Biogeochemical Processes Research Articles

High resolution concentration-discharge relationships in managed watersheds: a 30+ year analysis

Concentration-discharge (C-Q) relationships provide insight into solute transport and biogeochemical processes for watersheds. A 30+ year, high-resolution dataset from the North Appalachian Experimental Watershed (NAEW) offers an unparalleled opportunity to explore land use and land management impacts on C-Q relationships for small watersheds of varying land management histories (agricultural to forested). The NAEW was among the few hydrologic research sites where storm event runoff was sampled using proportional sampling. This method captures the concentration-discharge behavior associated with land use more effectively than instantaneous sampling, which favors rising limb or falling limb dynamics. In this study, we explore C-Q relationships by investigating baseflow and storm event flow across their total behavior. We also build a systems-understanding by comparing chemostatic behavior to soil geochemistry and land use history. Highly managed agricultural watersheds with no associated stream baseflow demonstrate near-chemostatic behavior for most solutes, while mixed use and forested watersheds with associated streams are more mutable depending on whether primary sources of water were groundwater or surface water. Using this unique high-resolution dataset, we show that concentration-discharge relationships are influenced by soil and baseflow geochemistry, pore fluid concentration, and land type/land use legacy effects.

Light attenuation parameterization in a highly turbid mega estuary and its impact on the coastal planktonic ecosystem

Light is essential for phytoplankton photosynthesis and many other biogeochemical processes in the aquatic system. However, light regimes vary greatly in the estuaries and coasts due to the optical complexity of the Case-2 waters. In this study, observed vertical profiles of photosynthetically active radiation (PAR; 400-700 nm) in a highly turbid mega estuary, the Changjiang (Yangtze River) Estuary, are used to quantify the effects of sedimentary and biogeochemical components on PAR attenuation in the water column and associated ecological impacts. The in-situ data suggest suspended sediment plays the most crucial role in light diffuse attenuation coefficient (Kd) distribution, followed by salinity (i.e., an index for colored dissolved organic matter) and phytoplankton chlorophyll-a. A new parameterization of Kd, based on suspended sediment, chlorophyll-a concentration, and salinity, is fitted using multiple linear regression. The previous and new Kd parameterizations are further applied to a coupled hydrodynamics-sediment-ecosystem model to simulate spring phytoplankton blooms. Comparative model runs reveal that the new Kd parameterization resulted in a better representation of the spring bloom patterns in magnitude, horizontal distribution, and vertical thickness of the high chlorophyll-a band offshore the turbidity maximum zone during the spring bloom. In summary, accurate representations of underwater light fields in the optically complex Case-2 water are critical in understanding biophysical processes that control planktonic ecosystem dynamics in the estuaries and coastal seas.

Satellite remote sensing reveals the footprint of biodiversity on multiple ecosystem functions across the NEON eddy covariance network

Abstract Biodiversity relates to ecosystem functioning by modulating biogeochemical cycles of carbon, water, energy, and nutrients within and between multiple biotic and abiotic components of the ecosystems. However, large-scale, systematic measurements of plant biodiversity are still lacking, and the effects of biodiversity on measured biogeochemical processes are understudied. Here, we combined alpha (α) and beta (β) taxonomic measurements, spectral diversity from satellite observations, structural properties of the vegetation, and climatic drivers to assess the effect of biodiversity on ecosystem functional properties. Ecosystem functional properties were computed from eddy-covariance fluxes at 44 sites of the National Ecological Observatory Network. Based on the spectral variation hypothesis, we used the near-infrared reflectance of vegetation (NIRv) derived from Sentinel-2 satellite imagery to compute Rao’s quadratic entropy (Rao Q), a distance metric related to spatial heterogeneity. Using an automatic model averaging technique, we found that biodiversity proxies hold substantial explanatory power when predicting several ecosystem functions related to carbon and water exchange. In particular, NIRv-based Rao Q (RaoQNIRv) reflected positive biodiversity effects on productivity, as expected from the literature. In contrast, traditional taxonomic α-diversity indices were generally not selected as relevant predictors of the ecosystem functional properties. Yet, β-diversity strongly contributed to the prediction of carbon use efficiency, surface conductance, and water use efficiency. We also found that the RaoQNIRv is less affected by issues of saturation and bare soil contribution compared to RaoQNDVI. We show that spectral heterogeneity based on remotely sensed NIRv holds the potential for globally characterizing the biodiversity-ecosystem functioning relationship (BEF). While systematic measurements of taxonomic diversity co-located at biogeochemical measurement stations could reduce the uncertainty surrounding the BEF relationship at whole-ecosystem scale, remotely- sensed metrics characterizing important functional and structural diversity aspects of the landscape will be crucial for continuous spatiotemporal monitoring of biodiversity with relevant implications for ecosystem services to humankind.

