetic and biochemical evidence that extracellular hydrolysis of phospholipids liberates the nitrogen-containing substrates ethanolamine and choline. Transporters for ethanolamine (EtoX) and choline (BetT) are ubiquitous and highly expressed in the global ocean throughout the water column, highlighting the importance of phospholipid and especially PE catabolism in situ. Thus, catabolic activation of the ethanolamine and choline degradation pathways, subsequent to phospholipid metabolism, specifically links, and hence unites, the phosphorus, nitrogen, and carbon cycles.

Diversity, distribution, and functional potentials of magroviruses from marine and brackish waters.

Marine group II (MGII) archaea (Ca. Poseidoniales) are among the most abundant microbes in global oceanic surface waters and play an important role in driving marine biogeochemical cycles. Magroviruses - the viruses of MGII archaea have been recently found to occur ubiquitously in surface ocean. However, their diversity, distribution, and potential ecological functions in coastal zones especially brackish waters are unknown. Here we obtained 234 non-redundant magroviral genomes from brackish surface waters by using homology searches for viral signature proteins highlighting the uncovered vast diversity of this novel viral group. Phylogenetic analysis based on these brackish magroviruses along with previously reported marine ones identified six taxonomic groups with close evolutionary connection to both haloviruses and the viruses of Marine Group I archaea. Magroviruses were present abundantly both in brackish and open ocean samples with some showing habitat specification and others having broad spectrums of distribution between different habitats. Genome annotation suggests they may be involved in regulating multiple metabolic pathways of MGII archaea. Our results uncover the previously overlooked diversity and ecological potentials of a major archaeal virial group in global ocean and brackish waters and shed light on the cryptic evolutionary history of archaeal viruses.

Genomic analysis and characterization of phages infecting the marine Roseobacter CHAB-I-5 lineage reveal a globally distributed and abundant phage genus.

Marine phages play an important role in marine biogeochemical cycles by regulating the death, physiological metabolism, and evolutionary trajectory of bacteria. The Roseobacter group is an abundant and important heterotrophic bacterial group in the ocean, and plays an important role in carbon, nitrogen, sulfur and phosphorus cycling. The CHAB-I-5 lineage is one of the most dominant Roseobacter lineages, but remains largely uncultured. Phages infecting CHAB-I-5 bacteria have not yet been investigated due to the lack of culturable CHAB-I-5 strains. In this study, we isolated and sequenced two new phages (CRP-901 and CRP-902) infecting the CHAB-I-5 strain FZCC0083. We applied metagenomic data mining, comparative genomics, phylogenetic analysis, and metagenomic read-mapping to investigate the diversity, evolution, taxonomy, and biogeography of the phage group represented by the two phages. The two phages are highly similar, with an average nucleotide identity of 89.17%, and sharing 77% of their open reading frames. We identified several genes involved in DNA replication and metabolism, virion structure, DNA packing, and host lysis from their genomes. Metagenomic mining identified 24 metagenomic viral genomes closely related to CRP-901 and CRP-902. Genomic comparison and phylogenetic analysis demonstrated that these phages are distinct from other known viruses, representing a novel genus-level phage group (CRP-901-type). The CRP-901-type phages do not contain DNA primase and DNA polymerase genes, but possess a novel bifunctional DNA primase-polymerase gene with both primase and polymerase activities. Read-mapping analysis showed that the CRP-901-type phages are widespread across the world's oceans and are most abundant in estuarine and polar waters. Their abundance is generally higher than other known roseophages and even higher than most pelagiphages in the polar region. In summary, this study has greatly expanded our understanding of the genetic diversity, evolution, and distribution of roseophages. Our analysis suggests that the CRP-901-type phage is an important and novel marine phage group that plays important roles in the physiology and ecology of roseobacters.

Potential Auxiliary Metabolic Capabilities and Activities Reveal Biochemical Impacts of Viruses in Municipal Wastewater Treatment Plants.

