Hybrid Ghost Phonon Polaritons in Thin-Film Heterostructure.

Ghost phonon polaritons (g-PhPs), a unique class of phonon polaritons in the infrared, feature ultralong diffractionless propagation (>20 µm) across the surface and tilted wavefronts in the bulk. Here, we study hybrid g-PhPs in a heterostructure of calcite and an ultrathin film of the phase change material (PCM) In3SbTe2, where the optical field is bound in the PCM film with enhanced confinement compared with conventional g-PhPs. Near-field optical images for hybrid g-PhPs reveal a lemniscate pattern in the momentum distribution. We fabricated In3SbTe2 gratings and investigated how different orientations and periodicities of gratings impact the propagation of hybrid g-PhPs. As the grating period decreases to zero, the wavefront of hybrid g-PhPs can be dynamically steered by varying the grating orientation. Our results highlight the promise of hybrid g-PhPs with tunable functionalities for nanophotonic studies.

Tropomyosin induces the synthesis of magnesian calcite in sea urchin spines.

Calcium carbonate is present in many biominerals, including in the exoskeletons of crustaceans and shells of mollusks. High Mg-containing calcium carbonate was synthesized by high temperatures, high pressures or high molecular organic matter. For example, biogenic high Mg-containing calcite is synthesized under strictly controlled Mg concentration at ambient temperature and pressure. The spines of sea urchins consist of calcite, which contain a high percentage of magnesium. In this study, we investigated the factors that increase the magnesium content in calcite from the spines of the sea urchin, Heliocidaris crassispina. X-ray diffraction and inductively coupled plasma mass spectrometry analyses showed that sea urchin spines contain about 4.8% Mg. The organic matrix extracted from the H. crassispina spines induced the crystallization of amorphous phase and synthesis of magnesium-containing calcite, while amorphous was synthesized without SUE (sea urchin extract). In addition, aragonite was synthesized by SUE treated with protease-K. HC tropomyosin was specifically incorporated into Mg precipitates. Recombinant HC-tropomyosin induced calcite contained 0.1-2.5% Mg synthesis. Western blotting of sea urchin spine extracts confirmed that HC tropomyosin was present in the purple sea urchin spines at a protein weight ratio of 1.5%. These results show that HC tropomyosin is one factor that increases the magnesium concentration in the calcite of H. crassispina spines.

Control of crystal growth during coccolith formation by the coccolithophore Gephyrocapsa oceanica.

Coccolithophores are marine phytoplankton that produce calcite mineral scales called coccoliths. Many stages in the synthesis of these structures are still unresolved, making it difficult to accurately quantify the energetic costs involved in calcification, required to determine the response coccolith mineralization will have to rising ocean acidification and temperature created by an increase in global CO2 concentrations. To clarify this, an improved understanding of how coccolithophores control the fundamental processes of crystallization, including nucleation, growth, and morphology, is needed. Here, we study how crystal growth and morphology is controlled in the coccolithophore Gephyrocapsa oceanica by imaging coccoliths at various stages of maturity using cryo-transmission electron microscopy (cryoTEM), scanning electron microscopy (SEM) and focused ion beam SEM (FIB-SEM). We reveal that coccolith units tightly interlock with each other due to the non-vertical alignment of the two-layered tube element, causing these mineral units to extend over the adjacent crystals. In specific directions, the growth of the coccolith tube seems to be impacted by the physical constraint created by the close association of neighbouring units around the ring, influencing the overall morphology and organization of the crystals that develop. Our findings contribute to the overall understanding of how biological systems can manipulate crystallization to produce functional mineralized tissues.

Visualization of Multiphase Reactive Flow and Mass Transfer in Functionalized Microfluidic Porous Media.

Multiphase reactive flow in porous media is an important research topic in many natural and industrial processes. In the present work, photolithography is adopted to fabricate multicomponent mineral porous media in a microchannel, microfluidics experiments are conducted to capture the multiphase reactive flow, methyl violet 2B is employed to visualize the real-time concentration field of the acid solution and a sophisticated image processing method is developed to obtain the quantitative results of the distribution of different phases. With the advanced methods, experiments are conducted with different acid concentration and inlet velocity in different porous structures with different phenomena captured. Under a low acid concentration, the reaction will be single phase. In the gaseous cases with higher acid concentration, preferential flow paths with faster flow and reaction are formed by the multiphase hydrodynamic instabilities. In the experiments with different inlet velocities, it is observed that a higher inlet velocity will lead to a faster reaction but less gas bubbles generated. In contrast, more gas bubbles would be generated and block the flow and reaction under a lower inlet velocity. Finally, in heterogeneous structures, fractures or cavities would significantly redirect the flow and promote the formation of preferential flow path nearby.