Geoenvironmental and geophysical methods applied to identify natural attenuation process on a complex hydrogeological environment contaminated by hydrocarbons

Environmental contamination found in urban areas generally has a chemical composition that favors the generation of a variety of physical, chemical and biological processes that differ from natural soil parameters. Thus, understanding natural attenuation processes in tropical environments is still a challenge, as is understanding how biogeochemical processes can influence and modify natural soil characteristics. The study aimed to apply methods that are not commonly used in investigations of contaminated areas, in order to assess the applicability of non-invasive methodology for detailed stratigraphic characterization and biogeochemical changes resulting from contamination by hydrocarbons in a complex hydrogeological environment site. To date, few studies have presented results obtained using non-invasive techniques to understand biochemical processes. The research was based on the interpretation of results obtained by high-resolution physical environment characterization techniques (such as gamma geophysical profiling and electrical conductivity surveys) and chemical analysis of groundwater. The data was interpreted to obtain a detailed characterization of the study area and evidence of the occurrence of natural attenuation of creosote contamination. The results indicated that the combination of geoenvironmental and geophysical methods is an interesting alternative for obtaining data and understanding the mineralogical and stratigraphic variation of the contaminated area. The physical parameters variations obtained by the methods suggested the presence of local geochemical alterations resulting from natural processes of attenuation of contamination by aliphatic and aromatic hydrocarbons in a tropical environment. The natural attenuation processes were confirmed through groundwater samples, biological analysis and metagenomic classification.

Relationships between abiotic factors, foliage chemistry and herbivory in a tropical montane ecosystem.

Herbivore-plant interactions are fundamental processes shaping ecosystems, yet their study is challenged by their complex connections within broader ecosystem processes, requiring a nuanced understanding of ecosystem dynamics. This study investigated the relationship between nutrient availability and insect herbivory in the Australian Wet Tropics. Our objectives were threefold. Firstly, to understand what factors influence nutrient availability for plants and herbivores across the landscape; secondly, to investigate how trees of different species respond to nutrient availability; and thirdly, to unravel how the relationships between resources and plant chemistry affect herbivory. We established a network of 25 study sites covering important abiotic gradients, including temperature, precipitation, and geology. Employing a hierarchical modelling approach, we assessed the influence of climate and geology on resource availability for plants, primarily in the form of soil nutrients. Then, we explored the influence of the above factors on the interaction between herbivory and foliage chemistry across three widespread rainforest tree species, comparing how these relationships emerged across genera. Our findings suggest an overarching influence of climate and geology over soil chemistry, foliar nitrogen, and insect herbivory, both directly and indirectly. However, individual constituents of soil fertility showed equivocal influences on spatial patterns of foliage chemistry once site geological origin was accounted for, suggesting a questionable relationship between individualsoil nutrients and foliar composition. We have demonstrated that herbivore-plant interactions are complex dynamics regulated by an intricate web of relationships spanning different biogeochemical processes. While our results provide some support to the notion that herbivory is affected by resource availability, different species growing under the same conditions can show differing responses to the same resources, highlighting the importance of identifying specific limiting factors rather than simpler proxies of resource availability.

