Cariaco Basin Research Articles

Plasmid-Borne Biosynthetic Gene Clusters within a Permanently Stratified Marine Water Column.

Plasmids are mobile genetic elements known to carry secondary metabolic genes that affect the fitness and survival of microbes in the environment. Well-studied cases of plasmid-encoded secondary metabolic genes in marine habitats include toxin/antitoxin and antibiotic biosynthesis/resistance genes. Here, we examine metagenome-assembled genomes (MAGs) from the permanently-stratified water column of the Cariaco Basin for integrated plasmids that encode biosynthetic gene clusters of secondary metabolites (smBGCs). We identify 16 plasmid-borne smBGCs in MAGs associated primarily with Planctomycetota and Pseudomonadota that encode terpene-synthesizing genes, and genes for production of ribosomal and non-ribosomal peptides. These identified genes encode for secondary metabolites that are mainly antimicrobial agents, and hence, their uptake via plasmids may increase the competitive advantage of those host taxa that acquire them. The ecological and evolutionary significance of smBGCs carried by prokaryotes in oxygen-depleted water columns is yet to be fully elucidated.

Increasing Long-Term Memory as an Early Warning Signal for a Critical Transition

Abstract In recent years, various early warning signals of critical transition have been presented, such as autocorrelation at lag 1 [AR(1)], variance, the propagator based on detrended fluctuation analysis (DFA-propagator), and so on. Many studies have shown that the climate system has the characteristics of long-term memory (LTM). Will the LTM characteristics of the climate system change as it approaches possible critical transition points? In view of this, the present paper first studies whether the LTM of several folding (folded bifurcation) models changes consistently as they approach their critical points slowly by the rescaled range (R/S) analysis. The results of numerical experiments show that when the control parameters of the folding model are close to its critical threshold, the Hurst exponent H exhibits an almost monotonic increase (significance level α = 0.05). We compare the performance of R/S with the existing indicators, including AR(1), variance, and DFA-propagator, and find that R/S is a perfectly valid alternative. When there is no extra false noise, AR(1) and variance have good early warning effects. After the addition of extra Gaussian white noise of different intensities, the values of AR(1) and variance change significantly. As a result, the DFA-propagator based on AR(1) calibration also changed significantly. Compared with the other three indicators, the early warning effect of H has stronger ability to resist the interference of external false signals. To further verify the validity of increasing H, paleoclimate reconstruction of Cariaco Basin sediment core grayscale record with long trends filtered out is studied by R/S analysis. The other three early warning signals are calculated in the same way. The data contain a well-known abrupt climate change: the transition between the Younger Dryas (YD) and the Holocene. We find that approximately 300 years before this abrupt climate change occurred, before 11.7 kyr BP, the LTM exponents for Cariaco Basin deglacial grayscale data present an obvious increasing trend at a significant level of α = 0.05. Meanwhile, the variation trend of H and DFA-propagator is basically similar. This shows that increasing H by R/S analysis is an effective early warning signal, which indicates that a dynamic system is approaching its possible critical transition points; H is a completely valid alternative signal for AR(1) and DFA-propagator. The main conclusion of this paper is based on numerical experiments. The precise relationship between H and the stability of the underlying state approaching the transition needs to be further studied. Significance Statement Dynamic systems have critical transition points, and these systems will suddenly change from a stable state to another alternative one beyond these points. Using several simple theoretical models and paleoclimate data, we study whether the characteristics of long-term memory, which are ubiquitous in complex systems in nature and society, change as a system approaches its critical transition point. The results show that the long-term memory of a dynamic system increases significantly with the approach of the critical point, whether in theoretical models or in paleoclimate data.

Biomass Storage in Anoxic Marine Basins: Initial Estimates of Geochemical Impacts and CO2 Sequestration Capacity

AbstractIn combination with dramatic and immediate CO2 emissions reductions, net‐negative atmospheric CO2 removal (CDR) is necessary to maintain average global temperature increases below 2.0°C. Many proposed CDR pathways involve the placement of vast quantities of organic carbon (biomass) on the seafloor in some form, but little is known about their potential biogeochemical impacts, especially at scales relevant for global climate. Here, we evaluate the potential impacts and durability of organic carbon storage specifically within deep anoxic basins, where organic matter (OM) is remineralized through anaerobic processes that may enhance its storage efficiency. We present simple biogeochemical and mixing models to quantify the scale of potential impacts of large‐scale OM addition to the abyssal seafloor in the Black Sea, Cariaco Basin, and the hypersaline Orca Basin. These calculations reveal that the Black Sea in particular may have the potential to accept biomass storage at climatically relevant scales with moderate changes to the geochemical state of abyssal water and limited communication of that impact to surface water. Still, all of these systems would require extensive further evaluation prior to consideration of megatonne‐scale CO2 sequestration. Many key unknowns remain, including the partitioning of breakdown among sulfate‐reducing and methanogenic metabolisms and the fate of methane in the environment. Given the urgency of responsible CDR development and the potential for anoxic basins to reduce ecological risks to animal communities, efforts to address knowledge gaps related to microbial kinetics, benthic processes, and physical mixing in these systems are critically needed.