Microbially induced calcium carbonate precipitation through CO2 sequestration via an engineered Bacillus subtilis.

BACKGROUND: Microbially induced calcium carbonate precipitation has been extensively researched for geoengineering applications as well as diverse uses within the built environment. Bacteria play a crucial role in producing calcium carbonate minerals, via enzymes including carbonic anhydrase-an enzyme with the capability to hydrolyse CO2, commonly employed in carbon capture systems. This study describes previously uncharacterised carbonic anhydrase enzyme sequences capable of sequestering CO2 and subsequentially generating CaCO3 biominerals and suggests a route to produce carbon negative cementitious materials for the construction industry. RESULTS: Here, Bacillus subtilis was engineered to recombinantly express previously uncharacterised carbonic anhydrase enzymes from Bacillus megaterium and used as a whole cell catalyst allowing this novel bacterium to sequester CO2 and convert it to calcium carbonate. A significant decrease in CO2 was observed from 3800 PPM to 820 PPM upon induction of carbonic anhydrase and minerals recovered from these experiments were identified as calcite and vaterite using X-ray diffraction. Further experiments mixed the use of this enzyme (as a cell free extract) with Sporosarcina pasteurii to increase mineral production whilst maintaining a comparable level of CO2 sequestration. CONCLUSION: Recombinantly produced carbonic anhydrase successfully sequestered CO2 and converted it into calcium carbonate minerals using an engineered microbial system. Through this approach, a process to manufacture cementitious materials with carbon sequestration ability could be developed.

New Insights into Calcite Dissolution Mechanisms under Water, Proton, or Carbonic Acid-Dominated Conditions.

Carbonate minerals are ubiquitous in nature, and their dissolution impacts many environmentally relevant processes including preferential flow during geological carbon sequestration, pH buffering with climate-change induced ocean acidification, and organic carbon bioavailability in melting permafrost. In this study, we advance the atomic level understanding of calcite dissolution mechanisms to improve our ability to predict this complex process. We performed high pressure and temperature (1300 psi and 50 °C) batch experiments to measure transient dissolution of freshly cleaved calcite under H2O, H+, and H2CO3-dominated conditions, without and with an inhibitory anionic surfactant present. Before and after dissolution experiments, we measured dissolution etch-pit geometries using laser profilometry, and we used density functional theory to investigate relative adsorption energies of competing species that affect dissolution. Our results support the hypothesis that calcite dissolution is controlled by the ability of H2O to preferentially adsorb to surface Ca atoms over competing species, even when dissolution is dominated by H+ or H2CO3. More importantly, we identify for the first time that adsorbed H+ enhances the role of water by weakening surface Ca-O bonds. We also identify that H2CO3 undergoes dissociative adsorption resulting in adsorbed HCO3- and H+. Adsorbed HCO3- that competes with H2O for Ca acute edge sites inhibits dissolution, while adsorbed H+ at the neighboring surface of CO3 enhances dissolution. The net effect of the dissociative adsorption of H2CO3 is enhanced dissolution. These results will impact future efforts to more accurately model the impact of solutes in complex water matrices on carbonate mineral dissolution.

Dynamic Inhibition of Calcite Dissolution in Flowing Acidic Pb2+ Solutions.

Reactions of mineral surfaces with dissolved metal ions at far-from-equilibrium conditions can deviate significantly from those in near-equilibrium systems due to steep concentration gradients, ion-surface interactions, and reactant transport effects that can lead to emergent behavior. We explored the effect of dissolved Pb2+ on the dissolution rate and topographic evolution of calcite (104) surfaces under far-from-equilibrium acidic conditions (pH 3.7) in a confined single-pass laminar-flow geometry. Operando measurements by digital holographic microscopy were conducted over a range of Pb2+ concentrations ([Pb2+] = 0 to 5 × 10-2 M) and flow velocities (v = 1.67-53.3 mm s-1). Calcite (104) surface dissolution rates decreased with increasing [Pb2+]. The inhibition of dissolution and the emergence of unique topographic features, including micropyramids, variable etch pit shapes, and larger scale topographic patterns, became increasingly apparent at [Pb2+] ≥ 5 × 10-3 M. A better understanding of such dynamic reactivity could be crucial for constructing accurate models of geochemical transport in aqueous carbonate systems.