The role of dissolved organic carbon in Great Smoky Mountains National Park streams impacted by long-term acid deposition.

Following reductions in acid deposition in the Great Smoky Mountains National Park (GRSM) since the 2000s, many streams remain acidic and the role of organic acids (OA-) remains unknown due to limited OA- data. This study investigated dissolved organic carbon (DOC) concentrations as a surrogate for OA- across GRSM and its relationships with watershed characteristics, seasons, flow, and stream chemistry. Baseflow water samples were collected from seven watersheds for 2years and stormflow samples from three watersheds for 1year. During baseflow, DOC concentrations ranged from < 0.04 to 2.29mg L-1 with watershed medians between 0.61 and 1.00mg L-1. Stormflow DOC concentrations ranged from 1.36 to 5.66mg L-1. During the summer, median DOC concentrations were about twice that of the other three seasons. Stream DOC concentrations decreased with increasing elevation during baseflow but increased with increasing elevation during stormflow. Considering high elevations historically received greater acid deposition, this gradient between baseflow and stormflow suggests higher elevation streams are more impacted by OA-. Based on an OA-/DOC acidity model, it was estimated that during baseflow OA- was a minor contributor to stream acidity, in the order of 5.3 μeq L-1, however stormflow OA- was estimated at 52.5 μeq L-1, contributing to nearly half of stream acidity. Baseflow DOC was significantly correlated with pH and Ca2+, suggesting stream acidification/recovery is governed by base cations and Ca2+ availability. Furthermore, this study provides essential data for future research to evaluate stream DOC trends during acidification recovery and changes in biogeochemical processes.

Bio-optical variability of particulate matter in the Southern Ocean

The composition and size distribution of particles in the ocean control their optical (scattering and absorption) properties, as well as a range of biogeochemical and ecological processes. Therefore, they provide important information about the pelagic ocean ecosystem’s structure and functioning, which can be used to assess primary production, particle sinking, and carbon sequestration. Due to its harsh environment and remoteness, the particulate bio-optical properties of the Southern Ocean (SO) remain poorly observed and understood. Here, we combined field measurements from hydrographic casts from two research voyages and from autonomous profiling floats (BGC-Argo) to examine particulate bio-optical properties and relationships among several ecologically and optically important variables, namely the phytoplankton chlorophyll a concentration (Chl), the particulate absorption coefficient (ap), the particulate backscattering coefficient (bbp), and the particulate organic carbon (POC) concentration. In the clearest waters of the SO (Chl &amp;lt; 0.2 mg m−3), we found a significant contribution to absorption by non-algal particles (NAP) at 442 nm, which was up to 10 times greater than the absorption by phytoplankton. This makes the particulate bio-optical properties there remarkably different from typical oceanic case 1 water. A matchup analysis confirms the impact of this larger NAP absorption on the retrieval of Chl from satellite ocean colour observations. For waters with Chl &amp;gt; 0.2 mg m−3, no significant differences are observed between the SO and temperate waters. Our findings also demonstrate consistency in predicting phytoplankton carbon from either Chl or bbp, suggesting that both methods are applicable in the SO.

Near-surface particulate backscattering observations with bio-optical Lagrangian drifters