Evaluation of three contrasting models in estimating primary production from ocean color remote sensing using long-term time-series data at oceanic and coastal sites

Accurate estimates of depth-integrated Net Primary Production (NPP, mg C m−2 d−1) and the creation of a robust climate data record of NPP for the global oceans are essential goals of the ocean color remote sensing community. Here, we take advantage of in situ NPP measurements from three long-term time-series sites, the HOT (Hawaii Ocean Time-series), BATS (Bermuda Atlantic Time-series Study) and CARIACO (Ocean Time-Series Program from the Cariaco basin), spanning over 30 years to evaluate three contrasting models in estimating NPP from ocean color remote sensing. These models for NPP estimation include the Absorption-based Model (AbPM), which relies on phytoplankton absorption coefficient, the Vertically Generalized Production Model (VGPM), which centers on chlorophyll-a concentration, and the Carbon-based Productivity Model (CbPM) centering on phytoplankton carbon. In addition to the accuracy of NPP estimation from these models, we laid great emphasis on evaluating their skills in capturing the monthly to seasonal variations and interannual trends in NPP at the three sites. Comparison with in situ NPP at all three long-term sites (∼20 years) showed that AbPM yielded the highest coefficient of determination (R2 = 0.67) and the lowest uncertainties (Bias = 0.03 and unbiased root mean square difference = 0.17). Seasonal and interannual variations apparent in the in situ NPP time-series records were best captured by AbPM. These results showcase the robust capabilities of AbPM and its superiority for global carbon cycling and climate change studies, largely because it takes into account optical and photosynthetic parameters of local phytoplankton.

Summer insolation controlled movements of Intertropical Convergence Zone during last glacial cycle in northern South America

A paradigm in paleoclimatology holds that shifts in the mean position of the Intertropical Convergence Zone were the dominant climatic mechanism controlling rainfall in the tropics during the last glacial period. We present a new paleo-rainfall reconstruction based on speleothem stable oxygen isotopes record from Colombia, which spans most of the last glacial cycle. The strength and positioning of the Intertropical Convergence Zone over northern South America were more strongly affected by summer insolation at high northern latitudes than by local insolation during the last glacial cycle, resulting in an antiphased relationship with climate in the Cariaco Basin. Our data also provide new insight into how orbital forcing amplified/dampened Intertropical Convergence Zone precipitation during millennial-scale events. During Greenland Stadial events, the Intertropical Convergence Zone was positioned close to the latitude of El Peñon, as expressed by more negative δ18O values. Greenland Interstadial events are marked by relatively high stable oxygen isotope values and reduced rainfall in the El Peñon record, suggesting a northward withdrawal of the Intertropical Convergence Zone. During some Heinrich Stadial events, and especially Heinrich Stadial 1, the Intertropical Convergence Zone must have been displaced away from its modern location near El Peñon, as conditions were very dry at both El Peñon and Cariaco.

Refined views of ancient ocean chemistry: Tracking trace element incorporation in pyrite framboids using atom probe tomography

