Solid Phase Research Articles

A Quick Joule‐Heating Coupled with Solid‐Phase Synthesis for Carbon‐Supported Pd–Se Nanoparticles Toward High‐Efficiency Electrocatalysis

AbstractWith respect to the potential of palladium (Pd)‐based nanomaterials in catalyzing typical electrochemical reactions, herein, a strategy that couples the quick Joule‐heating with a solid phase synthesis for producing carbon‐supported Pd–Se nanoparticles with welcome features is reported, e.g., fine sizes, clean surfaces, and controlled crystal phases toward electrocatalysis of oxygen reduction reaction (ORR) and ethanol oxidation reaction (EOR) in an alkaline medium. Principally, the introduction of Se into Pd alters its electronic properties and weakens the adsorption of key reaction intermediates on the Pd–Se nanoparticles during the ORR and EOR process, thus endowing them with better electrocatalysis for the same electrochemical reactions. Impressively, the carbon‐supported Pd–Se nanoparticles exhibit phase‐dependent electrocatalysis toward ORR and EOR. In particular, the cubic Pd17Se15 nanoparticles supported on carbon substrate show mass activity of 0.206 A mgPd−1 and specific activity of 0.546 mA cm−2 at 0.9 V for ORR in 0.1 m KOH electrolyte, while the orthorhombic PdSe2 nanoparticles show a mass activity of 3.79 A mgPd−1 for EOR, higher than that of their cubic counterpart and commercial Pd/C catalyst. The universality of this synthetic strategy in manufacturing carbon‐supported noble metal chalcogenide nanoparticles and highlighting its potential in designing highly efficient electrocatalysts are emphasized.

Non-targeted facilitation of primary sludge anaerobic fermentation by micro-aeration and the simultaneous nutrients transformations

Anaerobic fermentation is a widely used technology for resource recovery from municipal sludge (e.g., primary sludge). Micro-aeration is an emerging strategy which can be incorporated into this technology. However, the effect of micro-aeration on the anaerobic fermentation performance and the nutrients transformations are not well known. This study investigated the impact of micro-aeration on the production of volatile fatty acids (VFAs) from primary sludge as well as the simultaneous nitrogen (N) and phosphorus (P) transformations in the system. The obtained results indicated that application of micro-aeration improved the microbial activities and facilitated all the hydrolysis, acetogenesis and methanogenesis processes. Hydrogenotrophic methanogen was enriched by micro-aeration while the acetoclastic methanogenesis was still the dominant CH4 production pathway at gene level. The concentration of VFAs was lower with micro-aeration than in the control system, which could be attributed to the enhanced consumption of VFAs. The simultaneous transformations of N and P were observed with different patterns. Micro-aeration led to removal of up to 131.6 mg/L of N, with occurrence of nitrification and denitrification found to be responsible for the N removal. In contrast, the total P content remained unchanged in the reactor. However, micro-aeration was found to inhibit both extracellular organic-P mineralization and intracellular poly-P degradation, resulting in lower soluble PO43−-P and more P distributed in the organic-P fraction in solid phase. This study provides novel insights into the microscopic mechanisms of the micro-aeration on anaerobic fermentation and the simultaneous regulation of N and P release.

Solubility diagrams of phase equilibrium in quaternary system Na+, Ni2+//Cl−, SO42−–H2O in the temperature range[formula omitted]

Diagram of solubility in quaternary water-salt system Na+,Ni2+//Cl-,SO42--H2O in the temperature range −5 ÷ 90 °С was calculated on the base of classical Pitzer’s equations. Linear temperature approximation of solubility products of solid phases was used.

Crystal Phase Ionic Liquids for Energy Applications: Heat Capacity Prediction via a Hybrid Group Contribution Approach.

In the selection and design of ionic liquids (ILs) for various applications, including heat transfer fluids, thermal energy storage materials, fuel cells, and solvents for chemical processes, heat capacity is a key thermodynamic property. While several attempts have been made to develop predictive models for the estimation of the heat capacity of ILs in their liquid phase, none so far have been reported for the ILs' solid crystal phase. This is particularly important for applications where ILs will be used for thermal energy storage in the solid phase. For the first time, a model has been developed and used for the prediction of crystal phase heat capacity based on extending and modifying a previously developed hybrid group contribution model (GCM) for liquid phase heat capacity. A comprehensive database of over 5000 data points with 71 unique crystal phase ILs, comprising 42 different cations and 23 different anions, was used for parameterization and testing. This hybrid model takes into account the effect of the anion core, cation core, and subgroups within cations and anions, in addition to the derived indirect parameters that reflect the effects of branching and distribution around the core of the IL. According to the results, the developed GCM can reliably predict the crystal phase heat capacity with a mean absolute percentage error of 6.78%. This study aims to fill this current gap in the literature and to enable the design of ILs for thermal energy storage and other solid phase applications.