Abstract Particulate matter concentration is an essential ocean variable (EOV) useful for understanding biogeochemical processes, improving ocean productivity estimates, and constraining coupled physical and biogeochemical numerical models. While direct observations of this parameter are difficult to obtain, the optical backscattering coefficient of marine particles (bbp) can be used as a reliable proxy. However, most in-situ multi-spectral bbp measurements are ship-borne or obtained from moored systems, thus with a limited spatial and temporal coverage. Utilizing Surface Velocity Programme (SVP) drifting buoys with self-contained backscatter sensors designed for extended deployment periods offers a promising solution for collecting data in challenging marine environments. In this study, we presented for the first time the integration of a commercially available, high-frequency and multispectral optical backscatter sensor into an SVP drifter, the so-called BO-SVP drifter designed to collect bbp measurements near the ocean surface. bbp measurements obtained by the BO-SVP drifter were reliable over a wide range of environmental conditions, showing a good agreement with independent datasets (relative bias &lt; 10%; relative standard deviation &lt; 36%). The BO-SVP drifter captures the satellite sub- and pixel scale variability by combining the Lagrangian approach and a high frequency sampling. This configuration enables the acquisition of measurements across numerous pixels in a single day, enhancing validation activities for ongoing and future satellite products and the quantification of associated uncertainties. The measurements acquired by these platforms can offer valuable insights into particle distribution at fine spatial scales, daily variability, and its relationship with water masses type and ocean dynamics.

Rubber-Based Agroforestry Ecosystems Enhance Soil Enzyme Activity but Exacerbate Microbial Nutrient Limitations

Agroforestry ecosystems are an efficient strategy for enhancing soil nutrient conditions and sustainable agricultural development. Soil extracellular enzymes (EEAs) are important drivers of biogeochemical processes. However, changes in EEAs and chemometrics in rubber-based agroforestry systems and their mechanisms of action are still not fully understood. Distribution of EEAs, enzymatic stoichiometry, and microbial nutrient limitation characteristics of rubber plantations under seven planting patterns (RM, rubber monoculture system; AOM, Hevea brasiliensis-Alpinia oxyphylla Miq; PAR, Hevea brasiliensis-Pandanus amaryllifolius Roxb; AKH, Hevea brasiliensis-Alpinia katsumadai Hayata; CAA, Hevea brasiliensis-Coffea Arabica; CCA, Hevea brasiliensis-Cinnamomum cassia (L.) D. Don, and TCA, Hevea brasiliensis-Theobroma Cacao) were analyzed to investigate the metabolic limitations of microorganisms and to identify the primary determinants that restrict nutrient limitation. Compared with rubber monoculture systems, agroforestry ecosystems show increased carbon (C)-acquiring enzyme (EEAC), nitrogen (N)-acquiring enzyme (EEAN), and phosphorus (P)-acquiring enzyme (EEAP) activities. The ecoenzymatic stoichiometry model demonstrated that all seven plantation patterns experienced C and N limitation. Compared to the rubber monoculture system, all agroforestry systems exacerbated the microbial limitations of C and N by reducing the vector angle and increasing vector length. P limitation was not detected in any plantation pattern. In agroforestry systems, progression from herbs to shrubs to trees through intercropping results in a reduction in soil microbial nutrient constraints. This is primarily because of the accumulation of litter and root biomass in tree-based systems, which enhances the soil nutrient content (e.g., soil organic carbon, total nitrogen, total phosphorus, and ammonium nitrogen) and accessibility. Conversely, as soil depth increased, microbial nutrient limitations tended to become more pronounced. Partial least squares path modelling (PLS-PM) indicated that nutrient ratios and soil total nutrient content were the most important factors influencing microbial C limitation (−0.46 and 0.40) and N limitation (−0.30 and −0.42). This study presented novel evidence regarding the constraints and drivers of soil microbial metabolism in rubber agroforestry systems. Considering the constraints of soil nutrients and microbial metabolism, intercropping of rubber trees with arboreal species is recommended over that of herbaceous species to better suit the soil environment of rubber plantation areas on Hainan Island.

From complex histories to cohesive data, a long-term agricultural dataset from the Morrow Plots

Long-term agricultural experiments are essential to measure the impacts of farming practices on crop yields, soil fertility and biogeochemical processes. However, these impacts often only manifest at decadal timescales, requiring committed and consistent data collection that exceeds the timelines for most experiments. The second oldest agricultural experiment in the world, the Morrow Plots at University of Illinois Urbana-Champaign (USA) has examined the impact of crop rotation and fertility treatments on maize (Zea mays L.) yields since 1876. While results have been widely reported since 1888, the publicly available longitudinal dataset described here now allows for validation of those past results, as well as new analyses and investigations. A multi-disciplinary team identified, collected, and aggregated multiple historical data sources into one comprehensive and FAIR (Findable, Accessible, Interoperable and Reusable) dataset that synthesizes yield data and management practices from 1888–2021. Updated versions of the dataset will continue to be published as additional data from this ongoing experiment are made available and as new historical data sources are uncovered.