Functional Characterization of Core and Unique Calcite-Dissolving Bacteria Communities from Peanut Fields.

Calcium deficiency is a leading cause of reduced peanut (Arachis hypogaea) seed quality and has been linked to increased disease susceptibility, specifically to soilborne fungal pathogens. Sufficient calcium at flowering time is critical to ensure proper pod development. Calcite-dissolving bacteria (CDB) isolated from farming fields can dissolve calcite (CaCO3) on plates and increase soluble calcium levels in soil. However, the phylogenetic diversity and geographic distribution of CDB is unclear. Here, we surveyed soil samples from 15 peanut-producing fields in three regions in southern Georgia, representing distinct soil compositions. We isolated CDB through differentiating media and identified 52 CDB strains. CDB abundance was not associated with any of the soil characteristics we evaluated. Three core genera, represented by 43 strains, were found in all three regions. Paenibacillus was the most common CDB found in all regions, making up 30 of the 52 identified strains. Six genera, represented by eight strains, are unique to one region. Members of the core and unique communities showed comparable solubilization indexes on plates. We conclude that a diversified phylogenetic population of CDB is present in Georgia peanut fields. Despite the phylogenetic diversity, as a population, they exhibit comparable functions in solubilizing calcite on plates.

Effect of Sulfuric Acid Corrosion on Flotation Performance of Calcite by Changing Surface Roughness.

Surface roughness is a crucial factor that affects the flotation performance of minerals. In this study, the effect of sulfuric acid corrosion on the surface roughness of calcite flotation was investigated through microflotation tests, scanning electron microscopy (SEM-EDS), atomic force microscopy (AFM), Fourier transform infrared (FT-IR) spectroscopy, and contact angle analysis. Microflotation test results show that sulfuric acid treatment has a serious negative effect on the floatability of calcite. When the sulfuric acid dosage was 4 mL (3 mol/L), the flotation recovery of calcite was reduced to less than 19%. SEM-EDS and AFM results verified that the sulfuric acid treatment significantly changed the surface morphology of calcite, reduced the average surface roughness and surface area, and reduced the amount of active Ca2+ sites on the calcite surface. As characterized by FT-IR and contact angle analyses, the sulfuric acid treatment enhanced the hydrophilicity of the calcite surface and reduced the amount of sodium oleate adsorbed on the calcite surface. Consequently, sulfuric acid corrosion can reduce the average surface roughness of calcite and have a serious negative effect on the flotation performance of calcite.

Alkalinity control in sludge propels the conversion of concrete slurry waste into micro- and nano-sized biogenic CaCO3.

The utilization of Bacillus sp. for the production of bio-CaCO3 in concrete crack repair and strength enhancement has attracted considerable attention. However, microbial-induced calcium carbonate precipitation (MICP) has yet to be explored as a precedent with activated sludge. Here calcium sourced from concrete slurry waste (CSW) and carbon from sludge microbial ß-oxidation under alkaline were used to generate micro/nano CaCO3. The results indicate that the main crystalline form of the generated precipitated particles is calcite, with a particle size ranging from 0.7 to 10 µm. Minimal heavy metals were found in the supernatant following settling. And at the optimum pH of 8.5-9, carbon capture reached 743 mg L-1, and CaCO3 production reached 1,191 mg L-1, and dominant phylum were Proteobacteria and Bacteroidota, with Thauera being a prevalent genus adept in ß-oxidation. Mass balance analysis showed that alkali promotes microbial ß-oxidation of organisms to produce CO2 and facilitate storage. Thus, the alkaline regulation of metabolism between microbe and CSW provides a novel way of sludge to initiate MICP.

Effect of Ba2+ on the biomineralization of Ca2+ and Mg2+ ions induced by Bacillus licheniformis.

The effect of barium ions on the biomineralization of calcium and magnesium ions is often overlooked when utilizing microbial-induced carbonate precipitation technology for removing barium, calcium, and magnesium ions from oilfield wastewater. In this study, Bacillus licheniformis was used to bio-precipitate calcium, magnesium, and barium ions. The effects of barium ions on the physiological and biochemical characteristics of bacteria, as well as the components of extracellular polymers and mineral characteristics, were also studied in systems containing coexisting barium, calcium, and magnesium ions. The results show that the increasing concentrations of barium ions decreased pH, carbonic anhydrase activity, and concentrations of bicarbonate and carbonate ions, while it increased the contents of humic acids, proteins, polysaccharides, and DNA in extracellular polymers in the systems containing all three types of ions. With increasing concentrations of barium ions, the content of magnesium within magnesium-rich calcite and the size of minerals precipitated decreased, while the full width at half maximum of magnesium-rich calcite, the content of O-C=O and N-C=O, and the diversity of protein secondary structures in the minerals increased in systems containing all three coexisting ions. Barium ions does inhibit the precipitation of calcium and magnesium ions, but the immobilized bacteria can mitigate the inhibitory effect. The precipitation ratios of calcium, magnesium, and barium ions reached 81-94%, 68-82%, and 90-97%. This research provides insights into the formation of barium-enriched carbonate minerals and offers improvements for treating oilfield wastewater.

