Polyester microfiber impacts on coastal sediment organic matter consumption.

As plastic pollution continues to accumulate at the seafloor, concerns around benthic ecosystem functionality heightens. This research demonstrates the systematic effects of polyester microfibers on seafloor organic matter consumption rates, an important benthic ecosystem function connected to multiple reactions and processes. We used a field-based assay to measure the loss of organic matter, both with and without polyester microfiber contamination. We identified sediment organic matter content, mud content, and mean grain size as the main drivers of organic matter consumption, however, polyester microfiber contamination decoupled ecosystem relationships and altered observed organic matter cycling dynamics. Organic matter consumption rates varied across horizontal and vertical spaces, highlighting that consumption and associated plastic effects are dependent on environmental heterogeneity at both small (within sites) and larger (between sites) scales. Our results emphasize the important role habitat heterogeneity plays in seafloor organic matter consumption and the associated effects of plastic pollution on ecosystem function.

Effects of seasonal deposition-erosion cycle on sedimentary organic carbon remineralization and oxygen consumption in a large-river delta-front estuary.

Seasonal sediment deposition-erosion events are dominant drivers of particle-solute dynamics in large-river delta-front estuaries (LDEs), but their influence on elemental cycles is not yet fully understood. To better constrain the role of deposition-erosion events on elemental cycling in LDEs, benthic fluxes of dissolved inorganic carbon (DIC), oxygen, and pore-water solute profiles were measured over different seasons in the Changjiang LDE. Benthic DIC efflux (23.4 ± 6.0 mmol C m-2 d-1) was greater than oxygen influx (7.5 ± 2.0 mmol O2 m-2 d-1) in summer but less in winter (7.7 ± 1.2 mmol C m-2 d-1 and 10.1 ± 1.5 mmol O2 m-2 d-1, respectively). The additional oxygen consumption in sediments in winter was likely due to the oxidation of inorganic diagenetic reductive products (IDRP) (e.g., NH4+, Fe2+, and Mn2+) in deeper sediments exposed by erosion, which resulted in the development of an "oxygen debt". Sedimentary oxygen respiration accounted for at least 48 % of total oxygen consumption (oxygen consumption in both water column and sediment) in winter and was significantly greater than in summer (∼15 %); this highlighted the importance of winter sediment erosion in oxygen depletion. In addition to IDRP oxidation, the remineralization of resuspended sedimentary organic carbon in water column also contributed to the oxygen consumption. The global dataset on benthic DIC and oxygen fluxes provides evidence that the "oxygen debt" is likely to be widespread in LDEs, exerting a significant impact on global carbon and oxygen cycling.

The Global Turbidity Current Pump and Its Implications for Organic Carbon Cycling.

Submarine turbidity currents form the largest sediment accumulations on Earth, raising the question of their role in global carbon cycles. It was previously inferred that terrestrial organic carbon was primarily incinerated on shelves and that most turbidity current systems are presently inactive. Turbidity currents were thus not considered in global carbon cycles, and the burial efficiency of global terrestrial organic carbon was considered low to moderate (∼10-44%). However, recent work has shown that burial of terrestrial organic carbon by turbidity currents is highly efficient (>60-100%) in a range of settings and that flows occur more frequently than once thought, although they were far more active at sea-level lowstands. This leads to revised global estimates for mass flux (∼62-90 Mt C/year) and burial efficiency (∼31-45%) of terrestrial organic carbon in marine sediments. Greatly increased burial fluxes during sea-level lowstands are also likely underestimated; thus, organic carbon cycling by turbidity currents could play a role in long-term changes in atmospheric CO2 and climate.

Size-fractionated distribution of glycerol dialkyl glycerol tetraether core lipids in surface sediments of a large-river delta-front estuary.