Perovskite materials advance the potent sensor exploration

AbstractPerovskite materials with unique crystal structure have developed rapidly in recent years owing to their special physical and chemical properties, such as high light absorption and extraordinary electrocatalytic properties. Metal halide perovskites are quite attractive in various fields because of their simple manufacturing process, adjustable band gap, good charge transfer performance, and high theoretical photoelectric conversion efficiency. Therefore, perovskite oxides mixed with metal elements become ideal samples for studying the surface and catalytic performance of catalysts. In this review, various metal perovskites are clearly classified and introduced according to the corresponding synthesis methods, including hydrothermal method, sol–gel method, and high‐temperature solid phase, as well as coprecipitation. The excellent properties of perovskite make it extensively used in nanotechnology, chemistry, environmental protection, and material science, especially in solar cells and sensors. In particular, the nanosized perovskite materials are becoming more and more popular in sensors, which was reviewed in detail here. Most importantly, the design of electrochemical sensors using perovskite nanomaterials with low detection limit and high sensitivity will bring new insight into the detection of biomolecules. Both challenges and prospects of metal perovskites were discussed for promoting the development of biosensors in the end.

Hydrogen Formation from Water with Various Reducing Metals Catalyzed by In Situ-Generated Nickel Nanoparticles

Water is a potential green source for the generation of clean elemental hydrogen without contaminants. One of the most convenient methods for hydrogen generation is based on the oxidation of different metals by water. The inspection of the catalytic activity toward hydrogen formation from water performed in this study was carried out using four different metals, namely, zinc, magnesium, iron, and manganese. The process is catalyzed by in situ-generated nickel nanoparticles. The zinc–water system was found to be the most effective and exhibited 94% conversion in 4 h. The solid phase in the latter system was characterized by PXRD and SEM techniques. Several blank tests provided a fundamental understanding of the role of each constituent within the system, and a molecular mechanism for the catalytic cycle was proposed.

Ecological risk assessment of organochlorine pesticide residues in sediment samples from Lake Tana and Hayqe in Northwest Ethiopia

In most developing countries, including Ethiopia, the excessive use of toxic and persistent pesticides for agricultural and malaria control purposes poses a significant challenge. This study focuses on evaluating the concentration and ecological risks associated with organochlorine pesticides (OCPs) in the sediments of Lake Tana and Hayqe. Employing a laboratory-based cross-sectional approach, the residues of OCPs in sediment samples were extracted using the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method, followed by dispersive solid phase extraction cleanup (d-SPE) techniques and analyzed for 18 OCPs by gas chromatography coupled to tandem mass spectrometry (GC-MS). The risk Quotient (RQ) method was adopted for ecological risk assessments by using fish, daphnia, and algae as indicators. The concentration of OCPs ranged from 10.11 to 125.65 μg/kg and 10.96–45.17 μg/kg in Lake Tana and Hayqe, respectively. There was a statistically significant difference in the mean concentration of OCPs across the sampling sites in Lake Tana. Deltamethrin and lindane exhibit comparatively lower concentrations among the OCPs, whereas endrin, DDT, and their metabolites were the predominant pesticides in the study area, exceeding WHO and USEPA residue limits, except for endosulfan. Risk Quotient values ranged from 0.006 to 865.4 in Lake Tana and 0.005 to 729.9 in Lake Hayqe, indicating potential low to high ecological risks for aquatic organisms. High ecological risks are particularly evident in fish, daphnia, and algae species exposed to α and β-Endosulfan, DDT, and their metabolites, while specifically in daphnia, endrin poses high ecological risks. The ANOVA test revealed there were statistically significant differences (p-value <0.05) among sampling sites in Lake Tana and the mean values between Lake Tana and Lake Hayqe, underscoring the importance of addressing pesticide-related ecological concerns in the region.

Synthesis of Magnetic Attapulgite Nanoparticles Via a Novel Surface Covalent Reaction Method and its Application in the Magnetic Solid Phase Extraction.