Viruses influence biogeochemical cycles in oceans, freshwater, soil, and human gut through infection and by modulating virocell metabolism through virus-encoded auxiliary metabolic genes (vAMGs). However, the geographical distribution, potential metabolic function, and engineering significance of vAMGs in wastewater treatment plants (WWTPs) remain to be explored. Here, 752 single-contig viral genomes with high confidence, 510 of which belonged to Caudovirales, were recovered from the activated sludge metagenomes of 32 geographically distributed WWTPs. A total of 101 vAMGs involved in various metabolic pathways were identified, the most common of which were the queuosine biosynthesis genes folE, queD, and queE and the sulfur metabolism gene cysH. Phylogenetic analysis and virus-host relationship prediction revealed the probable evolutionary histories of vAMGs involved in carbon (acpP and prsA), nitrogen (amoC), sulfur (cysH), and phosphate (phoH) metabolism, which potentially mediate microbial carbon and nutrient cycling. Notably, 11 of the 38 (28.3%) vAMGs identified in the metagenomes with corresponding metatranscriptomes were transcriptionally expressed, implying an active functional state. This meta-analysis provides the first broad catalog of vAMGs in municipal WWTPs and how they may assist in the basic physiological reactions of their microbial hosts or nutrient cycling in the WWTPs, and therefore, may have important effects on the engineering of wastewater treatment processes.

Multiple parameters enable deconvolution of water-rock reaction paths in low-temperature vent fluids of the Kamaʻehuakanaloa (Lōʻihi) seamount

The contribution of venting fluids at mid-ocean ridges to global ocean biogeochemical cycles is well recognized. Less is known about the role of magmatically-active intra-plate volcanoes. In this study, new compositional fluid data were acquired from 20 to 50 °C vent fluids at Kamaʻehuakanaloa (previously known as Lōʻihi) seamount (Hawai’ian archipelago) and used to model the wide diversity of reaction conditions capable of producing the Fe-, Si- and CO2-rich vent fluids observed. Our conceptual model includes a first step where seawater reacts with increasing proportions of basalt and gas as the temperature increases, and a second step where the resulting hydrothermal fluid mixes with unaltered seawater while continuing to react with basalt until the fluid mixture reaches 20 °C. A series of reaction paths were chosen to vary: the maximum temperature during Step 1 (50 to 400 °C) and the proportions of basalt and gas reacting; the degree, F, of low-temperature basalt alteration during Step 2, which corresponds to the extent to which the hot fluid generated during Step 1 continues to react with more basalt as it ascends to the seafloor. Our model shows that the 20–50 °C vent fluids are greatly dependent on the degree of low-temperature basalt alteration during fluid upwelling. Indeed, the compositions of Kamaʻehuakanaloa vent fluids cannot be reconciled with a general model of subsurface mechanical mixing of high-temperature end-member vent fluid and seawater alone. Instead, they require both subsurface equilibrium mixing between a ≥350 °C hydrothermal fluid end-member and seawater and further basalt alteration that must occur as the fluid mixture rises to the seafloor. Although it involves only ∼4% of the amount of basalt having reacted during Step 1, this low-temperature basalt alteration during Step 2 leads to the characteristic enrichments in Fe observed in the Kamaʻehuakanaloa vent fluids and a concomitant depletion in H2S. We hypothesize that low-temperature basalt alteration during an extended path of fluid upwelling through the subseafloor might arise as a direct consequence of the height and steep-sloped topography of Kamaʻehuakanaloa seamount. If correct, this suggests a more general case - that input from magmatically-active intraplate volcanoes, which have been relatively overlooked throughout the history of submarine vent investigations to date, could differ significantly from global mid-ocean ridge fluxes and contribute more substantially than previously recognized to the global ocean Fe cycle.

Decline of anthropogenic lead in South Atlantic Ocean surface waters from 1990 to 2011: New constraints from concentration and isotope data

Anthropogenic emissions have severely perturbed the marine biogeochemical cycle of lead (Pb). Here, we present new Pb concentration and isotope data for surface seawater from GEOTRACES section GA02, sampled in the western South Atlantic in 2011. The South Atlantic is divided into three hydrographic zones: equatorial (0–20°S), subtropical (20–40°S), and subantarctic (40–60°S). The equatorial zone is dominated by previously deposited Pb transported by surface currents. The subtropical zone largely reflects anthropogenic Pb emissions from South America, whilst the subantarctic zone presents a mixture of South American anthropogenic Pb and natural Pb from Patagonian dust. The mean Pb concentration of 16.7 ± 3.8 pmol/kg is 34 % lower than in the 1990s, mostly driven by changes in the subtropical zone, with the fraction of natural Pb increasing from 24 % to 36 % between 1996 and 2011. Although anthropogenic Pb remains predominant, these findings demonstrate the effectiveness of policies that banned leaded gasoline.