Glycerol dialkyl glycerol tetraether core lipids (GDGTs) are microbial biomarkers ubiquitously distributed in terrestrial and marine environments. Dispersal and fate of GDGTs in an estuary largely depends on sediment grain size, however, their size distribution patterns remain poorly understood. Here, surface sediments collected from the Changjiang Estuary were separated into <20, 20-32, 32-63, 63-125 and >125 µm fractions, and analyzed for GDGTs as well as total organic carbon (TOC), stable isotopic composition (δ13C) of TOC and lignin phenols, to investigate the size and spatial distributions of GDGTs and the particle size effects on GDGTs proxies in this large river delta-front estuary. The concentrations of isoprenoidal GDGTs (isoGDGTs) were higher in the finest fractions and in off-estuary sites. On the contrary, branched GDGTs (brGDGTs) were high not only in the finest fractions but in coarser fractions (>32 µm fractions), and thus at both near- and off-estuary sites. The branched and isoprenoid tetraether (BIT) index increased with increasing grain size, and decreased sharply from the estuary (~0.52) to the shelf (~0.16). BrGDGTs were positively correlated with crenarcheaol in both high and low BIT regions. The brGDGTIIIa/IIa ratios in all size fractions were <0.59, further indicating that the brGDGTs were mainly derived from terrestrial input with minimum in-situ production. Fractional TOC source assignments derived from the BIT index was significantly positively correlated with the fractions of terrestrial OC from a mixing model based on δ13C-TOC and lignin contents, indicating that BIT may track a broader pool of terrestrial OC than just soil OC. This work provides novel, yet preliminary insights into the size fractionated distribution characteristics of GDGTs and the applicability of BIT as a proxy for OC sources in estuarine sediments. More work is needed to further clarify the particle size effects on other GDGTs proxies in estuarine systems.

An Improved Framework for Estimating Organic Carbon Content of Mangrove Soils Using loss-on-ignition and Coastal Environmental Setting.

The use of loss on ignition (LOI) measurements of soil organic matter (SOM) to estimate soil organic carbon (OC) content is a decades-old practice. While there are limitations and uncertainties to this approach, it continues to be necessary for many coastal wetlands researchers and conservation practitioners without access to an elemental analyzer. Multiple measurement, reporting, and verification (MRV) standards recognize the need (and uncertainty) for using this method. However, no framework exists to explain the substantial differences among equations that relate SOM to OC; consequently, equation selection can be a haphazard process leading to widely divergent and inaccurate estimates. To address this lack of clarity, we used a dataset of 1,246 soil samples from 17 mangrove regions in North, Central, and South America, and calculated SOM to OC conversion equations for six unique types of coastal environmental setting. A framework is provided for understanding differences and selecting an equation based on a study region's SOM content and whether mineral sediments are primarily terrigenous or carbonate in origin. This approach identifies the positive dependence of conversion equation slopes on regional mean SOM content and indicates a distinction between carbonate settings with mean (± 1 S.E.) OC:SOM of 0.47 (0.002) and terrigenous settings with mean OC:SOM of 0.32 (0.018). This framework, focusing on unique coastal environmental settings, is a reminder of the global variability in mangrove soil OC content and encourages continued investigation of broadscale factors that contribute to soil formation and change in blue carbon settings. Supplementary Information: The online version contains supplementary material available at 10.1007/s13157-023-01698-z.

Global fjords as transitory reservoirs of labile organic carbon modulated by organo-mineral interactions.

The global carbon cycle is strongly modulated by organic carbon (OC) sequestration and decomposition. Whereas OC sequestration is relatively well constrained, there are few quantitative estimates of its susceptibility to decomposition. Fjords are hot spots of sedimentation and OC sequestration in marine sediments. Here, we adopt fjords as model systems to investigate the reactivity of sedimentary OC by assessing the distribution of the activation energy required to break OC bonds. Our results reveal that OC in fjord sediments is more thermally labile than that in global sediments, which is governed by its unique provenance and organo-mineral interactions. We estimate that 61 ± 16% of the sedimentary OC in fjords is degradable. Once this OC is remobilized and remineralized during glacial maxima, the resulting metabolic CO2 could counterbalance up to 50 ppm of the atmospheric CO2 decrease during glacial times, making fjords critical actors in dampening glacial-interglacial climate fluctuations through negative carbon cycling loops.

A global assessment of the mixed layer in coastal sediments and implications for carbon storage.