In this study, the attapulgite nanoparticle was immobilized on the surface of magnetic nanoparticle Fe3O4 via a novel surface covalent reaction method for the magnetic solid phase extraction (MSPE) for the first time. The surface covalent reaction method has the advantages of controllable steps, and can make the magnetic attapulgite nanoparticle (MANP) have good homogeneity and high stability. Field emission scanning electron microscopy, equipped with an energy dispersive spectrometer, Nitrogen adsorption BET, X-ray diffraction and Fourier transform infrared spectroscopy were applied to characterize the prepared MANP, confirming that the attapulgite nanoparticle could be effectively immobilized on the surface of magnetic nanoparticle Fe3O4 via covalent reactions. Under optimal conditions of the MSPE experiment based on the MANP, the limits of detection were found to be 10ng/mL for melamine and 3ng/mL for cyromazine with a relative standard deviation < 10% by a high-performance liquid chromatography system. Meanwhile, 0.1mg/mL melamine in milk and 0.1mg/mL cyromazine in cucumber can also be detected according to our MSPE procedure. More importantly, the MANP still has good magnetism and enrichment efficiency after several decades of use. These results showed that the MANP prepared by our method is a kind of promising material for the MSPE.

Cultivar authentication of olive oil from Ionian islands using volatile compounds and chemometric analyses

AbstractTwo hundred and twenty-three olive samples of different olive cultivars (Koroneiki, Asprolia, Lianolia, Ntopia, Thiaki, Mavrolia, and Others) grown in the Ionian islands (Kefalonia, Kerkyra, Leukada, and Zakynthos) were subjected to headspace solid phase microextraction coupled to gas chromatography/mass spectrometry analysis. The aim of the study was to characterize the aroma pattern of these olive oil cultivars, and track whether specific volatile compounds could be used for olive oil cultivar authentication using chemometrics. Multivariate analysis of variance implemented on the semi-quantitative data of volatile compounds (alcohols, aldehydes, benzene derivatives, esters, hydrocarbons, ketones, and terpenoids), showed that olive cultivar had a significant impact on the volatile composition of olive oil samples. Factor analysis and linear discriminant analysis indicated those specific volatile compounds that could be related to olive oil cultivar and established statistical models for the olive oil cultivar authentication from Ionian islands, thus indicating a characteristic aroma fingerprint of these olive oils.

Interfacial Mass Diagnostics: Quantitative Perspective on Construction and Mechanism Understanding of Dye-Sensitized, Perovskite and Quantum Dots Solar Cells.

Dye-sensitized solar cells (DSSCs), quantum dot-sensitized solar cells (QDSSCs) and perovskite solar cells (PSCs) have attracted wide attention. DSSCs, QDSSCs and PSCs can be prepared by liquid phase or solid phase, which causes a certain range of interface micro-mass changes during preparation. In addition, the photoelectric conversion process occurring inside the device also inevitably causes interface micro-mass changes. Interpretation of these interface micro-mass changes can help to optimize the cell structure, improve the stability and performance repeatability of the device, as well as directly or indirectly infer, track and predict the internal photoelectric conversion mechanism of the device. Quartz crystal microbalance (QCM) is a powerful tool for studying surface mass changes, extending this technology to the fields of solar cells to directly obtain interface micro mass changes, which makes the research more in-depth and opens up a new perspective for explaining the basic principles of solar cells. This review summarizes the research progress of QCM application in DSSCs, QDSSCs and PSCs in recent years, and explores the challenges and new opportunities of QCM application in new solar cells in the future.

Control of Interface Migration in Nonequilibrium Crystallization of Li2SiO3 from Li2O-SiO2 Melt by Spatiotemporal Temperature and Concentration Fields.