Composite material in the sea urchin Cidaris rugosa: ordered and disordered micrometre-scale bicontinuous geometries.

The sponge-like biomineralized calcite materials found in echinoderm skeletons are of interest in terms of both structure formation and biological function. Despite their crystalline atomic structure, they exhibit curved interfaces that have been related to known triply periodic minimal surfaces. Here, we investigate the endoskeleton of the sea urchin Cidaris rugosa that has long been known to form a microstructure related to the Primitive surface. Using X-ray tomography, we find that the endoskeleton is organized as a composite material consisting of domains of bicontinuous microstructures with different structural properties. We describe, for the first time, the co-occurrence of ordered single Primitive and single Diamond structures and of a disordered structure within a single skeletal plate. We show that these structures can be distinguished by structural properties including solid volume fraction, trabeculae width and, to a lesser extent, interface area and mean curvature. In doing so, we present a robust method that extracts interface areas and curvature integrals from voxelized datasets using the Steiner polynomial for parallel body volumes. We discuss these very large-scale bicontinuous structures in the context of their function, formation and evolution.

New insights into the controversy of reactive mineral-controlled arsenopyrite dissolution and arsenic release.

Serious arsenic (As) contaminations could commonly result from the oxidative dissolution of As-containing sulfide minerals, such as arsenopyrite (FeAsS). Pyrite (Py) and calcite (Cal) are two typically co-existing reactive minerals and represent different geological scenarios. Previous studies have shown that a high proportion of Py can generate a stronger galvanic effect and acid dissolution, thereby significantly promoting the release of arsenic. However, this conclusion overlooks calcite's antagonistic effect on the release of As in the natural environment. That antagonistic effect could remodel the linear relationship of pyrite on the oxidative dissolution of arsenopyrite, thus altering the environmental risk of As. We examined As release from arsenopyrite along a gradient of Py to Cal molar ratios (Py:Cal). The results showed that the lowest As release from arsenopyrite was surprisingly found in co-existing Py and Cal systems than in the singular Cal system, let alone in the singular Py system. This phenomenon indicated an interesting possibility of Py assistance to Cal inhibition of As release, though Py has always been regarded as a booster, also evidenced in this research, for As release from arsenopyrite. In singular systems of Py and Cal, As continued to be released for 60 days. However, in co-existing Py and Cal systems, As was released non-linearly in three stages over time: initial release (0-1 Day), immobilization (1-15 Days), and subsequent re-release (>15 Days). This is a new short-term natural attenuation stage for As, but over time, this stage gradually collapses. During the re-release stage (> 15 Days), a higher molar ratio of Py:Cal (increasing from 1:9 to 9:1) results in a lower rate constant k (mg·L-1·h-1) of As release (range from 0.0011 to 0.0002), and a higher abundance of secondary minerals formed (up to 26 mg/g goethite and hematite at Py: Cal=9:1). This demonstrates that increasing the Py:Cal molar ratio results in the formation of more secondary minerals which compensate for the higher potential antagonistic mechanisms generated by pyrites, such as acid dissolution and galvanic effect. These results explain the mechanisms of the high-risk characteristics of As both in acidic mine drainage and karst aquifers and discover the lowest risk in pyrite and calcite co-existing regions. Moreover, we emphasize that reactive minerals are important variables that can't be ignored in predicting As pollution in the future.

Molecular and mineral responses of corals grown under artificial Calcite Sea conditions.

