ALBERT

Description: Sea spray aerosols (SSA) greatly affect the climate system by scattering solar radiation and acting as seeds for cloud droplet formation. The ecosystems in the Arctic Ocean are rapidly changing due to global warming, and the effects these changes have on the generation of SSA, and thereby clouds and fog formation in this region, are unknown. During the ship-based Arctic Century Expedition, we examined the dependency of forced SSA production on the biogeochemical characteristics of seawater using an on-board temperature-controlled aerosol generation chamber with a plunging jet system. Our results indicate that mainly seawater salinity and organic content influence the production and size distribution of SSA. However, we observed a 2-fold higher SSA production from waters with similar salinity collected north of 81°N compared to samples collected south of this latitude. This variability was not explained by phytoplankton and bacterial abundances or Chlorophyll-a concentration but by the presence of glucose in seawater. The synergic action of sea salt (essential component) and glucose or glucose-rich saccharides (enhancer) accounts for 〉80% of SSA predictability throughout the cruise. Our results suggest that besides wind speed and salinity, SSA production in Arctic waters is also affected by specific organics released by the microbiota.

Description: Groundwater discharge into the sea occurs along many coastlines around the world in different geological settings and constitutes an important component of global water and matter budget. Estimates of how much water flows into the sea worldwide vary widely and are largely based on onshore studies and hydrological or hydrogeological modeling. In this study, we propose an approach to quantify a deep submarine groundwater outflow from the seafloor by using autonomously measured ocean surface data, i.e., 222Rn as groundwater tracer, in combination with numerical modeling of plume transport. The model and field data suggest that groundwater outflows from a water depth of ∼100 m can reach the sea surface implying that several cubic meters per second of freshwater are discharged into the sea. We postulate an extreme rainfall event 6 months earlier as the likely trigger for the groundwater discharge. This study shows that measurements at the sea surface, which are much easier to conduct than discharge measurements at the seafloor, can be used not only to localize submarine groundwater discharges but, in combination with plume modeling, also to estimate the magnitude of the release flow rate.

Description: There is only sparse empirical data on the settling velocity of small, nonbuoyant microplastics thus far, although it is an important parameter governing their vertical transport within aquatic environments. This study reports the settling velocities of 4031 exemplary microplastic particles. Focusing on the environmentally most prevalent particle shapes, irregular microplastic fragments of four different polymer types (9-289 mu m) and five discrete length fractions (50-600 mu m) of common nylon and polyester fibers are investigated, respectively. All settling experiments are carried out in quiescent water by using a specialized optical imaging setup. The method has been previously validated in order to minimize disruptive factors, e.g., thermal convection or particle interactions, and thus enable the precise measurements of the velocities of individual microplastic particles (0.003-9.094 mm/s). Based on the obtained data, ten existing models for predicting a particle's terminal settling velocity are assessed. It is concluded that models, which were specifically deduced from empirical data on larger microplastics, fail to provide accurate predictions for small microplastics. Instead, a different approach is highlighted as a viable option for computing settling velocities across the microplastics continuum in terms of size, density, and shape

Description: Suspended particulate matter (SPM) carries a major fraction of metals in turbid coastal waters, markedly influencing metal bioaccumulation and posing risks to marine life. However, its effects are often overlooked in current water quality criteria for metals, primarily due to challenges in quantifying SPM’s contribution. This contribution depends on the SPM concentration, metal distribution coefficients (Kd), and the bioavailability of SPM-bound metals (assimilation efficiency, AE), which can collectively be integrated as a modifying factor (MF). Accordingly, we developed a new stable isotope method to measure metal AE by individual organisms from SPM, employing the widely distributed filter-feeding clam Ruditapes philippinarum as a representative species. Assessing SPM from 23 coastal sites in China, we found average AEs of 42% for Zn, 26% for Cd, 20% for Cu, 8% for Ni, and 6% for Pb. Moreover, using stable isotope methods, we determined metal Kd of SPM from these sites, which can be well predicted by the total organic carbon and iron content (R2 = 0.977). We calculated MFs using a Monte Carlo method. The calculated MFs are in the range 9.9-43 for Pb, 8.5-37 for Zn, 2.9-9.7 for Cu, 1.4-2.7 for Ni, and 1.1-1.6 for Cd, suggesting that dissolved-metal-based criteria values should be divided by MFs to provide adequate protection to aquatic life. This study provides foundational guidelines to refine water quality criteria in turbid waters and protect coastal ecosystems.