Pelagic microplastics in the North Pacific Subtropical Gyre: A prevalent anthropogenic component of the particulate organic carbon pool.

Due to its ever-increasing ocean inputs, fossil-based microplastics (MP) comprise a considerable constituent in the particulate organic carbon (POC) pool, which is instrumental in ocean biogeochemical cycling. Their distribution within the oceanic water column and the underpinning processes, however, remain unclear. Here we show that MP prevail throughout the water column of the eastern North Pacific Subtropical Gyre, comprising 334 #/m3 (84.5% of plastic particles <100 µm), with exponential relationships between concentrations and water depth in the upper 500-m layer and marked accumulation below this layer. Our results suggest that the biological carbon pump (BCP) strongly contributes to the water column MP redistribution in terms of polymer type, material density and particle size, which in turn could influence the efficiency of organic matter export to the deep sea. We further show that 14C-depleted plastic particles predictably are an emerging nonneglectable perturbation to radiocarbon signatures in the deep ocean through depletion of the 14C/C ratio in the POC pool. Our data provide insight into vertical MP flux and highlight the potential role of MP in alternating the marine particulate pool and interactions with the BCP.

A new dimethylsulfoniopropionate lyase of the cupin superfamily in marine bacteria.

Dimethylsulfoniopropionate (DMSP) is a marine organosulfur compound with important roles in stress protection, marine biogeochemical cycling, chemical signalling and atmospheric chemistry. Diverse marine microorganisms catabolize DMSP via DMSP lyases to generate the climate-cooling gas and info-chemical dimethyl sulphide. Abundant marine heterotrophs of the Roseobacter group (MRG) are well known for their ability to catabolize DMSP via diverse DMSP lyases. Here, a new DMSP lyase DddU within the MRG strain Amylibacter cionae H-12 and other related bacteria was identified. DddU is a cupin superfamily DMSP lyase like DddL, DddQ, DddW, DddK and DddY, but shares <15% amino acid sequence identity with these enzymes. Moreover, DddU proteins forms a distinct clade from these other cupin-containing DMSP lyases. Structural prediction and mutational analyses suggested that a conserved tyrosine residue is the key catalytic amino acid residue in DddU. Bioinformatic analysis indicated that the dddU gene, mainly from Alphaproteobacteria, is widely distributed in the Atlantic, Pacific, Indian and polar oceans. For reference, dddU is less abundant than dddP, dddQ and dddK, but much more frequent than dddW, dddY and dddL in marine environments. This study broadens our knowledge on the diversity of DMSP lyases, and enhances our understanding of marine DMSP biotransformation.

Benthic-pelagic coupling and isotopic fractionation of barium in Kiel Bight, SW Baltic Sea

Barium (Ba) isotopes are a promising new tracer for riverine freshwater input to the ocean and marine biogeochemical cycling. However, many processes that affect Ba cycling at continental margins have not yet been investigated with respect to Ba isotope fractionation. Here, we present a comprehensive data set of Ba concentration and isotope data for water column, pore water and sediment samples from Kiel Bight, a seasonally stratified and hypoxic fjord in the southwestern Baltic Sea. The surface water Ba concentration and Ba isotope inventory of the water column can generally be explained by mixing of riverine freshwater and Atlantic seawater. However, the deep-water below the seasonal pycnocline (10 - 15 m water depth) is characterized by a pronounced positive Ba concentration anomaly (up to 915 nM) that is accompanied by a δ138Ba of ~+0.25 ‰, which is lighter than expected from the seawater-freshwater mixing line (Ba: 77 nM, δ138Ba: +0.32 ‰ at a salinity of 18). Pore water profiles indicate a Ba flux across the sediment-water interface, which contributes to the enrichment in isotopically light Ba in the deep-water. Pore waters of surface sediments and deep-waters are oversaturated with respect to barite. Therefore, barite dissolution is unlikely to account for the benthic Ba flux. Water column Ba concentrations closely correlate with those of the nutrients phosphate and silica, which are removed from surface waters by biological processes and recycled from the sediment by diffusion across the sediment-water interface. As nutrient-to-Ba ratios differ among sites and from those observed in open-marine systems, we propose that Ba is removed from surface waters by adsorption onto biogenic particles (rather than assimilation) and regenerated within surface sediments upon organic matter degradation. Pore water data for subsurface sediments in Kiel Bight indicate preferential transfer of isotopically heavy Ba into an authigenic phase during early diagenesis. Quantifying the burial flux associated with this authigenic Ba phase along continental margins could potentially help to settle the isotopic imbalance between known Ba source and sink fluxes in the ocean.

