Selective leaching of indium from spent LCD screens by siderophore desferrioxamine E.

Given the criticality of indium (In) in high-tech applications, spent LCD screens can represent a viable secondary In resource. In this work, an innovative and alternative technology to selectively leach In from spent LCD screens using a microbial chelating agent, desferrioxamine E (DFOE), was developed. Indium was concentrated from spent LCD screens by implementing an adapted pre-treatment procedure, allowing the isolation of an indium-rich glassy fraction. During leaching, the competition between aluminum (Al) and In for complexation with DFOE leads to the precipitation of In(OH)3 at low DFOE concentrations (12-240 µM). After adjusting the optimal conditions (fraction size: 0-36 µM, pH: 5.5, S/L ratio: 1 g/L, 25 °C), the In leaching yield reached 32%, ten times higher than Al over 90 days with 5 mM DFOE. Thus, achieving high In recovery is possible through i) prolonging leaching durations, ii) selective leaching, and iii) minimizing Al interference. This is the first attempt to selectively leach In using a selected siderophore from end-of-life products with high concentrations of non-targeted elements (i.e. Al, Si, and Ca). This study demonstrates the potential of generating indium-rich leachates, which can be subsequently processed through the GaLIophore technology for In refining.

Redox control of chromium in the red soils from China evidenced by Cr stable isotopes.

With chromium isotopes, we study the intricate dynamics of adsorption and redox processes in soil ecosystems, focusing on chromium's behaviour, in red soil profiles enriched with iron-manganese nodules (FMNs) in South China. Key findings reveal that the primary geological source of chromium in the red soil profiles is the weathering of colluvium parent minerals. FMNs have higher chromium concentrations (325-1451 µg/g) compared to surrounding soils (95-247 µg/g) and display stable δ53Cr values (0.78 ± 0.17‰), indicating their role as stable chromium repositories, reflecting historical processes. Furthermore, by isolating chromium associated with iron oxides (FeO) and silicate minerals (ReS) within FMNs and surrounding soils using CBD extractions, we show that FeO predominantly carry chromium, particularly in FMNs. The δ53Cr values of FeO fractions consistently exhibit heavier signatures than ReS fractions, suggesting the sequestration of isotopically heavy chromium (VI) during Fe oxide precipitation. Fluctuations in soil's redox, rather than land use, play a pivotal role in controlling the precipitation of Fe oxides in surrounding soils and the formation of FMNs, thus influencing chromium mobility. This highlights the significance of these factors when utilizing chromium isotopic techniques for source tracking in soil systems, contributing to our understanding of chromium's behaviour in soil environments.

Recovery technologies for indium, gallium, and germanium from end-of-life products (electronic waste) - A review.

Advanced high-tech applications for communication, renewable energy, and display, heavily rely on technology critical elements (TCEs) such as indium, gallium, and germanium. Ensuring their sustainable supply is a pressing concern due to their high economic value and supply risks in the European Union. Recovering these elements from end-of-life (EoL) products (electronic waste: e-waste) offers a potential solution to address TCEs shortages. The review highlights recent advances in pre-treatment and hydrometallurgical and biohydrometallurgical methods for indium, gallium, and germanium recovery from EoL products, including spent liquid crystal displays (LCDs), light emitting diodes (LEDs), photovoltaics (PVs), and optical fibers (OFs). Leaching methods, including strong mineral and organic acids, and bioleaching, achieve over 95% indium recovery from spent LCDs. Recovery methods emphasize solvent extraction, chemical precipitation, and cementation. However, challenges persist in separating indium from other non-target elements like Al, Fe, Zn, and Sn. Promising purification involves solid-phase extraction, electrochemical separation, and supercritical fluid extraction. Gallium recovery from spent GaN and GaAs LEDs achieves 99% yield via leaching with HCl after annealing and HNO3, respectively. Sustainable gallium purification techniques include solvent extraction, ionic liquid extraction, and nanofiltration. Indium and gallium recovery from spent CIGS PVs achieves over 90% extraction yields via H2SO4 with citric acid-H2O2 and alkali. Although bioleaching is slower than chemical leaching (several days versus several hours), indirect bioleaching shows potential, achieving 70% gallium extraction yield. Solvent extraction and electrolysis exhibit promise for pure gallium recovery. HF or alkali roasting leaches germanium with a high yield of 98% from spent OFs. Solvent extraction achieves over 90% germanium recovery with minimal silicon co-extraction. Solid-phase extraction offers selective germanium recovery. Advancements in optimizing and implementing these e-waste recovery protocols will enhance the circularity of these TCEs.