The sediment-water interface in the coastal ocean is a highly dynamic zone controlling biogeochemical fluxes of greenhouse gases, nutrients, and metals. Processes in the sediment mixed layer (SML) control the transfer and reactivity of both particulate and dissolved matter in coastal interfaces. Here we map the global distribution of the coastal SML based on excess 210Pb (210Pbex) profiles and then use a neural network model to upscale these observations. We show that highly dynamic regions such as large estuaries have thicker SMLs than most oceanic sediments. Organic carbon preservation and SMLs are inversely related as mixing stimulates oxidation in sediments which enhances organic matter decomposition. Sites with SML thickness >60 cm usually have lower organic carbon accumulation rates (<50 g C m-2 yr-1) and total organic carbon/specific surface area ratios (<0.4 mg m-2). Our global scale observations reveal that reworking can accelerate organic matter degradation and reduce carbon storage in coastal sediments.

Increased levels of perfluorooctanesulfonic acid (PFOS) during Hurricane Dorian on the east coast of Florida.

Per- and polyfluoroalkyl substances (PFAS) are a class of synthetic chemicals commonly found in everyday consumer products and are an emerging concern due to their ubiquitous presence in ecosystems around the world. PFAS exposure, which often occurs through contaminated water, has been linked to several adverse health effects in humans and wildlife. PFAS can be transported in surface water and storm runoff in the nearshore environment. Episodic events, such as hurricanes, are projected to increase in frequency and intensity, and a critical unanswered question is: how do episodic events influence the concentrations and distributions of emerging contaminants, such as PFAS, in coastal systems? Here, we investigated the impact of the 2019 Hurricane Dorian on the Florida coast to assess how natural disasters, such as hurricanes, influence the fate and transport of PFAS in surface water. Water samples collected throughout the St. Augustine Intracoastal waterway before, during, and after the storm were analyzed and compared with baseline concentrations. Ultra-high-pressure liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) was used in the detection and quantification of 23 and 17 PFAS, respectively. Perfluorooctane sulfonic acid (PFOS) was the compound with the highest concentration across all sampling sites. Mean PFOS levels showed the highest increase of 177% during the hurricane and returned to baseline levels after two days. Our findings highlight the need for continued research focused on understanding how large storms near all coastlines can impact the transport of environmental pollutants, such as PFOS, that can have adverse effects on human and environmental health. Further monitoring of PFAS in coastal systems is necessary to identify potential PFAS hotspots, investigate the impacts of episodic events on PFAS transport, develop mitigation practices capable of reducing the risk of PFAS exposure.

Plastics in the Earth system.

Plastic contamination of the environment is a global problem whose magnitude justifies the consideration of plastics as emergent geomaterials with chemistries not previously seen in Earth's history. At the elemental level, plastics are predominantly carbon. The comparison of plastic stocks and fluxes to those of carbon reveals that the quantities of plastics present in some ecosystems rival the quantity of natural organic carbon and suggests that geochemists should now consider plastics in their analyses. Acknowledging plastics as geomaterials and adopting geochemical insights and methods can expedite our understanding of plastics in the Earth system. Plastics also can be used as global-scale tracers to advance Earth system science.

A call to evaluate Plastic's impacts on marine benthic ecosystem interaction networks.

Plastic pollution continues to seep into natural and pristine habitats. Emerging laboratory-based research has evoked concern regarding plastic's impact on ecosystem structure and function, the essence of the ecosystem services that supports our life, wellbeing, and economy. These impacts have yet to be observed in nature where complex ecosystem interaction networks are enveloped in environmental physical and chemical dynamics. Specifically, there is concern that environmental impacts of plastics reach beyond toxicity and into ecosystem processes such as primary production, respiration, carbon and nutrient cycling, filtration, bioturbation, and bioirrigation. Plastics are popularly regarded as recalcitrant carbon molecules, although they have not been fully assessed as such. We hypothesize that plastics can take on similar roles as natural recalcitrant carbon (i.e., lignin and humic substances) in carbon cycling and associated biogeochemistry. In this paper, we review the current knowledge of the impacts of plastic pollution on marine, benthic ecosystem function. We argue for research advancement through (1) employing field experiments, (2) evaluating ecological network disturbances by plastic, and (3) assessing the role of plastics (i.e., a carbon-based molecule) in carbon cycling at local and global scales.