Geochemical Characteristics of Iron in a Sediment Core at 63°40′ E, Eastern Southwest Indian Ridge: Implications on Regional Hydrothermal Activities and Source Origin

Iron is a limiting nutrient in the marine biogeochemical cycle, and hydrothermal processes at mid-ocean ridges are well-known as one of its sources to the water column. However, a major portion of the hydrothermal iron is precipitated near the source and plays an essential role in oceanic elemental cycling. Here, we carried out a detailed study on the geochemical characteristics of Fe, using a sequential chemical extraction protocol, in a short sediment core collected from the eastern Southwest Indian Ridge (SWIR) to understand the iron association in individual mineral phases. Major and trace and rare-earth element concentrations, positive europium anomaly, and rare-earth fractionation show that the source components in the sediment core are composed of biogenic, local mafic, ultramafic, and hydrothermal origin. Solid-phase Fe speciation results indicate that &gt;60% of Fe is associated with the Fe-oxides phase and indicate the hydrothermal plume particulates settled from the water column. A relatively low concentration of Fe associated with the pyrite and silicate (FeRes) phase suggests an erosion of sulphide and silicate minerals from the nearby vent field. The down-core variation reflects the transformation of primary ferrihydrite to more stable oxide mineral goethite/hematite and, to some extent, the formation of silicate minerals.

The biogeochemistry of zinc and cadmium in the Amundsen Sea, coastal Antarctica

The trace metals zinc (Zn) and cadmium (Cd) are both involved in the metabolic processes of marine phytoplankton, and as such, both metals play important roles in ocean biogeochemical cycles. In Antarctica, the Amundsen Sea (AS) experiences rapid ice shelf melting, and the Amundsen Sea polynya (ASP) hosts seasonal phytoplankton blooms in austral summer, with important implications for atmospheric carbon dioxide drawdown. However, the effects of ice melting and phytoplankton blooms on the biogeochemistry and distributions of Zn and Cd in the ASP remain poorly studied. Here, we present the first combined dataset of dissolved and particulate Zn and Cd in the AS (including the inflow and outflow to and from the Dotson and Getz ice shelves) collected as part of the GEOTRACES process study GPpr12. We use this dataset to assess the sources of both elements to the AS region and characterize the particle composition in the ASP. We find that the main source of both dissolved Zn and Cd in the AS is Circumpolar Deep Water (CDW), with an additional small flux of both metals from shelf sediments. By contrast, aerosol deposition, ice shelf melt, and sea ice melt are all deemed insignificant sources for either Zn or Cd in the AS. Labile particulate Zn and Cd dominate the total particulate pool in the surface layer, indicating that biological uptake is a predominant process for the cycling of both metals in the ASP, whereas sediment resuspension and ice shelf melt do not supply a significant amount of either particulate Zn or Cd. Additionally, we use two commonly used approaches to estimate biogenic and lithogenic particulate concentrations. We find high biogenic particulate concentrations at the surface, decreasing with depth, indicating remineralization plays an important role in the cycling of particulate metals. In contrast, lithogenic particulate metal concentrations remain low throughout the water column. We also show that the estimated uptake ratios of Zn and Cd relative to phosphate in the surface layer are lower than reported for the open Southern Ocean, likely related to the spatial and temporal variability of Fe in the AS. Overall, these new observations provide insight into the biogeochemistry of both Zn and Cd in the AS, a region that is subject to the influence of rapid climate change, which may have implications for the larger-scale cycling of trace metals in the Southern Ocean. Specifically, the amount of Zn and Cd supplied to the surface ASP will increase, given that the volume of CDW that flows towards the Dotson Ice Shelf is predicted to increase.

Growth dynamics and transcriptional responses of a Red Sea Prochlorococcus strain to varying temperatures.