Quantifying Bioluminescent Light Intensity in Breaking Waves Using Numerical Simulations

AbstractBreaking‐wave induced bioluminescence is a critical component of the biogeochemical process in the ocean. Understanding bioluminescence is important for monitoring red tides caused by bioluminescent microorganisms. In this study, we present the first numerical effort to quantify bioluminescent light intensity based on high‐fidelity direct numerical simulations of breaking waves and a quantitative bioluminescent model. The dynamics of breaking waves are extensively validated through comparison with existing studies. We find that the time‐averaged and Lagrangian‐averaged shear stress saturates as surface tension effects decrease and wave steepness increases. The spatial distribution of light intensity correlates with the wave crest overturning and air bubbles generated in plunging breakers. Furthermore, we observe that the maximum light intensity asymptotically approaches the emission of single cells, suggesting the potential for cost‐effective prediction models in future studies.

Insights into the plankton community seasonal variations in a finer scale of the Bohai Sea: biodiversity, trophic linkage, and biotic-abiotic interplay

Plankton play an indispensable role in the biogeochemical processes of marine ecosystem. However, unraveling the intricate interactions among biodiversity, trophic linkages, and biotic-abiotic interplay between phytoplankton-zooplankton remains a significant challenge. Here, we conducted field studies in the neritic area of the Bohai Sea during autumn 2023 and spring 2024 to explore seasonal variations of both phytoplankton and zooplankton through microscope. Our analysis revealed a sharp decline in trophic interactions across phytoplankton and zooplankton, with an abundance ratio in autumn 2023 being 5.5 times higher than in spring 2024. Additionally, dominant plankton species (Y ≥ 0.02) exhibited obvious differences between the two seasons, with higher species diversity observed in autumn. Moreover, each dominant zooplankton species had distinct preferred food items in both seasons, with Rhizosolenia setigera being favored by Noctiluca scintillans and Acartia pacifica. Furthermore, a multivariate biota-environment analysis indicated that each dominant plankton species had unique correlation with specific environmental parameters, highlighting how plankton can fully exploit external environmental conditions to survive in seasonal variations. Ultimately, our findings emphasize significant seasonal dynamics and provide a solid foundation for assessing the potential impacts of environmental changes on plankton in coastal marine realm.

Impact of humic acid on iron (oxyhydr)oxide transport in the presence of phosphate in saturated porous media

The subsurface flow of particular phosphate (P) has been recently regarded as a vital P transport path. Humic acid (HA) and P usually coexist in the natural environment and show a strong affinity to iron (Fe) (oxyhydr)oxide. The impact of P and HA on Fe (oxyhydr)oxide stability and transport is critical for evaluating the vertical transport of particular P and biogeochemical processes of Fe and P. This study investigated the effect of inorganic (IP) and organic (OP) phosphate on the stability and transport of ferrihydrite and goethite with HA through stability tests and column experiments. The adsorption of IP or OP on Fe (oxyhydr)oxide enhanced the stability and transport of Fe (oxyhydr)oxide, and OP showed a stronger enhancement than IP due to its stronger binding capacity and more negative surface. Compared with ferrihydrite, goethite had fewer adsorption sites for IP or OP and showed strong stability and transport at low IP (50 μM) or OP (10 μM) concentration. HA decreased IP or OP adsorption on Fe (oxyhydr)oxide through competition adsorption and electrostatic repulsion. The formed ternary phosphate-Fe (oxyhydr)oxide-HA complex showed a more negative surface and strong stability and transport. Our findings provide direct insights into the distinct role of IP and OP on Fe (oxyhydr)oxide stability and transport in the presence of HA, which provides essential information for evaluating the transport of particular Fe (oxyhydr)oxide-facilitated P in soils and subsurface environments rich in iron, phosphate, and dissolved carbon.