The trace element chemistry of pyrite can be used to determine the origin, timing, and conditions of formation of ore deposits; as a vectoring tool for mineral exploration; and to determine the evolution of the Earth’s oceanic and atmospheric chemistry. However, little is known about whether trace elements are held with the pyrite structure or within nano-inclusions of other phases. This distinction is important for two primary reasons. First, trace element incorporation into the pyrite structure can affect the partitioning of other trace elements. Second, if trace elements are held within nano-inclusions, the partition coefficient of the mineral phases that make up the nano-inclusion, rather than pyrite, are the critical consideration in related interpretations. Previous studies addressing this topic have used laser ablation inductively coupled plasma mass spectrometry; however, the resulting data do not provide sufficient spatial resolution to delineate trace element distributions unless the inclusions are large. Further, they use these flat element profiles in time resolved laser ablation output graphs to argue that pyrite trace element content provides a direct relationship between trace element content of seawater and pyrite trace element content. To improve resolution, we have used atom probe tomography to characterize trace element distributions in pyrite framboids from the Cariaco Basin and Demerara Rise in three-dimensions at sub-nanometer resolution. Manganese was found to be concentrated in the pyrite nanocrystal part of the original framboid structure. In contrast, Ni was mostly found along the grain boundary, though it still appeared to be contained within the pyrite structure. Copper was concentrated in later pyrite overgrowths, and As varied in its location. These observations suggest that some important trace elements are incorporated into pyrite during early diagenesis, even in euxinic settings dominated by water-column pyrite formation. Statistical analysis was used to determine whether trace elements were incorporated in the lattice or within nanoscale inclusions (referred to here are nano-inclusions). We found that As, Ni, Cu, and Mn were commonly held within the pyrite structure, but As, Ni, and Cu can also be held as nano-inclusions or within grain interfaces. Incorporation of As is known to enhance the incorporation of other trace elements and in this case appears to correlated to elevated Ni and Cu concentrations in the Cariaco Basin samples. Understanding these relationships strongly impacts our ability to utilize pyrite trace metal concentrations to analyze and quantify early ocean chemistry and its evolution through time.

Atlantic ITCZ variability during the Holocene based on high-resolution speleothem isotope records from northern Venezuela

Few high-resolution paleoclimate proxy records exist in the region located under the direct influence of the Intertropical Convergence Zone (ITCZ) in South America and most of them were retrieved from the Cariaco Basin off the coast of Venezuela. Here we present new ẟ18O and ẟ13C records of Venezuelan speleothems collected in caves adjacent to Cariaco, covering the mid- and late-Holocene. We document previously undetected secular-to multidecadal-scale climate variability in the core region of the ITCZ, which is compared to other high-resolution records from the North Atlantic, Caribbean and tropical South America. Over the mid-Holocene our record exhibits broad swings between periods of reduced (8.3–8.0, 6.5–5.0, 4.1–3.6 ka BP) and increased (8.5, 8.0–6.5, 4.9–4.2 ka BP) rainfall. In particular, between 5.5 and 5.0 ka BP, increases in polar and subpolar North Atlantic ice rafted debris and a reduction in North Atlantic Deep Water (NADW) formation might have contributed to the southward displacement of the North Atlantic Subtropical High (NASH) and the ITCZ, which led to severe dry conditions in north central Venezuela and an enhancement of the South American Monsoon System (SAMS). During the late-Holocene, contrary to data from Cariaco reported in previous studies, our results point to drier conditions during the Medieval Climate Anomaly (MCA, 900–1100 CE), which were further amplified during positive Atlantic Multidecadal Oscillation (AMO) phases. Wet conditions, however, prevailed during the first part of the Little Ice Age (LIA, 1400–1500 CE). No speleothem deposition occurred during the main LIA period, which might be related to drier conditions in response to a southward displacement of the ITCZ that led to major moisture convergence over the SASM domain. Our new records from Venezuela provide a reliable proxy for ITCZ behavior over the Atlantic – South America domain and document past dynamics in relation to other climate systems (NASH and SAMS), while providing new evidence of ITCZ – North Atlantic teleconnections during the Holocene.

Revisiting paleoenvironmental changes on the Upper Yangtze Block during the Ordovician-Silurian transition: New insights from elemental geochemistry

Temporal and spatial patterns of paleoenvironmental change on the Upper Yangtze Block during the Ordovician-Silurian transition remain debatable and somewhat self-contradictory. The present study is a reassessment of how regional and global events may have influenced the paleoenvironmental evolution of the Upper Yangtze Block. Abundances of redox-sensitive trace elements, including Mo and U, suggest a general ascending stratigraphic pattern from the oxic to anoxic (euxinic) conditions during Late Katian time. High-resolution fluctuations of redox conditions may reflect frequent eustatic sea-level changes. The Kuanyinchiao Bed accumulated under less reducing conditions during the climax of Hirnantian glaciation. Post-glacial transgression during the latest Hirnantian to Early Rhuddanian was accompanied by the re-establishment of euxinic bottom-water conditions. Authigenic MoU covariation and Mo/TOC values of the studied stratigraphic successions suggest that the Upper Yangtze Shelf Sea was weakly to moderately restricted. Patterns of Cd/Mo and Co (ppm) × Mn (wt%) values suggest that the study area of the basin did not experience persistent upwelling. Instead, only seasonal upwelling occurred on the outer shelf, which is somewhat analogous with the modern Cariaco Basin. Terrestrial inputs, as reflected by Si/Al values, correspond with periods of diminished sedimentation rates and the establishment of anoxic conditions. Uplift associated with the Kwangsian Orogeny during latest Hirnantian to the early Rhuddanian time caused an increase in sedimentation rates in the eastern region of the study area. Strong covariance of Baxs and Eu/Eu* suggests that paleoproductivity was enhanced by regional hydrothermal events. Our results suggest that redox conditions and clastic inputs during deposition of the Ordovician-Silurian transition succession of the Upper Yangtze shelf were linked to climatically-induced sea-level fluctuations whereas the spatial gradient of redox conditions and clastic inputs from inner shelf to outer shelf was strongly controlled by paleogeography and orogenic movements.