Prochlorococcus play a crucial role in the ocean's biogeochemical cycling, but it remains controversial how they will respond to global warming. Here we assessed the response to temperature (22-30°C) of the growth dynamics and gene expression profiles of a Red Sea Prochlorococcus strain (RSP50) in a non-axenic culture. Both the specific growth rate (0.55-0.80 day-1 ) and cell size (0.04-0.07 μm3 ) of Prochlorococcus increased significantly with temperature. The primary production released extracellularly ranged from 20% to 34%, with humic-like fluorescent compounds increasing up to fivefold as Prochlorococcus reached its maximum abundance. At 30°C, genes involved in carbon fixation such as CsoS2 and CsoS3 and photosynthetic electron transport including PTOX were downregulated, suggesting a cellular homeostasis and energy saving mechanism response. In contrast, PTOX was found upregulated at 22°C and 24°C. Similar results were found for transaldolase, related to carbon metabolism, and citrate synthase, an important enzyme in the TCA cycle. Our data suggest that in spite of the currently warm temperatures of the Red Sea, Prochlorococcus can modulate its gene expression profiles to permit growth at temperatures lower than its optimum temperature (28°C) but is unable to cope with temperatures exceeding 30°C.

Genomic diversity and ecological distribution of marine Pseudoalteromonas phages

Pseudoalteromonas, with a ubiquitous distribution, is one of the most abundant marine bacterial genera. It is especially abundant in the deep sea and polar seas, where it has been found to have a broad metabolic capacity and unique co-existence strategies with other organisms. However, only a few Pseudoalteromonas phages have so far been isolated and investigated and their genomic diversity and distribution patterns are still unclear. Here, the genomes, taxonomic features and distribution patterns of Pseudoalteromonas phages are systematically analyzed, based on the microbial and viral genomes and metagenome datasets. A total of 143 complete or nearly complete Pseudoalteromonas-associated phage genomes (PSAPGs) were identified, including 34 Pseudoalteromonas phage isolates, 24 proviruses, and 85 Pseudoalteromonas-associated uncultured viral genomes (UViGs); these were assigned to 47 viral clusters at the genus level. Many integrated proviruses (n = 24) and filamentous phages were detected (n = 32), suggesting the prevalence of viral lysogenic life cycle in Pseudoalteromonas. PSAPGs encoded 66 types of 249 potential auxiliary metabolic genes (AMGs) relating to peptidases and nucleotide metabolism. They may also participate in marine biogeochemical cycles through the manipulation of the metabolism of their hosts, especially in the phosphorus and sulfur cycles. Siphoviral and filamentous PSAPGs were the predominant viral lineages found in polar areas, while some myoviral and siphoviral PSAPGs encoding transposase were more abundant in the deep sea. This study has expanded our understanding of the taxonomy, phylogenetic and ecological scope of marine Pseudoalteromonas phages and deepens our knowledge of viral impacts on Pseudoalteromonas. It will provide a baseline for the study of interactions between phages and Pseudoalteromonas in the ocean.

The Predominance of Ammonia-Oxidizing Archaea in an Oceanic Microbial Community Amended with Cyanobacterial Lysate.

When the oligotrophic microbial community was amended with Synechococcus-derived dissolved organic matter (SDOM) and incubated under the dark condition, archaea relative abundance was initially very low but made up more than 60% of the prokaryotic community on day 60, and remained dominant for at least 9 months. The archaeal sequences were dominated by Candidatus Nitrosopumilus, the Group I.1a Thaumarchaeota. The increase of Thaumarchaeota in the dark incubation corresponded to the period of delayed ammonium oxidation upon an initially steady increase in ammonia, supporting the remarkable competency of Thaumarchaeota in energy utilization and fixation of inorganic carbon in the ocean. IMPORTANCE Thaumarchaeota, which are ammonia-oxidizing archaea (AOA), are mainly chemolithoautotrophs that can fix inorganic carbon to produce organic matter in the dark. Their distinctive physiological traits and high abundance in the water column indicate the significant ecological roles they play in the open ocean. In our study, we found predominant Thaumarchaeota in the microbial community amended with cyanobacteria-derived lysate under the dark condition. Furthermore, Thaumarchaeota remained dominant in the microbial community even after 1 year of incubation. Through the ammonification process, dissolved organic matter (DOM) from cyanobacterial lysate was converted to ammonium which was used as an energy source for Thaumarchaeota to fix inorganic carbon into biomass. Our study further advocates the important roles of Thaumarchaeota in the ocean's biogeochemical cycle.