Assessment of bi-metal paleo-redox proxies in the Bakken Formation black shales, Williston Basin, North Dakota, USA

The influence of paleoredox conditions and water-mass restriction on trace metal (TM) accumulation in the lower (LBS) and upper black shales (UBS) of the Devonian–Mississippian (D–M) Bakken Formation was assessed utilizing V/Cr, V/(V + Ni), Ni/Co, U/Th, and enrichment factors (EF) for Mo vs. U. These assessments were compared to previously published estimates based on degree of pyritization (DOPT), sulfur‑iron and C–S–Fe relationships, and sedimentological data. Bi–metal ratios suggest >80 % of samples were deposited under suboxic to anoxic/euxinic conditions, whereas DOPT results suggest >60 % of samples were deposited under dysoxic (0.42–0.75 DOPT) bottom–water conditions. DOPT results are in good agreement with C–S–Fe and total S vs. Fe assessments of paleoredox conditions and sedimentological evidence. Good agreement is also seen between Mo/TOC and Mo EF/U EF that both suggest the Bakken shales were deposited under a relatively unrestricted water mass conditions resulting in consistent renewal of TMs into the basin. With TM resupply outpacing drawdown, the basin could support enhanced primary productivity as well as high concentrations of TMs. Trace metal concentrations for the Bakken Fm. show considerable range for Co (0–10,324 ppm), Mo (0–2018 ppm), Ni (0–1574 ppm), U (0–1604 ppm), and V (0–3194 ppm), and bi–metal ratios for the Bakken Fm. are up to 5× greater than those reported for other D–M black shale formations. Bivariate and principal component analysis indicate Mo, Ni, U, and V accumulation was more closely associated with the organic fraction than with reducing conditions, thus accumulation of organic matter during deposition and generation, migration, and biodegradation of hydrocarbons during diagenesis may have influenced the accumulation and distribution of these TMs. Furthermore, changes in biogeochemical processes during the D–M transition may have fundamentally altered marine chemistry, with the evolution of vascular land plants and enhanced terrestrial weathering leading to an increased influx of nutrients into marine waters resulting in the Annulata, Dasberg, and Hangenberg black shale events. Factors controlling TM accumulation during time of deposition (e.g., TM availability, bottom-water redox conditions, adsorption onto organic matter) and during diagenesis and catagenesis (e.g., alteration and break down of organic matter, movement of fluid hydrocarbons or other basinal fluids) likely contribute to the lack of agreement between redox proxies, and subsequently, the lack of applicability of bi–metal ratios in assessing bottom–water conditions for the Bakken shales. Therefore, it is suggested that these bi-metal redox proxies are not an effective means to describe bottom-water conditions during the deposition of the Bakken shales.

Differential Exudation Creates Biogeochemically Distinct Microenvironments during Rhizosphere Evolution.

Plant roots and associated microbes release a diverse range of functionally distinct exudates into the surrounding rhizosphere with direct impacts on soil carbon storage, nutrient availability, and contaminant dynamics. Yet mechanistic linkages between root exudation and emergent biogeochemical processes remain challenging to measure nondestructively, in real soil, over time. Here we used a novel combination of in situ microsensors with high-resolution mass spectrometry to measure, nondestructively, changing exudation and associated biogeochemical dynamics along single growing plant roots (Avena sativa). We found that metabolite and dissolved organic carbon (DOC) concentrations as well as microbial growth, redox potential (EH), and pH dynamics vary significantly among bulk soil, root tip, and more mature root zones. Surprisingly, the significant spike of rhizosphere DOC upon root tip emergence did not significantly correlate with any biogeochemical parameters. However, the presence of sugars significantly correlated with declines in EH following the arrival of the root tip, likely due to enhanced microbial oxygen demand. Similarly, the presence of organic acids significantly correlated to declines in pH upon root tip emergence. Overall, our in situ measurements highlight how different exudates released along growing roots create functionally distinct soil microenvironments that evolve over time.