Geochemical and Stable Fe Isotopic Analysis of Dissimilatory Microbial Iron Reduction in Chocolate Pots Hot Spring, Yellowstone National Park.

Chocolate Pots hot spring (CP) is an Fe-rich, circumneutral-pH geothermal spring in Yellowstone National Park. Relic hydrothermal systems have been identified on Mars, and modern hydrothermal environments such as CP are useful for gaining insight into potential pathways for generation of biosignatures of ancient microbial life on Earth and Mars. Fe isotope fractionation is recognized as a signature of dissimilatory microbial iron oxide reduction (DIR) in both the rock record and modern sedimentary environments. Previous studies in CP have demonstrated the presence of DIR in vent pool deposits and show aqueous-/solid-phase Fe isotope variations along the hot spring flow path that may be linked to this process. In this study, we examined the geochemistry and stable Fe isotopic composition of spring water and sediment core samples collected from the vent pool and along the flow path, with the goal of evaluating whether Fe isotopes can serve as a signature of past or present DIR activity. Bulk sediment Fe redox speciation confirmed that DIR is active within the hot spring vent pool sediments (but not in more distal deposits), and the observed Fe isotope fractionation between Fe(II) and Fe(III) is consistent with previous studies of DIR-driven Fe isotope fractionation. However, modeling of sediment Fe isotope distributions indicates that DIR does not produce a unique Fe isotopic signature of DIR in the vent pool environment. Because of rapid chemical and isotopic communication between the vent pool fluid and sediment, sorption of Fe(II) to Fe(III) oxides would produce an isotopic signature similar to DIR despite DIR-driven generation of large quantities of isotopically light solid-associated Fe(II). The possibility exists, however, for preservation of specific DIR-derived Fe(II) minerals such as siderite (which is present in the vent pool deposits), whose isotopic composition could serve as a long-term signature of DIR in relic hot spring environments.

Sea-level rise and the emergence of a keystone grazer alter the geomorphic evolution and ecology of southeast US salt marshes.

Keystone species have large ecological effects relative to their abundance and have been identified in many ecosystems. However, global change is pervasively altering environmental conditions, potentially elevating new species to keystone roles. Here, we reveal that a historically innocuous grazer-the marsh crab Sesarma reticulatum-is rapidly reshaping the geomorphic evolution and ecological organization of southeastern US salt marshes now burdened by rising sea levels. Our analyses indicate that sea-level rise in recent decades has widely outpaced marsh vertical accretion, increasing tidal submergence of marsh surfaces, particularly where creeks exhibit morphologies that are unable to efficiently drain adjacent marsh platforms. In these increasingly submerged areas, cordgrass decreases belowground root:rhizome ratios, causing substrate hardness to decrease to within the optimal range for Sesarma burrowing. Together, these bio-physical changes provoke Sesarma to aggregate in high-density grazing and burrowing fronts at the heads of tidal creeks (hereafter, creekheads). Aerial-image analyses reveal that resulting "Sesarma-grazed" creekheads increased in prevalence from 10 ± 2% to 29 ± 5% over the past <25 y and, by tripling creek-incision rates relative to nongrazed creekheads, have increased marsh-landscape drainage density by 8 to 35% across the region. Field experiments further demonstrate that Sesarma-grazed creekheads, through their removal of vegetation that otherwise obstructs predator access, enhance the vulnerability of macrobenthic invertebrates to predation and strongly reduce secondary production across adjacent marsh platforms. Thus, sea-level rise is creating conditions within which Sesarma functions as a keystone species that is driving dynamic, landscape-scale changes in salt-marsh geomorphic evolution, spatial organization, and species interactions.

Multiple biomarkers highlight the importance of water column processes in treatment wetland organic matter cycling.