Biogeochemical cycling of dissolved manganese in the Arabian Sea

The study of marine biogeochemical cycling of Mn, a bio-essential trace metal, is crucial to decipher its relative role in controlling the production and diversity of marine phytoplankton. Furthermore, Mn oxides and oxyhydroxides act as sinks for other trace elements in the water column, and Mn redox cycling may exert a major control on the vertical distribution of these elements. Dissolved Mn (dMn) concentrations are measured along two GEOTRACES-India (GI) transects, GI05 and GI10, for a basin-wide investigation of biogeochemical controls on the dMn distribution in the Arabian Sea (AS). Surface dMn distribution shows a strong spatial gradient, with relatively dMn-rich levels in the eastern AS (3.4–5.7 nmol kg−1) compared to the central and western AS (1.2–2.3 nmol kg−1). This correlates with the higher model estimates of soluble Mn input from the atmospheric dust deposition in the eastern AS (∼1.5–2.0 times of input in the western and central AS), and probable additional Mn input from riverine discharge and shallow shelf region of the eastern AS. In the south-eastern AS, a correlated increase in surface dMn with a decrease in salinity indicates the Mn input by the advection of dMn-rich, low-salinity Bay of Bengal (BoB) surface waters to the AS under the influence of the Northeast Monsoon Current. Our mass balance estimates for dMn in the euphotic waters (upper 100 m) suggest important contributions from atmospheric Mn deposition (14–99% of the total estimated input flux), and dMn input/dilution (13–74% of the total estimated input or removal flux) due to lateral/vertical advective-eddy diffusive mixing. Mn-oxidation and passive scavenging are determined to be the dominant processes for the dMn removal (61–99%) from the euphotic zone (upper 100 m), while export via Mn bio-assimilation is comparatively negligible.In the AS denitrification zone, the observed dMn maxima in the upper thermocline depths (∼200–400 m) result from the in situ reductive dissolution of Mn oxides and oxyhydroxides, and lateral advective-eddy diffusive Mn flux from the reducing sediments of the western Indian margin. Outside the denitrification zone, in the northern and western AS, a shift of dMn maxima to the lower thermocline waters (∼500 m) indicates the change in the source region and dMn input from the reducing margins of the north (Pakistan Margin) and north-western AS (Oman Margin), intersecting the core of the oxygen minima at the depth range of 400–600 m.Deep water (>1500 m) dMn concentrations are low (<0.3 nmol kg−1) in most of the AS regions. Anomalous dMn enrichment in the deep waters is observed in the southern and western AS, presumably indicating the influence of hydrothermal plumes emanating from the active hydrothermal vents over the Carlsberg Ridge and spreading ridges in the Gulf of Aden. A correlated and localized increase in dMn and dAl levels close to the Murray Ridge hints at dMn input from the sediment resuspension over the ridge and subsequent Mn dissolution in low-oxygen waters (DO < 20 µM) and/or diffusive flux from the Mn-rich pore waters.

Molecular investigation of the multi-phase photochemistry of Fe(III)-citrate in aqueous solution.

Iron (Fe) is ubiquitous in nature and found as FeII or FeIII in minerals or as dissolved ions Fe2+ or Fe3+ in aqueous systems. The interactions of soluble Fe have important implications for fresh water and marine biogeochemical cycles, which have impacts on global terrestrial and atmospheric environments. Upon dissolution of FeIII into natural aquatic systems, organic carboxylic acids efficiently chelate FeIII to form [FeIII-carboxylate]2+ complexes that undergo a wide range of photochemistry-induced radical reactions. The chemical composition and photochemical transformations of these mixtures are largely unknown, making it challenging to estimate their environmental impact. To investigate the photochemical process of FeIII-carboxylates at the molecular level, we conduct a comprehensive experimental study employing UV-visible spectroscopy, liquid chromatography coupled to photodiode array and high-resolution mass spectrometry detection, and oil immersion flow microscopy. In this study, aqueous solutions of FeIII-citrate were photolyzed under 365 nm light in an experimental setup with an apparent quantum yield of (φ) ∼0.02, followed by chemical analyses of reacted mixtures withdrawn at increment time intervals of the experiment. The apparent photochemical reaction kinetics of Fe3+-citrates (aq) were expressed as two generalized consecutive reactions of with the experimental rate constants of j1 ∼ 0.12 min-1 and j2 ∼ 0.05 min-1, respectively. Molecular characterization results indicate that R and I consist of both water-soluble organic and Fe-organic species, while P compounds are a mixture of water-soluble and colloidal materials. The latter were identified as Fe-carbonaceous colloids formed at long photolysis times. The carbonaceous content of these colloids was identified as unsaturated organic species with low oxygen content and carbon with a reduced oxidation state, indicative of their plausible radical recombination mechanism under oxygen-deprived conditions typical for the extensively photolyzed mixtures. Based on the molecular characterization results, we discuss the comprehensive reaction mechanism of FeIII-citrate photochemistry and report on the formation of previously unexplored colloidal reaction products, which may contribute to atmospheric and terrestrial light-absorbing materials in aquatic environments.