Origin and preservation mechanisms of organic matter in carbonate concretions from Lower Cambrian black shales in South China

Carbonate concretions are widely used in paleoclimate, paleoenvironmental, and paleontological studies, and even in the study of potential life on Mars. These petrological, elemental, isotopic, and lipid biomarker signals in Meso-Cenozoic carbonate concretions (relatively low thermal maturity) can effectively preserve details of seawater conditions and benthic ecosystems during the deposition of their host sediments/rocks. However, such research on Precambrian-Cambrian carbonate concretions under highly mature conditions remains scarce, and the ability of these ancient carbonate concretions to retain their original biogenic information remains uncertain. To achieve that, this study examines two Cambrian carbonate concretions, using samples from the center, transition, and rim of each, and their adjacent host black shales from the Lower Cambrian Qiongzhusi Formation in the Yangtze Block, South China. Organic and inorganic geochemical analyses were combined to elucidate the origin and preservation process of organic matter (OM) in these ancient Cambrian carbonate concretions. The results show that the thermal maturity of OM within these concretions (1.8 % EqVRo) is relatively low compared to their adjacent host shales (2.9 % EqVRo). Hopanes and steranes are detectable in both free and calcite-occluded hydrocarbons within these concretions, with concentrations of individual compounds ranging from 0.001 to 0.800 μg/g TOC, whereas kerogen-bound hydrocarbons lack detectable biomarkers. The results indicate that the two Cambrian carbonate concretions were formed mainly within the iron reduction and bacterial sulfate reduction zones, extending to depths of 10 to 38 m below the sediment-water interface. The OM within these concretions mainly inherited the initial unaltered signature of OM from the Qiongzhusi host shale. The carbonate concretions protected the internal OM from further thermal and secondary (e.g., biodegradation) alteration processes and might also prevent the formation of the conventional macromolecular skeletal kerogen manifested by the absence of bound biomarkers. The biomarkers, in both free and occluded forms, in the Cambrian carbonate concretions still retained their original source information, providing valuable insights into ancient biogeochemical processes during sediment burial and ancient seawater chemistry during the early Cambrian.

Hydrogeochemical dynamics under saltwater-freshwater mixing in a mangrove wetland over tidal cycles

Seawater and groundwater interactions shape the hydrogeochemical profile of mangrove aquifers, revealing how biogeochemical processes adapt to saline-freshwater mixing via the fluctuating patterns of key hydrochemical indicators and primary biogenic elements. This study, utilizing a multi-level monitoring profile spanning the entire submerged aquifer within a mangrove wetland, analyzed the spatiotemporal dynamics of DO, ORP, pH, alkalinity and biogenic elements (C, N, S). The results revealed that among the basic hydrochemical parameters, total alkalinity showed the most stable spatiotemporal distribution and was positively correlated with salinity. pH demonstrated a significant negative correlation with salinity, whereas the correlations of ORP and DO with salinity were not substantial. The discharge of terrestrial freshwater into the mangrove wetland is marked by hydrogeochemical reactions favoring the input of Mg2+ and DIC, with potential iron mineral precipitation within the aquifer. Spatial distribution of biogenic elements in the groundwater showed no apparent pattern across sampling periods. DOC concentrations ranged from 0.3 to 1.3 mmol/L. Three components of dissolved organic matter were identified using three-dimensional fluorescence spectroscopy, with high molecular weight components (C1 + C2) accounting for an average of 47 to 73 %. Both elevated DOC concentrations and high molecular weight component ratios were primarily found in shallow layers of dense mangrove areas, decreasing with depth. Concentrations of ammonia, nitrite, and nitrate varied dynamically, reflecting active biochemical processes in the shallow to mid-layers of the aquifer. Furthermore, sulfate and sulfide concentrations, ranging from 0 to 26 mmol/L and 0.4 to 576.8 μmol/L, respectively, underscore the interplay of biogeochemical reactions, especially sulfate reduction. These findings highlight valuable insights into the complex biogeochemical processes within mangrove aquifers and provide theoretical guidance for protecting the ecological health of mangrove wetlands.