Titanium nanoparticles fate in small-sized watersheds under different land-uses.

Surface waters from three catchments having contrasting land-uses (forested, agricultural, and urban) were sampled monthly and analysed for nanoparticulate titanium dioxide (NPs-TiO2) by single particle ICPMS and electron microscopy. We report one-year of data for NPs-TiO2 having average number and mass concentrations of 9.1 × 108 NPs-TiO2 particles L-1 and 11 µg NPs-TiO2 L-1 respectively. An increase in concentration during warmer months is observed in the forested and agricultural catchments. Both concentrations of NPs-TiO2 are within the range of recently reported values using similar analytical approaches. The positive correlations for NPs-TiO2 mass concentration or particle number with the concentration of some trace elements and DOC in the forested and agricultural catchments suggest the detected NPs-TiO2 in these two systems are mostly from geogenic origin. Additionally, microscopy imaging confirmed the presence of NPs in the three catchments. Furthermore, the land-area normalized annual flux of NPs-TiO2 (1.65 kg TiO2 year-1 km-2) was highest for the agricultural catchment, suggesting that agricultural practices have a different impact on the NPs-TiO2 dynamics and exports than other land-uses (urban or forestry). A similar trend is also found by the reanalysis of recent literature data.

Detection of nanoparticles by single-particle ICP-MS with complete transport efficiency through direct nebulization at few-microlitres-per-minute uptake rates.

Measurement of nanoparticle (NP) concentration and size by single-particle inductively coupled plasma mass spectrometry (spICP-MS) usually requires the use of a NP reference material to determine the loss of NPs and/or ions during their transport from the sample solution to the detection system. The determination of this loss, qualified as nebulization efficiency (ηNebulization) and/or transport efficiency (ηTransport), is time-consuming, costly and lacks reliability. Nebulization of the NPs directly into the plasma (without a spray chamber) results in ηNebulization = 100% and is thus a promising strategy to avoid these calibration steps. In this work, we used the µ-dDIHEN introduction system: a demountable direct injection high-efficiency nebulizer (dDIHEN) hyphenated to a flow-injection valve and a gas displacement pump. For the first time with a continuous flow nebulizer, complete transport efficiency was reached (i.e. ηTransport = 100%). Operated at a very low uptake rate (as low as 8 µL min-1), the µ-dDIHEN accurately and reproducibly determined average diameters of Au-, Ag- and Pt-NPs, in full agreement with their reference values. It was also successfully tested for Au-NPs in complex matrices, such as surface waters. spICP-MS analyses with the µ-dDIHEN sample introduction system only require a dissolved standard calibration to determine NP average diameter (dNPs in nm) and number concentration (NNPs) from the simplified set of equations: [Formula: see text] and [Formula: see text]Graphical abstract.

Comparison of the properties of standard soil and aquatic fulvic and humic acids based on the data of differential absorbance and fluorescence spectroscopy.

This study compared effects of pH, ionic strength and complexation with Mg2+ on the chromophores and fluorophores of aquatic and terrestrial NOM exemplified by the standard isolates Suwannee River fulvic and humic acid (SRFA and SRHA) and Pahokee Peat fulvic and humic acids (PPFA and PPHA) provided by the International Humic Substance Society (IHSS). The intensity of the differential spectra of the NOM isolates increased monotonically with pH. These spectra comprised contributions of similar chromophore systems associated with the carboxylic and phenolic moieties. The intensity of SRFA and PPFA fluorescence changed non-monotonically vs. pH indicating that the deprotonation of the phenolic fluorophores decreased their emission yields. Examination of the effects of pH on the slopes of the log-transformed absorbance of NOM showed that the influence of deprotonation on the conformations of PPFA and PPHA molecules was less prominent than those for SRFA but not dissimilar to those of SRHA. Changes of the differential spectra and spectral slopes showed that Mg2+/PPFA and Mg2+/PPHA complexation was more effected by electrostatic interactions while the involvement of phenolic groups was notable for SRFA. The observed trends highlight similarities and differences in the properties of the chromophores and fluorophores in the standard isolates of soil and aquatic NOM. These results necessitate further systematic comparison of the properties of NOM isolates and those of unaltered NOM.

Solid/liquid ratios of trace elements and radionuclides during a Nuclear Power Plant liquid discharge in the Seine River: Field measurements vs geochemical modeling.