During liquid-solid transformation, bulk mass and thermal diffusion, along with the evolved interfacial latent heat, work in tandem to generate interfacial thermodynamic and kinetic forces, the interplay of which decides the solidification velocity and consequently the solidified phase attributes. Hence, access to interface dynamics information in dependence of bulk transfer processes is pivotal to tailor the desired quantity of solid phases of unique compositions. It finds particular application for engineering concentrated Lithium (Li) phases out of Li-ion battery slags, thus generating a high value-added product from a conventional waste process stream. However, considerable challenge exists to predict the impact of the diverse external cooling rates on the evolving internal transfer processes and thus tuning solidification routes for achieving phases of interest. Hence, in this work, a thermodynamically consistent nonequilibrium model, by considering spatiotemporal temperature and concentration fields, is developed and applied to study solidification of Li2SiO3 from a Li2O-SiO2 melt that constitutes an important subsystem of the Li containing battery-recycling slags. The approach treats the sharp solid/liquid interface as a moving heat source. In the presence of different heat extraction profiles, it evaluates the spatial temperature heterogeneity and its implicit correlation to internal material fluxes resulting from maximization of dissipation and consequently the interrelation to interface velocities. Model calculations revealed that irrespective of the external cooling rate, for an initial short time duration, the magnitude of which increased with decreasing cooling rates, the interface velocities show a reducing trajectory directly relatable to the reducing thermodynamic forces due to localized interfacial temperature rise from the generated latent heat of fusion from the initial solidification. This is followed by a thermodynamically controlled regime, whereby for each cooling rate, the interface velocities increase until a maxima, the magnitude of which decreases with decreasing cooling rates. Finally, the interface propagation speeds decrease as controlled by the kinetic regime.

Formation of Peroxynitrite, [O-N-O-O]-, via a Cascade of Reactions between Ozonide and Ammonia.

We report on an unexpected reaction between ammonia and potassium ozonide dissolved in liq. NH3 resulting in the formation of peroxynitrite, [ONOO]-, which exclusively happens in the presence of a specific partially fluorinated aniline-based ammonium cation. High-resolution structural data of the peroxynitrite anion in cis-conformation have been obtained. We further studied this molecule anion by single crystal Raman spectroscopy. The cis and trans isomers of peroxynitrite were analysed computationally with respect to their relative energies, the cis-trans transition barrier and their decomposition pathways to the nitrate anion. By experimentally examining cations decorated with fluorine ligands to different degrees, we demonstrate that fluorine specific interactions play a crucial role in the unexpected formation of peroxynitrite and as a conspicuously structure directing factor for the underlying crystalline solid phases, exhibiting distinct micro-separations of fluorine and hydrogen enriched regions.

Numerical Simulation of Chemical Reactive Flow of Boger Fluid Over a Sheet with Heat Source and Local Thermal Non-Equilibrium Conditions

In this article, the effect of nonlinear heat source on chemical reactive flow of magnetized Boger fluid over a sheet with Marangoni convection and porous medium is explored. In the modelling, local thermal non-equilibrium (LTNE) conditions and heat sources are taken into account. The unique heat transport for both liquid and solid phases is provided by the LTNE model, which is based on thermal equations. As a result, various temperature profiles are used in this work for both the solid and fluid phases. It is essential for streamlining industrial procedures, improving material processing methods, comprehending biological systems like blood flow for medicine delivery, determining the environmental impact of pollutant dispersion, and increasing the effectiveness of oil and gas transportation. This model supports crucial decision-making processes in numerous disciplines by offering insights into the intricate interplay between reactive fluids, heat transmission, and chemical reactions. The appropriate similarity variables are used to compress the model equation system, and the shooting method and the conventional bvp4c solver are then used to solve the system numerically. Optimal homotopy approach is used to achieve residual errors. There are suggested best estimates for auxiliary variables. Results show that for larger values of the solvent fraction parameter, Boger fluid exhibits an enhanced velocity profile and a declining thermal profile of the liquid phase. The concentration and thermal profiles of both the solid and liquid phases are declined and enhanced the velocity of the Boger fluid for higher values of the Marangoni convection parameter.

Search for new green natural solid phases for sample preparation for PAHs determination in seafood samples followed by LC and GC–MS/MS analysis

Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic organic pollutants found in various environments, notably aquatic ecosystems and the food chain, posing significant health risks. Traditional methods for detecting PAHs in food involve complex processes and considerable reagent usage, raising environmental concerns. This study explores eco-friendly approaches suing solid phases derived from natural sources in matrix solid phase dispersion. We aimed to develop, optimize, and validate a sample preparation technique for seafood, employing natural materials for PAH analysis. Ten natural phases were compared with a commercial reference phase. The methodology involved matrix solid phase dispersion and pressurized liquid extraction, followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). Three solid phases (perlite, sweet manioc starch, and barley) showed superior performance in LC-MS/MS and were further evaluated with gas chromatography-tandem mass spectrometry (GC–Ms/MS), confirming perlite as the most effective phase. Validation followed Brazilian regulatory guidelines and European Community Regulation 2021/808/EC. The resulting method offered advantages in cost-effectiveness, reduced environmental impact, cleaner extracts, and enhanced analytical performance compared to the reference solid phase and LC-MS/MS. Proficiency analysis confirmed method reliability, with over 50% alignment with green analytical chemistry principles. In conclusion, this study developed an environmentally sustainable sample preparation technique for seafood analysis using natural solid phases, particularly perlite, for PAH determination.