Diverse secondary metabolites are expressed in particle-associated and free-living microorganisms of the permanently anoxic Cariaco Basin

Secondary metabolites play essential roles in ecological interactions and nutrient acquisition, and are of interest for their potential uses in medicine and biotechnology. Genome mining for biosynthetic gene clusters (BGCs) can be used for the discovery of new compounds. Here, we use metagenomics and metatranscriptomics to analyze BGCs in free-living and particle-associated microbial communities through the stratified water column of the Cariaco Basin, Venezuela. We recovered 565 bacterial and archaeal metagenome-assembled genomes (MAGs) and identified 1154 diverse BGCs. We show that differences in water redox potential and microbial lifestyle (particle-associated vs. free-living) are associated with variations in the predicted composition and production of secondary metabolites. Our results indicate that microbes, including understudied clades such as Planctomycetota, potentially produce a wide range of secondary metabolites in these anoxic/euxinic waters.

Transport-limited reactions in microbial systems.

Predicting microbial metabolic rates and emergent biogeochemical fluxes remains challenging due to the many unknown population dynamical, physiological and reaction-kinetic parameters and uncertainties in species composition. Here, we show that the need for these parameters can be eliminated when population dynamics and reaction kinetics operate at much shorter time scales than physical mixing processes. Such scenarios are widespread in poorly mixed water columns and sediments. In this 'fast-reaction-transport' (FRT) limit, all that is required for predictions are chemical boundary conditions, the physical mixing processes and reaction stoichiometries, while no knowledge of species composition, physiology or population/reaction kinetic parameters is needed. Using time-series data spanning years 2001-2014 and depths 180-900 m across the permanently anoxic Cariaco Basin, we demonstrate that the FRT approach can accurately predict the dynamics of major electron donors and acceptors (Pearson r ≥ 0.9 in all cases). Hence, many microbial processes in this system are largely transport limited and thus predictable regardless of species composition, population dynamics and kinetics. Our approach enables predictions for many systems in which microbial community dynamics and kinetics are unknown. Our findings also reveal a mechanism for the frequently observed decoupling between function and taxonomy in microbial systems.

Vegetation history of a Mexican Neotropical basin from the late MIS 6 to early MIS 3: The pollen record of Lake Chalco

A new detailed pollen record of the penultimate glacial–interglacial–glacial cycle corresponding to the late marine isotopic stages (MISs) 6–3 (146–35 ka ago) has been obtained from Lake Chalco, in the Basin of Mexico. This record provides an insight into vegetation dynamics and climate variability at the northern limit of the American tropics. The pollen record displays a high temporal resolution with a mean sampling interval of ∼230 years. The changes in plant composition were reconstructed by pollen analysis and differences in plant composition between distinct periods were established. The wettest cold stage, indicated by a combination of diverse open vegetation and mesophytic taxa correlates with the penultimate late glacial MIS 6 (146–130 ka), when Lake Chalco was a deep freshwater lake. The penultimate interglacial MIS 5e (126.5–123.6 ka) shows a dominance of Pinus forests, with tropical taxa suggesting warmer than present conditions; environmental proxies indicate drier conditions and that the lake transitioned into a saline water body. Open communities and Pinus and Quercus forests with mesophytic taxa and, during the stadial periods, MIS 5 d, 5c, and 5 b (125–90 ka), with tropical taxa, characterize the record of interstadials. Pinus-dominated forests characterize the landscape during MIS 5a. MIS 5c to MIS 3 showed lower and variable evenness and palynological richness, along with an increase in fire activity. During MIS 4 and 3, a trend towards drier conditions was also recorded with enhanced carbonate precipitation and proxies indicating saline conditions. Tree-line changes in response to climate change and taxa migration were documented. A comparison with long records from the Greenland ice cores, the marine Cariaco Basin and insolation parameters revealed that the pollen data and the Pinus pollen accumulation rates evidence the response of the vegetation to glacial and interglacial changes and to millennial-scale variability. Wetter conditions were inferred to exist during the Greenland interstadials, while drier conditions persisted during Heinrich events.