This study focuses on the determination of field solid/liquid ratios (Rd) values of trace element (TE) and radionuclide (RN) in the Seine River (France) during a concerted low radioactivity level liquid regulatory discharge performed by a Nuclear Power Plant (NPP) and their confrontation with Kd values calculated from geochemical modeling. This research focuses on how field Rd measurements of TE and RN can be representative of Kd values and how Kd models should be improved. For this purpose 5 sampling points of the Seine River during a NPP's liquid discharge were investigated: upstream from the discharge in order to assess the natural background values in the area of effluent discharge, the total river water mixing distance (with transect sampling), and 2 points downstream from this last area. The main parameters required determining field Rd of TE and RN and their geochemical modeling (Kd) were acquired. Filtered waters were analyzed for alkalinity, anions, cations, dissolved organic carbon (DOC), TE, and RN concentrations. Suspended particulate matter (SPM) was analyzed for particulate organic carbon (POC), TE and RN concentrations and mineralogical composition. Field Rd and Kd values are in good agreement for stable Cd, Cu, Ni, Pb and Zn and for 7Be. Conversely, measured field Rd for stable Ag, Ba, Sr, Co and Cs are systematically higher than modeled Kd values. Even if only the lowest possible values were obtained for 137Cs and 60Co Rd measurements, these estimated limits are higher than calculated Kd for 137Cs and in good agreement for 60Co. Finally, only two RN exhibit field Rd lower than calculated Kd: 234Th and 210Pb. Comparison of field Rd vs. modeled Kd values for TE and RN allows the identification, for each element, of the main involved adsorption phases and geochemical mechanisms controlling their fate and partitioning in river systems.

Effect of natural organic matter on thallium and silver speciation.

Natural organic matter (NOM) is known to play an important role in the transport and binding of trace metal elements in aquatic and soil systems. Thallium is a pollutant for which the extent of the role played by NOM is poorly known. Consequently, this study investigates thallium(I) and its complexation to a purified humic substance as proxy for NOM. Experiments were performed with the Donnan Membrane Technique to separate, for the first time, the free Tl+ ion from its complexed form in the bulk solution. Various pH and concentrations were investigated at constant ionic strength and constant NOM proxy concentrations in solution. Experimental results were described with NICA-Donnan model. Thallium complexation was compared to silver complexation using literature data and using the same NICA-Donnan formalism. Parameters for these two cations (Tl+ and Ag+) are reported in this article, for the first time. Results display low thallium complexation to the NOM proxy while silver competes with divalent cations for the NOM binding sites. Calculated speciation for dissolved thallium highlights the dominance of free thallium (Tl+) in solution whereas Tl-NOM complexes contribute roughly 15% to total Tl(I) species in river and lake type waters. Similar results are obtained for soil solutions, Tl-bound to NOM < 30% of total, from UK soils with different land use and geochemistry.

Flow and fate of silver nanoparticles in small French catchments under different land-uses: The first one-year study.

This study focused on surface waters from three small creeks, within the Seine River watershed, which are characterized by different land-uses, namely forested, agricultural and urban. Silver nanoparticles (Ag-NPs) in these waters were detected and quantified by single-particle ICPMS during one-year of monthly sampling. Their temporal and spatial variations were investigated. Ag-NPs, in the three types of surface water, were found to range from 1.5 × 107 to 2.3 × 109 particles L-1 and from 0.4 to 28.3 ng L-1 at number and mass concentrations, respectively. These values are in consistent with the very few previous studies. In addition, the role of factors driving process and potential sources are discussed with correlations between Ag-NPs concentrations and biogeochemical parameters, like dissolved organic carbon concentration and divalent cations concentrations. For the forested watershed NOM controls the stability (number and mass) of the Ag-NPs as recently observed in the field in lake water in Germany. In the case of the agricultural and urban watersheds major cations such as Ca would control the number and mass of Ag-NPs. Dilution processes are rejected as conductivity and Cl- ions do not show significant correlations with Ag-NPs or other major geochemical parameters. The specific exportation rates of Ag-NPs for artificial, agricultural and forested areas were calculated based on the monthly data for the full year and are equal to 5.5 ± 3.0, 0.5 ± 0.3 and 0.2 ± 0.2 gy-1km-2, respectively. These data suggest a constant release of Ag-NPs from consumer products into freshwaters in artificial areas, for instance, from textiles, washing machines, domestic tap-water filters, outdoor paints. These first data of Ag-NPs fluxes in surface waters of France enlarge the very limited database of field measurements. Moreover, for the first time, the influence of time, land-use and aquatic geochemistry parameters on Ag-NPs in real natural water samples is reported. It is also helpful to further understand the fate and the process of Ag-NPs in natural waters, as well as to the ecotoxicity studies in real-world environment.