Description: CO2 injection has been deemed a promising method for CH4 production from gas hydrate-bearing sediments for its potential in stabilizing the host sediments and balancing carbon emission. However, the process is yet to be fully understood, as it involves interactions of multi-physical and chemical processes including the generation of water-immiscible CH4–CO2 fluid mixtures, the evolution of chemical reaction kinetics for both CH4 and CO2 hydrates, heat emission and absorption during hydrate formation and dissociation, and stress redistribution caused by spatially evolving responses of CH4–CO2 hydrate-bearing sediments. This paper develops a coupled thermo-hydro-chemo-mechanical formulation that captures the complexity of these processes and applies it to investigate the behavior of CH4 hydrate-bearing sediments subjected to CO2 injection. The capabilities of this coupled formulation are validated through numerical simulations of laboratory experiments of CO2 injection into CH4 hydrate-bearing soil. Moreover, the application of this formulation in a field-scale scenario reveals insights into the efficiencies of CH4 production and CO2 storage and the geomechanical implications. Notably, the study finds that compared to the depressurization-only method, the combined hot CO2 injection and depressurization method could increase CH4 production by approximately 400%. In addition, this method could sequester about 70% of injected CO2 into solid hydrates, while exhibiting smaller maximum slope of differential displacement. These outcomes highlight the viability and benefits of CH4 hydrate production through CO2 injection, increasing the prospects of this approach.

Description: Detailed geochemical and mineralogical insights into some of the richest rare earth elements and yttrium (REY)-containing bioapatites from ocean-floor sediments have been provided by combining laser ablation inductively coupled plasma diffraction analysis, and Ce L3-edge high energy-resolution X-ray absorption near edge structure (HR-XANES) spectroscopy. Bioapatites at 1.94 and 4.70 m below the seafloor (mbsf) of the Clarion-Clipperton Zone (CCZ) of the Pacific Ocean have 26,600 (RSD = 15.7%, n = 20) and 30,300 (RSD = 14.6%, n = 10) mg/kg (mg/kg) total REY, respectively, and bioapatites at 2.28 and 6.95 mbsf of the Peru Basin have 15,500 (RSD = 15.6%, n = 20) and 15,700 (RSD = 17.8%, n = 29) mg/kg total REY, respectively. All bioapatite specimens have a variety of isomorphic substitutions in all atomic positions of the crystallographic structure. The average crystallochemical formula of bioapatites at 6.95 mbsf of the Peru Basin is [(PO4)2.71(SiO4)0.04(CO3,SO4)0.25][Ca4.57Na0.29Y0.04][F0.87Cl0.21]. All other substituents are below 0.04 atoms per formula unit. HR-XANES provides the first direct evidence for trivalent Ce in sediment apatites. The strong negative geochemical anomaly of Ce in fossil bioapatites is well explained by the occurrence of four valent Ce-MnO2 and CeO2 within the sediment and in seafloor ferromanganese nodules.

Description: The air-blood partition coefficient (Kab) is extensively employed in human health risk assessment for chemical exposure. However, current Kab estimation approaches either require an extensive number of parameters or lack precision. In this study, we present two novel and parsimonious models to accurately estimate Kab values for individual neutral organic compounds, as well as their complex mixtures. The first model, termed the GC×GC model, was developed based on the retention times of nonpolar chemical analytes on comprehensive two-dimensional gas chromatography (GC×GC). This model is unique in its ability to estimate the Kab values for complex mixtures of nonpolar organic chemicals. The GC×GC model successfully accounted for the Kab variance (R2 = 0.97) and demonstrated strong prediction power (RMSE = 0.31 log unit) for an independent set of nonpolar chemical analytes. Overall, the GC×GC model can be used to estimate Kab values for complex mixtures of neutral organic compounds. The second model, termed the partition model (PM), is based on two types of partition coefficients: octanol to water (Kow) and air to water (Kaw). The PM was able to effectively account for the variability in Kab data (n = 344), yielding an R2 value of 0.93 and root-mean-square error (RMSE) of 0.34 log unit. The predictive power and explanatory performance of the PM were found to be comparable to those of the parameter-intensive Abraham solvation models (ASMs). Additionally, the PM can be integrated into the software EPI Suite, which is widely used in chemical risk assessment for initial screening. The PM provides quick and reliable estimation of Kab compared to ASMs, while the GC×GC model is uniquely suited for estimating Kab values for complex mixtures of neutral organic compounds. In summary, our study introduces two novel and parsimonious models for the accurate estimation of Kab values for both individual compounds and complex mixtures.