Toward a metabolic theory of catchments: Scaling of water and carbon fluxes with size

Allometric scaling relations are widely used to link biological processes to body size in nature. Several studies have shown that such scaling laws hold also for natural ecosystems, including individual trees and forests, riverine metabolism, and river network organization. However, the derivation of scaling laws for catchment-scale water and carbon fluxes has not been achieved so far. Here, we focus on scaling relations of catchment green metabolism, defined as the set of ecohydrological and biogeochemical processes through which vegetation assemblages in catchments maintain their structure and react to the surrounding environment. By revising existing plant size-density relationships and integrating them across large-scale domains, we show that the ecohydrological fluxes occurring at the catchment scale are invariant with respect to the above-ground vegetation biomass per unit area of the basin, while they scale linearly with catchment size. We thus demonstrate that the sublinear scaling of plant metabolism results in an isometric scaling at catchment and regional scales. Deviations from such predictions are further shown to collapse onto a common distribution, thus incorporating natural fluctuations due to resource limitations into a generalized scaling theory. Results from scaling arguments are supported by hyperresolution ecohydrological simulations and remote sensing observations.

Influence of Oxygen Exposure on Lignin Preservation during Sediment Lateral Transport in the Ocean: Insights from Molecular Dynamics Simulations.

Understanding the fate of terrestrial organic carbon (terrOC) preservation in the marine environments is critical for deciphering the biogeochemical processes associated with the global carbon cycle and the Earth's climate change. The mechanisms controlling terrOC preservation are not completely understood, while lateral oxygen exposure time (OET) is considered as a critical controlling factor. Here, we first utilized molecular dynamics simulations to investigate the structural properties of lignin under anoxic, suboxic, and oxic conditions for understanding the mechanisms of terrOC preservation during sediment lateral transport in the ocean. Our finding suggested that oxygen exposure was indispensable for terrOC degradation through influencing the structural stability and reactivity of lignin. Our simulated results showed that in suboxic environments, prolonged OET may enhance terrOC preservation. Our organic geochemical results suggested that terrOC preferably preserved in coarse silts (20-63 μm) than fine silts (<20 μm) in suboxic environments, largely due to hydrodynamics-driven prolonged OET in coarse sediments, which may efficiently reduce CO2 emissions. Overall, our study sheds new light on the mechanisms of lateral OETs on terrOC preservation in suboxic conditions and, from a unique molecular structural perspective, provides insights into the impact of prolonged OETs on terrOC oxidative degradation in the marine environment.

Spatial variability in residence time of Beryllium in the Indian Ocean

Residence time of an element in the ocean is a consequence of its chemical behaviour and the various biogeochemical processes governing its distribution, sources, and sinks. Precise estimation of the residence time of beryllium(Be) is necessary for its application as a tracer for understanding present and paleo-environmental processes. We utilise cosmogenic 10Be and terrestrially derived 9Be measurements from surface sediments to estimate the residence time of Be in the Indian Ocean. Significant variation in Be residence time is observed, which ranges between 370 and 620 years in the central Indian Ocean, 64–205 years in the Bay of Bengal, 41–117 years in the Andaman Sea, and 179–443 years in the Arabian Sea. Large heterogeneity in the residence time of Be can be attributed to its variable scavenging efficiency in different regions. Active scavenging of Be by sediment particles contributed through various major rivers draining into the northern Indian Ocean results in short residence time of Be. The results of this study have significant implications for the selection of sample sites and the use of Be as a tracer in paleo reconstructions.