Theory of elastic wave propagation in a fluid-saturated multi-porous medium with multi-permeability

This paper establishes the concept of elastic wave propagation in a multi-porous medium with different permeabilities by assuming there are n distinct pore fluid phases. The dynamic equation of motion of elastic wave propagation through this multi-porous medium is derived based on Lagrangian mechanics. In this regard, the generalized form of mass coefficients and then the energy loss due to the fluid phases in terms of dissipation coefficients are presented for low-frequency limits with the help of Darcy’s Law of multi-phases system. The elastic coefficients of the constitutive equation in terms of compliance matrix are identified using a series of Gedanken experiments. Some significant results regarding the compressional and rotational waves in a multi-porosity medium are derived. The validation of the theory has been shown by comparing it with the existing theory of single and double porosity. It is observed that there are ( n + 1 ) compressional waves corresponding to solid and fluid phases, whereas only one rotational wave is associated with the solid phase. The concept of multi-porosity theory can contribute to a deeper understanding of wave behaviour in a porous medium.

Structural pathway for nucleation and growth of topologically close-packed phase from parent hexagonal crystal

The solid diffusive phase transformation involving the nucleation and growth of new phase particles is universal and frequently employed but has not yet been fully understood at the atomic level. Here, our first-principles calculations reveal a structural formation pathway of a series of topologically close-packed (TCP) phases within the hexagonally close-packed (hcp) matrix. The results show that the nucleation follows a nonclassical nucleation process, and apart from atomic diffusion, the entire hcp→TCP transformation only involves shuffle-based displacements, with a specific 3-layer unstable hcp-ordering serving as the basic structural transformation unit (BSTU). The thickening of plate-like TCP phases relies on the formation of these unstable hcp-orderings at their coherent TCP/matrix interface to nucleate a ledge, but the ledge lacks the dislocation characteristics which is commonly considered in the conventional view. Additionally, the atomic structure of the critical nucleus for the Mg2Ca and MgZn2 Laves phases was predicted in terms of Classical Nucleation Theory (CNT). The formation of polytypes and off-stoichiometry in TCP precipitates is found to be related to the nonclassical nucleation behavior. These insights contribute to a deeper understanding of solid diffusive phase transformations at the atomic level and provide a foundation for investigating other technologically significant transformations.

A crystallization method with significant industrial potential for the separation and enrichment of silver from crude lead

Approximately 60 % of silver is produced through lead smelting systems, where silver is mainly concentrated in crude lead. Silver in crude lead is usually separated and enriched during lead refining processes. However, these methods are disadvantageous owing to their lengthy processes and high energy consumption. In this study, a novel, green, and efficient process for silver separation and enrichment via crystallization was developed. Theoretical analysis showed that the equilibrium distribution coefficient (K0) is less than 1. At 327.50 °C, silver was completely separated in the solid phase, while at 304.10 °C, silver was enriched to 2.5 wt% in the liquid phase. Experimental studies showed that, through crystallization, the silver content in low-silver lead was reduced to 0.0047 wt%, achieving a separation rate of 95.41 %. Concurrently, the silver content in rich-silver lead was enriched to 0.5690 wt% with an enrichment ratio of 7.10, consuming 185 kW·h/t of electricity. The silver content in low-silver lead was found to be lower than the Standard Specification for Refined lead, and the rich-silver lead was used for silver refining. Compared to existing processes, this method can efficiently enrich silver from crude lead in a single step. This study provides a sustainable method for silver recovery from crude Pb, offering advantages such as a short process duration, cleanliness, and ease of industrial implementation and promotion. This study offers important theoretical and technological guidance for the extraction of silver from crude lead, ensuring a secure supply of silver for major national projects.

MOSARIX: Multi-crystal spectrometer in the tender x-ray range at SOLEIL synchrotron.