Development of lacustrine primary productivity in the Amazon Basin during the Holocene

The Amazon Basin is one of the most productive regions in the world and an important carbon sink. However, lake productivity has varied throughout the Holocene, as preserved in lacustrine sedimentary records. Concentrations of chlorophyll pigmented derivatives that are mainly derived from phytoplankton and macrophyte populations can be used to infer lake production levels. Here we use the chlorophyll derivatives concentrations analyzed by spectrophotometer in sediment cores from nine lakes distributed throughout the Brazilian Amazon Basin to document the continental-scale changes in lake production during the Holocene. Chlorophyll derivatives have varied with changes in precipitation rate throughout the last 10,000 years, similar to other climate records in tropical South America, including Ti concentration from the Cariaco Basin, δ13C from Lake Titicaca, and refractory black carbon in Nevado Illimani. Increasing precipitation is responsible for increasing the nutrient supply into the lake, which stimulates primary production. Our analysis was compared to climate-related parameters, suggesting an increasing trend of lake production rates during the wetter Late and Early Holocene, while lower production rates characterized the dry phase of the Middle Holocene. Therefore, the chlorophyll derivatives concentrations generally follow precipitation changes in the Amazon Basin during the Holocene.

Eukaryotic Parasites Are Integral to a Productive Microbial Food Web in Oxygen-Depleted Waters.

Oxygen-depleted water columns (ODWCs) host a diverse community of eukaryotic protists that change dramatically in composition over the oxic-anoxic gradient. In the permanently anoxic Cariaco Basin, peaks in eukaryotic diversity occurred in layers where dark microbial activity (chemoautotrophy and heterotrophy) were highest, suggesting a link between prokaryotic activity and trophic associations with protists. Using 18S rRNA gene sequencing, parasites and especially the obligate parasitic clade, Syndiniales, appear to be particularly abundant, suggesting parasitism is an important, but overlooked interaction in ODWC food webs. Syndiniales were also associated with certain prokaryotic groups that are often found in ODWCs, including Marinimicrobia and Marine Group II archaea, evocative of feedbacks between parasitic infection events, release of organic matter, and prokaryotic assimilative activity. In a network analysis that included all three domains of life, bacterial and archaeal taxa were putative bottleneck and hub species, while a large proportion of edges were connected to eukaryotic nodes. Inclusion of parasites resulted in a more complex network with longer path lengths between members. Together, these results suggest that protists, and especially protistan parasites, play an important role in maintaining microbial food web complexity, particularly in ODWCs, where protist diversity and microbial productivity are high, but energy resources are limited relative to euphotic waters.

The Re/Mo redox proxy reconsidered

Compared to continental crust, marine sediments accumulating beneath O2 depleted waters are enriched in Re and Mo, with Re/Mo ratios that vary by more than two orders of magnitude, a remarkably large range. Deposition of both elements begins simultaneously, and both come to finite aqueous concentration asymptotes together, neither being drawn down to analytical detection limits. To explain these aqueous-phase observations and to reconcile them with laboratory evidence, a previous coprecipitation hypothesis is further developed here. The proposed coprecipitate is a nanoscale sulfide, Fe(Mo,Re)S4 that transforms irreversibly by internal electron transfer to a product represented as Fe(Mo,Re)(S2)S2. Irreversibility preserves information about redox conditions at the time of sedimentation unless sedimentary rocks later become subjected to oxidation or thermal maturation. Compelling support for this mechanism comes from the continuously euxinic Black Sea. A Rayleigh fractionation process characterized by a partition coefficient of 0.38 explains Re/Mo ratios in both its water column and its sediments. On the other hand, in sediments where overlying waters range from oxic to intermittently euxinic, and where Re and Mo deposition occurs only beneath the sediment–water interface, the observed >100-fold range of Re/Mo ratios is too large to be explained solely by Rayleigh fractionation. Instead, it is attributed to modification of pore waters by decomposition of unstable precursory phases. Low solid phase Re/Mo ratios are produced by pore waters modified by dissolution of Mo-rich, Mn,Fe oxyhydroxides; high ratios reflect dissolution of the so-far uncharacterized Re-rich particles that are known to create dissolved Re anomalies in shallow pore waters. Rhenium often follows iodine in biology, suggesting that the Re-rich particles could be biogenic and might participate in the marine iodine cycle. A significant correlation between particulate Re/Mo ratios and biogenic CaCO3 in the Cariaco Basin water column suggests that some of these Re-rich particles could be unstable biocalcification precursors like vaterite and amorphous CaCO3. Compared to δ98Mo, another redox proxy, Re/Mo ratios provide more nuanced redox information, especially under conditions that fall between oxic and sulfidic extremes. Thus Re/Mo ratios are potentially advantageous redox proxies that so far have been underutilized.