The formation of skeletal structures composed of different calcium carbonate polymorphs (e.g. aragonite and calcite) appears to be both biologically and environmentally regulated. Among environmental factors influencing aragonite and calcite precipitation, changes in seawater conditions-primarily in the molar ratio of magnesium and calcium during so-called 'Calcite' (mMg:mCa below 2) or 'Aragonite' seas (mMg:mCa above 2)-have had profound impacts on the distribution and performance of marine calcifiers throughout Earth's history. Nonetheless, the fossil record shows that some species appear to have counteracted such changes and kept their skeleton polymorph unaltered. Here, the aragonitic octocoral Heliopora coerulea and the aragonitic scleractinian Montipora digitata were exposed to Calcite Sea-like mMg:mCa with various levels of magnesium and calcium concentration, and changes in both the mineralogy (i.e. CaCO3 polymorph) and gene expression were monitored. Both species maintained aragonite deposition at lower mMg:mCa ratios, while concurrent calcite presence was only detected in M. digitata. Despite a strong variability between independent experimental replicates for both species, the expression for a set of putative calcification-related genes, including known components of the M. digitata skeleton organic matrix (SkOM), was found to consistently change at lower mMg:mCa. These results support the previously proposed involvements of the SkOM in counteracting decreases in seawater mMg:mCa. Although no consistent expression changes in calcium and magnesium transporters were observed, down-regulation calcium channels in H. coerulea in one experimental replicate and at an mMg:mCa of 2.5, pointing to a possible active calcium uptake regulation by the corals under altered mMg:mCa.

Interfacial processes underlying the temperature-dependence of friction and wear of calcite single crystals.

HYPOTHESIS: This study posits that thermal effects play a substantial role in influencing interfacial processes on calcite, and consequently impacting its mechanochemical properties. EXPERIMENTS: This work interrogates the temperature-dependence of friction and wear at nanoscale contacts with calcite single crystals at low air humidity (≤ 3-10 % RH) by AFM. FINDINGS: Three logarithmic regimes for the velocity-dependence of friction are identified. BelowTc âˆ¼ 70 °C, where friction increases with T, there is a transition from velocity-weakening (W1) to velocity-strengthening friction (S1). AboveTc âˆ¼ 70 °C, where friction decreases with T, a second velocity-strengthening friction regime (S0) precedes velocity-weakening friction (W1). The low humidity is sufficient to induce atomic scale changes of the calcite cleavage plane due to dissolution-reprecipitation, and more so at higher temperature and 10 % RH. Meanwhile, the surface softens above Tc -likely owing to lattice dilation, hydration and amorphization. These interfacial changes influence the wear mechanism, which transitions from pit formation to plowing with increase in temperature. Furthermore, the softening of the surface justifies the appearance of the second velocity-strengthening friction regime (S0). These findings advance our understanding of the influence of temperature on the interfacial and mechanochemical processes involving calcite, with implications in natural processes and industrial manufacturing.

Chitin/calcite composite extracted from shell waste as a low-cost adsorbent for removal of tetracycline and ciprofloxacin: Effects and mechanisms.

Recently, water contamination caused by the misuse of antibiotics has become a growing concern. In this study, an economical chitin/calcite composite (CCA) was extracted from crab shell waste, and the effects and mechanisms of its removal of ciprofloxacin (CIP) and tetracycline (TC) from aqueous solution were investigated. The functional groups of chitin and the metal phase of calcite gave CCA the ability to remove antibiotics. Experiments on kinetics, isothermal adsorption, thermodynamics, co-removal, and reusability were conducted to systematically explore the adsorption performances of CCA toward antibiotics. The pseudo-second-order (FSO) and Langmuir models suited the data obtained from experiments best and displayed a good fit for the chemisorption and a certain homogeneity of adsorption sites. At 25 °C, the maximum adsorption capacities (Qmax) toward CIP and TC were 228.86 and 150.76 mg g-1, respectively. The adsorption mechanisms of CCA with TC and CIP are pH dependent since pH can affect the surface charge of CCA and the form in which CIP and TC are existing. The X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) demonstrated that the keto-O and carboxyl groups of CIP and the carbonyl, hydroxyl, and amido groups of TC could be responsible for the binding with the calcite and the functional groups of chitin through surface complexation, cation bridge and hydrogen bonding.

A mini review of enzyme-induced calcite precipitation (EICP) technique for eco-friendly bio-cement production.