A suite of biomarkers, including amino acids, pigments, and lignin phenols coupled with high resolution mass spectrometry were used to evaluate differences in the sources and fate of organic matter (OM) in Everglades treatment wetlands as a model for OM cycling in shallow water wetlands. Five components of the system (water column particulate matter, vertical traps, flocculent material, periphyton, and surface soil) were assessed for OM transformations down-profile (i.e. water column to soil) and between treatment cells dominated by emergent aquatic vegetation (EAV) and submerged aquatic vegetation (SAV), with comparisons to reference sites within the remnant Everglades. We found that OM cycling is fundamentally different between EAV and SAV wetlands, and that SAV wetlands have some shared characteristics with similar habitats in the remnant Everglades. Other than locations densely populated by Typha spp., water column particulate organic C was predominantly derived from microbial/cryptomonad sources, rather than macroscopic sources (vascular plants and algal mats). Bacterial amino acid biomarkers were positively correlated with amino acid degradation indices and organic P (Po), respectively suggesting that microbial abundance is associated with less degraded OM, and that further investigation into relationships between microbial biomass and Po is warranted. Overall, this multi-biomarker approach can elucidate the relative degradation of OM pools, identify sources of OM, and highlight the importance of water column processes in shallow water wetlands.

Author Correction: The future of Blue Carbon science.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

The future of Blue Carbon science.

The term Blue Carbon (BC) was first coined a decade ago to describe the disproportionately large contribution of coastal vegetated ecosystems to global carbon sequestration. The role of BC in climate change mitigation and adaptation has now reached international prominence. To help prioritise future research, we assembled leading experts in the field to agree upon the top-ten pending questions in BC science. Understanding how climate change affects carbon accumulation in mature BC ecosystems and during their restoration was a high priority. Controversial questions included the role of carbonate and macroalgae in BC cycling, and the degree to which greenhouse gases are released following disturbance of BC ecosystems. Scientists seek improved precision of the extent of BC ecosystems; techniques to determine BC provenance; understanding of the factors that influence sequestration in BC ecosystems, with the corresponding value of BC; and the management actions that are effective in enhancing this value. Overall this overview provides a comprehensive road map for the coming decades on future research in BC science.

Moving beyond the van Krevelen Diagram: A New Stoichiometric Approach for Compound Classification in Organisms.

van Krevelen diagrams (O/C vs H/C ratios of elemental formulas) have been widely used in studies to obtain an estimation of the main compound categories present in environmental samples. However, the limits defining a specific compound category based solely on O/C and H/C ratios of elemental formulas have never been accurately listed or proposed to classify metabolites in biological samples. Furthermore, while O/C vs H/C ratios of elemental formulas can provide an overview of the compound categories, such classification is inefficient because of the large overlap among different compound categories along both axes. We propose a more accurate compound classification for biological samples analyzed by high-resolution mass spectrometry based on an assessment of the C/H/O/N/P stoichiometric ratios of over 130 000 elemental formulas of compounds classified in 6 main categories: lipids, peptides, amino sugars, carbohydrates, nucleotides, and phytochemical compounds (oxy-aromatic compounds). Our multidimensional stoichiometric compound classification (MSCC) constraints showed a highly accurate categorization of elemental formulas to the main compound categories in biological samples with over 98% of accuracy representing a substantial improvement over any classification based on the classic van Krevelen diagram. This method represents a signficant step forward in environmental research, especially ecological stoichiometry and eco-metabolomics studies, by providing a novel and robust tool to improve our understanding of the ecosystem structure and function through the chemical characterization of biological samples.

Grazing enhances belowground carbon allocation, microbial biomass, and soil carbon in a subtropical grassland.

Despite the large contribution of rangeland and pasture to global soil organic carbon (SOC) stocks, there is considerable uncertainty about the impact of large herbivore grazing on SOC, especially for understudied subtropical grazing lands. It is well known that root system inputs are the source of most grassland SOC, but the impact of grazing on partitioning of carbon allocation to root tissue production compared to fine root exudation is unclear. Given that different forms of root C have differing implications for SOC synthesis and decomposition, this represents a significant gap in knowledge. Root exudates should contribute to SOC primarily after microbial assimilation, and thus promote microbial contributions to SOC based on stabilization of microbial necromass, whereas root litter deposition contributes directly as plant-derived SOC following microbial decomposition. Here, we used in situ isotope pulse-chase methodology paired with plant and soil sampling to link plant carbon allocation patterns with SOC pools in replicated long-term grazing exclosures in subtropical pasture in Florida, USA. We quantified allocation of carbon to root tissue and measured root exudation across grazed and ungrazed plots and quantified lignin phenols to assess the relative contribution of microbial vs. plant products to total SOC. We found that grazing exclusion was associated with dramatically less overall belowground allocation, with lower root biomass, fine root exudates, and microbial biomass. Concurrently, grazed pasture contained greater total SOC, and a larger fraction of SOC that originated from plant tissue deposition, suggesting that higher root litter deposition under grazing promotes greater SOC. We conclude that grazing effects on SOC depend on root system biomass, a pattern that may generalize to other C4-dominated grasslands, especially in the subtropics. Improved understanding of ecological factors underlying root system biomass may be the key to forecasting SOC and optimizing grazing management to enhance SOC accumulation.