Can We Better Constrain the Timing of GNAIW/UNADW Variability in the Western Equatorial Atlantic and Its Relationship to Climate Change During the Last Deglaciation?

AbstractWe have revisited the well‐trod VM28‐122 core retrieved from the deep Colombian Basin, which includes sediments that reflect modern Upper North Atlantic Deep Water and extends through the last deglaciation into the last glacial period when the site was bathed in Glacial North Atlantic Intermediate Water. Here, we leverage the nearby Cariaco Basin's surface water radiocarbon reconstruction (reservoir age, and ΔR) on the IntCal20 timescale to recast the period of the last deglaciation with a newly constrained age model. Based on the revised age model, we observe that the multimillennial decrease in benthic δ13C and B/Ca (which record δ13C of dissolved inorganic carbon and Δ[CO3−2], respectively) began at 18,100 ± 240 (95% CI) calibrated years BP, synchronous with Termination 1, as identified by changes in the Antarctic Ice Sheet composite and by the onset of rapid glacier recession in the Southern Hemisphere (Denton et al., 2010, https://doi.org/10.1126/science.1184119; Denton et al., 2021, https://10.1016/j.quascirev.2020.106771). The beginning of the decrease in benthic δ18O is concurrent with the changes in carbon chemistry or at most, a few hundred years later. It is no later than 17,700 ± 300 (95% CI) yrs BP in our record, at the putative start of Heinrich Stadial 1. With sufficient data density (more than 2–3 control points per kyr) and an independent record of past surface water radiocarbon variations, it is possible to achieve late glacial and deglacial chronologies with fidelities similar to those of ice cores. Doing so in more oceanographic locations should shed light more broadly on the mechanisms instrumental to abrupt climate change.

Ground-truthing the pyrite trace element proxy in modern euxinic settings

Abstract Pyrite trace element (TE) chemistry is now widely employed in studies of past ocean chemistry. Thus far the main proof of concept has been correlation between large data sets of pyrite and bulk analyses emphasizing redox sensitive TE data from ancient samples spanning geologic time. In contrast, pyrite TE data from modern settings are very limited. The sparse available data are averages from samples from the Cariaco Basin without stratigraphic resolution and from estuarine sediments. To fill this gap, we present TE data (Co, Ni, Cu, Zn, Mo, Ag, Pb, Bi) from the two largest euxinic basins on Earth today, locations where the majority of the pyrite formed within the water column, the Black Sea and Cariaco Basin. These locations have different water column TE contents due to their relative degrees of restriction from the open ocean, thus providing an ideal test of the relationship between pyrite precipitated under euxinic conditions from basins with different degrees of basin restriction and dissolved TE concentration. At each site we observed that down-core trends for pyrite increase before reaching relatively steady values for most TE. This observation suggests that instead of all the TE being sourced directly from the water column, some are incorporated from the sediments, presumably desorbing from detrital materials. However, since much of the adsorbed TE is adsorbed from the overlying water, the pyrite chemistry still seems to reflect the water chemistry at or near the surface. Indeed, for Mo, there is less variation in pyrite than in bulk sediment. Additionally, we found that pyrite formed during diagenesis due to sulfide diffusion into iron-rich muds revealed low-TE contents, except for siderophile elements likely to have been adsorbed onto Fe (hydr)oxides, highlighting the risk of potential false negatives from pyrite formed under these conditions. This relationship highlights the need for detailed understanding of the full context, including the use of complementary geochemical data such as sulfur isotope trends, in efforts to use pyrite TE to interpret conditions in the global ocean.