This paper has presented a mini review of previously published articles dealing with bio-cement production using enzyme-induced calcite precipitation (EICP) technique. EICP is a biological, sustainable, and natural way of producing calcite without the direct involvement of microorganisms from urea and calcium chloride using urease enzyme in water-based solution with minimum energy consumption and eco-friendly. Calcite is a renewable bio-material that acts as a binder to improve the mechanical properties of soils like strength, stiffness, and water permeability. EICP has many real applications such as fugitive duct control with low cost comparing with water application or pouring, self-healing cracked concretes, and upgrade or change the low-volume road surfaces that are difficult for road constructions. The crystal structure of finally produced calcium carbonate (CaCO3), calcite is affected by the source of calcium ion; the calcite produced from calcium chloride has a rhombohedral crystal structure. The urease enzyme used for EICP applications could be produced in a laboratory-scale from different plant species, bacteria, some yeasts, fungi, tissues of humans, and invertebrates. Nevertheless, urease enzyme produced from jack beans has showed urease enzyme activity around 2700-3500U/g, and the tendency to replace the urease enzyme found in the global market. All urease enzymes have 12-nm size, and this smaller size makes EICP preferable for all types of soil or sands including fine and silt sands.

Hydrothermal calcite formation in Campi Flegrei caldera, Italy: unraveling carbon sink processes in alkaline volcanic systems.

Understanding carbon dioxide emissions variability in volcanic regions is vital for detecting instabilities in the subvolcanic plumbing system, crucial for managing both volcanic and environmental risks. While changes in magmatic sources drive these variations, non-magmatic processes can complicate signal interpretation, especially in caldera environments. Here, geothermal systems can sequester CO2 within the bedrock through hydrothermal calcite precipitation, significantly impacting surface-level CO2 emissions. Unfortunately, few studies have explored this phenomenon, examining hydrothermal calcite origins and their effects on carbon balances and temporal gaseous patterns in active volcanic settings. Our study developed a specialized methodology for quantifying CO2 sequestered in hydrothermal calcites within alkaline caldera systems. We focused on analyzing hydrothermal calcite in lithics from volcanic deposits of eruptions of varying ages, Volcanic Explosivity Index (VEI), and eruptive vent locations to enhance the representativeness of the entire caldera bedrock. Unlike core samples from geothermal wells, which are infrequent and limited to specific depths, lithics can be easily collected, offering a comprehensive understanding of CO2 sequestration. Through extensive 3D textural characterization and isotopic investigations on hydrothermal calcite within lithic fragments from selected alkaline volcanic deposits in the Campi Flegrei caldera, our findings emphasized the significant influence of calcite sinks on the overall CO2 budget released by volcanoes throughout their evolution.

Composite biomediated engineering approaches for improving problematic soils: Potentials and opportunities.

Several conventional chemical stabilizers are used for soil stabilization, among which cement is widely adopted. However, the high energy consumption and environmental challenges associated with these stabilizers have necessitated the transition toward the adoption/deployment of eco-friendly approaches for soil stabilization. Biomediated techniques are sustainable soil improvement methods adopting less toxic microorganisms, enzymes, or polymers for cementing soil. However, these processes also have several drawbacks, such as slow hardening, environmental impact, high cost, and lack of compatibility with different types of soils. It is hypothesized that these limitations may be overcome by exploring the prospects and opportunities offered by hybrid technological approaches involving the integration of nontraditional stabilizers and microbial-induced biomineralization processes for improving problematic soils. This paper discusses selected previous studies integrating different technologies and their benefits and challenges. The emerging fungi-based bio-mediation techniques and the possibility of forming sustainable fungal-based biocomposites to improve problematic soils are also highlighted.

Preferential deposition of buoyant small microplastics in surface sediments of the Three Gorges Reservoir, China: Insights from biomineralization.

Sediments act as sinks of microplastics (MPs) derived from terrestrial ecosystems. However, the fate and transport of MPs at the zone of sediment-overlying water in reservoir environment are poorly understood. Here, the MPs distribution patterns in surface sediments of the Three Gorges Reservoir (TGR) and dominant mechanisms responsible for the sinking of MPs at the zone of sediment-overlying water were comprehensively investigated. The predominant occurrence of small microplastics (<300 µm, SMPs) in surface sediments of the TGR was found, with buoyant polyethene (PE) was dominant polymer types. Interestingly, the high abundance of SMPs in sediments correlated well with the Ca2+/Mg2+ in overlying water, suggesting that divalent cations in overlying water may enhance the preferential deposition of SMPs. Simulation sinking experiments under the presence of Microcystis aeruginosa and two divalent cations using different-sized PE MPs demonstrated that the greater deposition of SMPs was mainly the result of the formation of biogenic calcite on the surface of MPs rather than magnesium minerals, which provides stronger ballasting effects for SMPs than for large MPs. This study first highlights that the impact of biomineralization on preferential sinking of SMPs and enhances the understanding of the transport behaviour of MPs in aquatic environment.