The spatial distribution of soil organic carbon in tidal wetland soils of the continental United States.

Tidal wetlands contain large reservoirs of carbon in their soils and can sequester carbon dioxide (CO2 ) at a greater rate per unit area than nearly any other ecosystem. The spatial distribution of this carbon influences climate and wetland policy. To assist with international accords such as the Paris Climate Agreement, national-level assessments such as the United States (U.S.) National Greenhouse Gas Inventory, and regional, state, local, and project-level evaluation of CO2 sequestration credits, we developed a geodatabase (CoBluCarb) and high-resolution maps of soil organic carbon (SOC) distribution by linking National Wetlands Inventory data with the U.S. Soil Survey Geographic Database. For over 600,000 wetlands, the total carbon stock and organic carbon density was calculated at 5-cm vertical resolution from 0 to 300 cm of depth. Across the continental United States, there are 1,153-1,359 Tg of SOC in the upper 0-100 cm of soils across a total of 24 945.9 km2 of tidal wetland area, twice as much carbon as the most recent national estimate. Approximately 75% of this carbon was found in estuarine emergent wetlands with freshwater tidal wetlands holding about 19%. The greatest pool of SOC was found within the Atchafalaya/Vermilion Bay complex in Louisiana, containing about 10% of the U.S. total. The average density across all tidal wetlands was 0.071 g cm-3 across 0-15 cm, 0.055 g cm-3 across 0-100 cm, and 0.040 g cm-3 at the 100 cm depth. There is inherent variability between and within individual wetlands; however, we conclude that it is possible to use standardized values at a range of 0-100 cm of the soil profile, to provide first-order quantification and to evaluate future changes in carbon stocks in response to environmental perturbations. This Tier 2-oriented carbon stock assessment provides a scientific method that can be copied by other nations in support of international requirements.

Composition and depth distribution of hydrocarbons in Barataria Bay marsh sediments after the Deepwater Horizon oil spill.

In 2010, an estimate 4.1 million barrels of oil were accidentally released into the Gulf of Mexico (GoM) during the Deepwater Horizon (DWH) Oil Spill. One and a half years after this incident, a set of subtidal and intertidal marsh sediment cores were collected from five stations in Barataria Bay, Louisiana, USA, and analyzed to determine the spatial and vertical distributions and source of hydrocarbon residues based on their chemical composition. An archived core, collected before the DWH oil spill from the same area, was also analyzed to assess the pre-spill hydrocarbon distribution in the area. Analyses of aliphatic hydrocarbons, polycyclic aromatic hydrocarbons (PAHs) and stable carbon isotope showed that the distribution of petroleum hydrocarbons in Barataria Bay was patchy and limited in areal extent. Significant TPH and ΣPAH concentrations (77,399 µg/g and 219,065 ng/g, respectively) were detected in the surface sediments of one core (i.e., core A) to a depth of 9 cm. Based on a sedimentation rate of 0.39 cm yr(-1), determined using (137)Cs, the presence of anthropogenic hydrocarbons in these sediment core deposited ca. 50 to 60 years ago. The historical background hydrocarbon concentrations increased significantly at the sediment surface and can be attributed to recent inputs. Although the oil present in the bay's sediments has undergone moderate weathering, biomarker analyses performed on core A samples likely indicated the presence of hydrocarbons from the DWH oil spill. The effects of oiling events on Barataria Bay and other marsh ecosystems in this region remain uncertain, as oil undergoes weathering changes over time.