The microbiome of the Black Sea water column analyzed by shotgun and genome centric metagenomics

BackgroundThe Black Sea is the largest brackish water body in the world, although it is connected to the Mediterranean Sea and presents an upper water layer similar to some regions of the former, albeit with lower salinity and temperature. Despite its well-known hydrology and physicochemical features, this enormous water mass remains poorly studied at the microbial genomics level.ResultsWe have sampled its different water masses and analyzed the microbiome by shotgun and genome-resolved metagenomics, generating a large number of metagenome-assembled genomes (MAGs) from them. We found various similarities with previously described Black Sea metagenomic datasets, that show remarkable stability in its microbiome. Our datasets are also comparable to other marine anoxic water columns like the Cariaco Basin. The oxic zone resembles to standard marine (e.g. Mediterranean) photic zones, with Cyanobacteria (Synechococcus but a conspicuously absent Prochlorococcus), and photoheterotrophs domination (largely again with marine relatives). The chemocline presents very different characteristics from the oxic surface with many examples of chemolithotrophic metabolism (Thioglobus) and facultatively anaerobic microbes. The euxinic anaerobic zone presents, as expected, features in common with the bottom of meromictic lakes with a massive dominance of sulfate reduction as energy-generating metabolism, a few (but detectable) methanogenesis marker genes, and a large number of “dark matter” streamlined genomes of largely unpredictable ecology.ConclusionsThe Black Sea oxic zone presents many similarities to the global ocean while the redoxcline and euxinic water masses have similarities to other similar aquatic environments of marine (Cariaco Basin or other Black Sea regions) or freshwater (meromictic monimolimnion strata) origin. The MAG collection represents very well the different types of metabolisms expected in this kind of environment. We are adding critical information about this unique and important ecosystem and its microbiome.

Millennial-Scale Environmental Variability in Late Quaternary Deep-Sea Sediments from the Demerara Rise, NE Coast of South America

We carried out a rock magnetic study of two deep-sea gravity cores from the Demerara Rise, NE South America. Our previous studies provided radiocarbon and paleomagnetic chronologies for these cores. This study presents detailed rock magnetic measurements on these cores in order to characterize the rock magnetic mineralogy and grain size as indicators of the overall clastic fraction. We measured the magnetic susceptibility, anhysteretic remanence, and isothermal remanence and demagnetized the remanences at several alternating field demagnetization levels. The magnetic intensities estimate the magnetic material concentration (and indirectly the overall clastic fraction) in the cores. Ratios of rock magnetic parameters indicate the relative grain size of the magnetic material (and indirectly the overall clastic grain size). Rock magnetic intensity parameters and rock magnetic ratios both vary systematically and synchronously over the last 30,000 years in both cores. There is a multi-millennial-scale cyclicity, with intervals of high magnetic intensity (high magnetic and clastic content) with low magnetic ratios (coarser magnetic and clastic grain size), alternating in sequence with intervals of low magnetic intensity with high magnetic ratios (finer grain size). There is also a higher-frequency millennial-scale variability in intensity superposed on the multi-millennial-scale variability. There are nine (A–I) multi-millennial-scale intervals in the cores. Intervals A, C, E, G, and I have high magnetic and clastic content with coarser overall magnetic and clastic grain size and are likely intervals of enhanced rainfall and runoff from the NE South American margin to the coastal ocean. In contrast, intervals B, D, F, and H have lower clastic flux with finer overall grain size, probably indicating lower continental rainfall and runoff. During the Holocene, high rainfall and runoff intervals can be related to cooler times and low rainfall and runoff to warmer times. The opposite pattern existed during the Pleistocene, with higher rainfall and runoff during interstadial conditions and lower rainfall and runoff during stadial conditions. We noted a similar pattern of Pleistocene multi-millennial-scale variability in a transect of deep-sea sediment cores along the NE Brazilian margin, from the Cariaco Basin (~10 N) to the NE Brazilian margin (~1° N–4° S). However the NW part of this transect (Cariaco Basin, Demerara Rise, Amazon Fan) has an out-of-phase relationship with the SE part of the transect (NE Brazilian margin) between warm–cold and wet–dry conditions. One possible cause of the high–low rainfall and runoff patterns might be oscillation of the Intertropical Convergence Zone (ITCZ), with higher rainfall and runoff associated with a more southerly average position of the ITCZ and lower rainfall and runoff associated with a more northerly average position of the ITCZ.