We have built and commissioned a novel standalone multi-crystal x-ray spectrometer (MOSARIX) in the von Hamos configuration based on highly annealed pyrolytic graphite crystals. The spectrometer is optimized for the energy range of 2-5keV, but this range can be extended up to 20keV by using higher reflection orders. With its nine crystals and a Pilatus detector, MOSARIX achieves exceptional detection efficiency with good resolving power (better than 4000), opening the door to study small cross section phenomena and perform fast in situ measurements. The spectrometer operates under a He atmosphere, which provides a flexible sample environment for measurements in gas, liquid, and solid phases.

Temporal and spatial evolution of different heavy metal fractions and correlation with environmental factors after prolonged acid mine drainage irrigation: A column experiment

Acid mine drainage (AMD) has global significance due to its low pH and elevated heavy metal content, which have received widespread attention. After AMD irrigation in mining areas, heavy metals are distributed among soil layers, but the influencing factors and mechanisms remain unclear. AMD contamination of surrounding soil is primarily attributed to surface runoff and irrigation and causes significant environmental degradation. A laboratory soil column experiment was conducted to investigate the temporal and spatial distribution of the heavy metals Cd and Cu, as well as the impact of key environmental factors on the migration and transformation of these heavy metals following long-term soil pollution by AMD. After AMD addition, the soil exhibited a significant increase in acidity, accompanied by notable alterations in various environmental parameters, including soil pH, Eh, Fe(II) content, and iron oxide content. Over time, Cd and Cu in the soil mainly existed in the exchangeable and carbonate-bound fractions. In spatial terms, exchangeable Cu increased with increasing depth. Pearson correlation analysis indicated significant negative correlations between pH and Cu, Cd, and Eh in pore water, as well as negative correlations between pH and the exchangeable fraction of Cd (F1), carbonate-bound fraction of Cd (F2), and exchangeable fraction of Cu (F1) in the solid phase. Additionally, a positive correlation was observed between pH and the residual fraction of Cu (F5). Furthermore, the soil total Cd content exhibited a positive correlation with pyrophosphate-Fe (Fep) and dithionite-Fe (Fed), while CdF1, CdF2, total Cu, and CuF1 displayed positive correlations with Fep. Our findings indicate that the presence of AMD in soil leads to alterations in the chemical fractions of Cd and Cu, resulting in enhanced bioavailability. These results offer valuable insights for developing effective remediation strategies for soils near mining sites.

Solid phase speciation controls copper mobilisation from marine sediments by methanobactin

Although marine environments represent huge reservoirs of the potent greenhouse gas methane, they currently contribute little to global net methane emissions. Most of the methane is oxidized by methanotrophs, minimizing escape to the atmosphere. Aerobic methanotrophs oxidize methane mostly via the copper (Cu)-bearing enzyme particulate methane monooxygenase (pMMO). Therefore, aerobic methane oxidation depends on sufficient Cu acquisition by methanotrophs. Because they require both oxygen and methane, aerobic methanotrophs reside at oxic-anoxic interfaces, often close to sulphidic zones where Cu bioavailability can be limited by poorly soluble Cu sulphide mineral phases. Under Cu-limiting conditions, certain aerobic methanotrophs exude Cu-binding ligands termed chalkophores, such as methanobactin (mb) exuded by Methylosinus trichosporium OB3b. Our main objective was to establish whether chalkophores can mobilise Cu from Cu sulphide-bearing marine sediments to enhance Cu bioavailability.Through a series of kinetic batch experiments, we investigated Cu mobilisation by mb from a set of well-characterized sulphidic marine sediments differing in sediment properties, including Cu content and phase distribution. Characterization of solid-phase Cu speciation included X-ray absorption spectroscopy and a targeted sequential extraction. Furthermore, in batch experiments, we investigated to what extent adsorption of metal-free mb and Cu-mb complexes to marine sediments constrains Cu mobilisation.Our results are the first to show that both solid phase Cu speciation and chalkophore adsorption can constrain methanotrophic Cu acquisition from marine sediments. Only for certain sediments did mb addition enhance dissolved Cu concentrations. Cu mobilisation by mb was not correlated to the total Cu content of the sediment, but was controlled by solid-phase Cu speciation. Cu was only mobilised from sediments containing a mono-Cu-sulphide (CuSx) phase. We also show that mb adsorption to sediments limits Cu acquisition by mb to less compact (surface) sediments. Therefore, in sulphidic sediments, mb-mediated Cu acquisition is presumably constrained to surface-sediment interfaces containing mono-Cu-sulphide phases.