Description: Coastal waters are contaminated globally with millions of metric tons of munitions from the two world wars which constitute a potential threat to ecosystems and humans. Laboratory-based chemical methods for the detection of munition compounds (MCs) in seawater typically take weeks to months between sample collection and analysis. The current work details a novel, field-deployable system for rapid (under 10 min) analysis of four common MCs (1,3-dinitrobenzene (DNB), amino-4,6-dinitrotoluene (ADNT), 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX)). The system uses a fluidic preconcentration unit with high-performance liquid chromatography (HPLC) and detection by electrospray-ionization mass spectrometry and UV–vis spectroscopy. The fluidic unit comprises two solid-phase extraction (SPE) columns for preconcentration of target MCs from the seawater matrix and allows loading and analysis of two samples simultaneously. Seven SPE resins were tested for extraction efficiency and robustness, with Porapak RDX showing best performance. Chromatographic separation of target MCs was performed using a C8 reversed-phase HPLC column. Limits of detection (LODs) were 3.7, 1.8, 3.6, and 10.7 ng L–1 for DNB, ADNT, TNT, and RDX, respectively. The system’s analytical performance and automated data processing procedure were demonstrated in the Baltic Sea.

Description: The world adds about 51 Gt of greenhouse gases to the atmosphere each year, which will yield dire global consequences without aggressive action in the form of carbon dioxide removal (CDR) and other technologies. A suggested guideline requires that proposed CDR technologies be capable of removing at least 1% of current annual emissions, about half a gigaton, from the atmosphere each year once fully implemented for them to be worthy of pursuit. Basalt carbonation coupled to direct air capture (DAC) can exceed this baseline, but it is likely that implementation at the gigaton-per-year scale will require increasing per-well CO2 injection rates to a point where CO2 forms a persistent, free-phase CO2 plume in the basaltic subsurface. Here, we use a series of thermodynamic calculations and basalt dissolution simulations to show that the development of a persistent plume will reduce carbonation efficiency (i.e., the amount of CO2 mineralized per kilogram of basalt dissolved) relative to existing field projects and experimental studies. We show that variations in carbonation efficiency are directly related to carbonate mineral solubility, which is a function of solution alkalinity and pH/CO2 fugacity. The simulations demonstrate the sensitivity of carbonation efficiency to solution alkalinity and caution against directly extrapolating carbonation efficiencies inferred from laboratory studies and small-injection-rate field studies conducted under elevated alkalinity and/or pH conditions to gigaton-per-year scale basalt carbonation. Nevertheless, all simulations demonstrate significant carbonate mineralization and thus imply that significant mineral carbonation can be expected even at the gigaton-per-year scale if basalts are given time to react.

Description: Certain cyanobacteria of the secondary metabolite-rich order Nostocales can establish permanent symbioses with a large number of cycads, by accumulating in their coralloid roots and shifting their metabolism to dinitrogen fixation. Here, we report the discovery of two new lipoglycopeptides, desmamides A (1) and B (2), together with their aglycone desmamide C (3), from the nostocalean cyanobacterium Desmonostoc muscorum LEGE 12446 isolated from a cycad (Cycas revoluta) coralloid root. The chemical structures of the compounds were elucidated using a combination of 1D and 2D NMR spectroscopy and mass spectrometry. The desmamides are decapeptides featuring O-glycosylation of tyrosine (in 1 and 2) and an unusual 3,5-dihydroxy-2-methyldecanoic acid residue. The biosynthesis of the desmamides was studied by substrate incubation experiments and bioinformatics. We describe herein the dsm biosynthetic gene cluster and propose it to be associated with desmamide production. The discovery of this class of very abundant (〉1.5% d.w.) bacterial lipoglycopeptides paves the way for exploration of their potential role in root endosymbiosis.