Assessing the contribution of the La Luna Sea to the global sink of organic carbon during the Cenomanian-Turonian Oceanic Anoxic Event 2 (OAE2)

Epicontinental seas were important features of the paleogeographic landscape during the Cretaceous; however, the role they played as sinks of organic carbon is still poorly understood. The La Luna Formation (Albian-Coniacian) is a series of organic-rich limestones deposited in northwestern South America on an epicontinental sea (the La Luna Sea). This formation offers a forty-million-year continuous record of environmental change characterized by periods of oceanic anoxia in an epicontinental sea. The La Luna Sea, may have played an important role –although so far unexplored– in carbon cycling through the ocean during the Cretaceous, specifically during short-term, global-scale disruptions in the carbon cycle known as oceanic anoxic events (OAEs). To evaluate the role of the La Luna Sea in global carbon cycle perturbations, we conducted a detailed lithological and chemostratigraphic analysis of two stratigraphic sections from the Upper Magdalena Basin of Colombia, both of which encompass the Oceanic Anoxic Event 2 (OAE2) at the Cenomanian–Turonian boundary. Compared to deposits in the modern ocean, the La Luna Formation has high total organic carbon (TOC) before, during, and after OAE2. Foraminifera and nannoplankton assemblages also imply a stressed upper water column during OAE2. Geochemical and paleontological evidence suggests that the sediment-water interface was anoxic across the late Cenomanian and early Turonian. Strata deposited just after OAE2, however, contain inoceramid bivalves, consistent with short-lived re‑oxygenation of the benthic layer. Estimates of primary productivity, the covariation of Mo and U enrichment factors, and relations between Cd, Mo, Co, and Mn also reveal that the La Luna Sea was biogeochemically similar to the modern Cariaco Basin. Despite high concentrations of organic carbon found in the La Luna Formation, mass-accumulation rates of organic carbon are low, a finding that can be explained by a reduction in the accumulation rate of sediments caused by the peak of sea-level transgression that took place at the Cenomanian–Turonian transition. Based on the areal extent of the La Luna Sea and mass-accumulation rates of organic carbon, 1.7 Eg of C were removed from the ocean over 500 ky and deposited in the La Luna Sea. Interestingly, although the La Luna Sea was one-third the size of the Western Interior Seaway (WIS), the amount of organic carbon buried in the WIS during OAE2 was similar (1.4 Eg of C). In these two epicontinental seas, 3.1 Eg of C were removed from the ocean during OAE2, accounting only for 3.4% of the total C needed to cause a perturbation of the carbon cycle similar to that observed during OAE2. The low amount of organic carbon buried in the La Luna Sea and the WIS suggests that neither of these inland seas were responsible for the efficient removal of organic carbon from the ocean during OAE2. This conclusion challenges the explanation that epicontinental seas were major sinks of organic carbon—and therefore they did not play a significant role in the carbon cycle during the Mesozoic OAEs and other disruptions of the carbon cycle in Earth's history.

Using the Stable Isotopic Composition of Heliconoides inflatus Pteropod Shells to Determine Calcification Depth in the Cariaco Basin

Pteropods have been hailed as the “canary in the coal mine” for ocean acidification, however, questions remain about their life history, habitat, and the environmental parameters that the isotopic composition of their shells reflect. In order to use pteropods as recorders of ocean chemistry, it is first necessary to understand where they calcify and how this may change through the year, whether this signal is affected by dissolution, and if shells are retained in the subfossil, and eventually fossil, record. Here we create the first annual record of the stable isotopic composition of shells of the pteropodHeliconoides inflatusin the Cariaco Basin, Venezuela utilizing samples and data from the CARIACO time series. Sixty-fourH. inflatusspecimens from 17 sediment trap samples between November 1996 and April 1998, and 22 specimens from the late Holocene-aged CAR2000-MC-2 core were analyzed for shell condition (an assessment of the amount of dissolution that a shell has experienced), size, and carbon and oxygen isotopic composition. Carbon isotopic measurements of juveniles (< 1mm) were more variable than those in adults (>1 mm), suggesting juvenile pteropods likely have a higher growth rate, and therefore different metabolic vital effects, and a more varied diet than adult pteropods.H. inflatuswas found to have an apparent calcification depth of 51.2 ± 34.0 m, suggesting they calcify at the shallowest part of their diurnal migration in the mixed layer (10–35 m in the Cariaco Basin).H. inflatusshell calcification will therefore only be impacted by changes in water chemistry at mixed layer depths. The shell condition did not impact the stable isotopic composition of the shells in either the sediment trap or core sample, suggesting the potential for using the isotopic composition of pteropod shells as oceanographic proxies when they are preserved. Comparisons between sediment trap and core sample show a 0.5°C warming that is marginally significant and a significant 0.45‰ decrease in δ13C between the late Holocene and the late 1990's. These measurements reflect changes in oceanic conditions linked to anthropogenic fossil fuel emissions known as the Suess effect, and lay the groundwork for establishing pteropods as paleoceanographic proxies in the future.