First Estimate Biosiliceous Sedimentation Flux in the Pearl River Estuary from 2000–2020 by Satellite Remote Sensing

Biosiliceous sedimentation, closely related to carbon sedimentation in water, has a significant impact on the marine biogeochemical cycle. However, large-scale monitoring data are scarce due to the constraints of biosiliceous sedimentation flux (BSF) gathering methods. There are few reports on the spatiotemporal variation of BSF in estuaries and offshore waters. Additionally, few studies have used satellite remote sensing methods to retrieve BSF. In the paper, satellite images from 2000 to 2020 were used for the first time to estimate the BSF distribution of the Pearl River Estuary (PRE) over the past 20 years, based on a remote sensing model combined with particulate organic carbon (POC) deposition data and water depth data. The results showed that the BSF ranged from 100 to 2000 mg/(m2 × d). The accuracy tests indicated that the correlation coefficient (R2) and significance (P) of Pearson correlation analysis were 0.8787 and 0.0018, respectively. The BSF value varied seasonally and increased every year. The BSF did not follow a simple trend of decreasing along the coast to open water. Shenzhen Bay (SZB) generally had a higher BSF value than the Dragon’s Den Waterway (DDW). The BSF in autumn and winter was investigated using empirical orthogonal function analysis (EOF). In autumn, the BSF of the PRE’s eastern bank showed little change, while the BSF of the western bank showed obvious differences. In winter, the BSF in Hong Kong waters and inlet shoals fluctuated less, whereas the BSF in DDW and Lingding Waterway (LW) fluctuated more. The grey correlation analysis (GRA) identified two factors affecting BSF: chromophoric dissolved organic matter (CDOM) and total suspended solids (TSS). Most BSF were primarily affected by TSS during winter. In spring, the two effects were balanced. TSS affected the east coast in summer, and CDOM was the dominant effect in autumn. Four main parameters influencing the distribution of BSF in the PRE were analyzed: ecosystem, reef, flow field and flocculation. This study showed that using satellite remote sensing to estimate BSF has excellent potential, which is worthy of further discussion in terms of spatiotemporal resolution and model optimization.

Rates of seafloor and continental weathering govern Phanerozoic marine phosphate levels

Phosphate is an essential macronutrient for all organisms with a key role in setting levels of marine primary productivity. Despite its importance for marine biogeochemical cycles and its role in shaping the evolution of marine organisms, the factors controlling phosphate bioavailability on geologic timescales remain poorly understood. Here we develop a statistical model of the coupled cycles of phosphate, carbon, oxygen and calcium to constrain the weathering-derived fluxes and seawater concentrations of phosphate through Phanerozoic time (541 million years ago to the present). Our model includes input parameters and time-dependent forcings derived from geologic and geochemical data. We find that the climate sensitivity of chemical weathering of the oceanic crust by low-temperature fluids exerts a first-order control on phosphate availability. Specifically, continental weathering is a source of the limiting nutrient phosphate, but seafloor weathering is considered to be a minor phosphate sink. Consequently, times in Earth history during which seafloor weathering constituted a large fraction of the total (seafloor + continental) weathering were also times during which phosphate influxes to and concentrations in the ocean were relatively low. Lower seawater phosphate levels during those times probably resulted in lower primary productivity and oceanic and atmospheric oxygen concentrations.