A frugal implementation of Surface Enhanced Raman Scattering for sensing Zn2+ in freshwaters - In depth investigation of the analytical performances.

Surface Enhanced Raman Scattering (SERS) has been widely praised for its extreme sensitivity but has not so far been put to use in routine analytical applications, with the accessible scale of measurements a limiting factor. We report here on a frugal implementation of SERS dedicated to the quantitative detection of Zn2+ in water, Zn being an element that can serve as an indicator of contamination by heavy metals in aquatic bodies. The method consists in randomly aggregating simple silver colloids in the analyte solution in the presence of a complexometric indicator of Zn2+, recording the SERS spectrum with a portable Raman spectrometer and analysing the data using multivariate calibration models. The frugality of the sensing procedure enables us to acquire a dataset much larger than conventionally done in the field of SERS, which in turn allows for an in-depth statistical analysis of the analytical performances that matter to end-users. In pure water, the proposed sensor is sensitive and accurate in the 160-2230 nM range, with a trueness of 96% and a precision of 4%. Although its limit of detection is one order of magnitude higher than those of golden standard techniques for quantifying metals, its sensitivity range matches Zn levels that are relevant to the health of aquatic bodies. Moreover, its frugality positions it as an interesting alternative to monitor water quality. Critically, the combination of the simple procedure for sample preparation, abundant SERS material and affordable portable instrument paves the way for a realistic deployment to the water site, with each Zn reading three to five times cheaper than through conventional techniques. It could therefore complement current monitoring methods in a bid to solve the pressing needs for large scale water quality data.

Theoretical and experimental investigation of the focusing position in asymmetrical flow field-flow fractionation (AF4).

To better understand the focusing process and to determine the focusing position (zfoc) in Asymmetrical Flow Field-Flow Fractionation (AF4), theoretical and experimental studies were performed. A new theoretical expression that allows the calculation of zfoc in AF4 channels of any shape having an axial plane of symmetry was established. The equation was then applied to the particular case of a trapezoidal AF4 channel with tapered ends. The applicability of this equation was verified by comparing the calculated results with the experimental measures of the focusing position obtained using blue dextran dye under different flow conditions. The calculated values and the experimental results were in good agreement. The total uncertainty associated with the calculated zfoc was evaluated and was lower than 10%. A good repeatability and reproducibility of the focusing position was obtained. Moreover, the effects of the sample-injection position, the spacer thickness, the membrane aging, and the nature of the injected sample on the focusing position were investigated: zfoc was not influenced by these parameters, proving the universal applicability of the equation given in this work for predicting the focusing position, when the assumption of constancy of the cross-flow velocity at the membrane, which underlies this equation, is fulfilled. Additionally, it is notable that this theoretical expression is suitable for different models of AF4 channel and not peculiar to specific suppliers.

Trace metals dynamics under contrasted land uses: contribution of statistical, isotopic, and EXAFS approaches.

Three sub-basins of the Seine River (France) under contrasted land uses (i.e., forested, agricultural, and urban) have been investigated in order to assess the origin and seasonal variation of trace metals, and evaluate their geochemical background and dynamics. Our results highlight a high anthropogenic impact on all elements for both the dissolved and particulate fractions. The main source for each element in the dissolved phase was determined and shows that transition and post-transition metals mainly originate from forested areas, while alkali and alkaline earth elements, metalloids, and halogens rather originate from agricultural land use. Conversely, for the particulate phase, most of the elements cannot be associated with a specific land use. Seasonal variation of elements was assessed according to the forested and agricultural land uses, and geochemical backgrounds were determined using average export rates, highlighting that the geochemical background for the forested land use is higher than the agricultural one for most of the elements. Finally, to confirm those results, Zn dynamics in the three characteristic sub-basins and between the different land uses was investigated using a combination of Zn speciation, Zn isotopic ratio, and Zn export rates.

Speciation and reactivity of lead and zinc in heavily and poorly contaminated soils: Stable isotope dilution, chemical extraction and model views.

Correct characterization of metal speciation and reactivity is a prerequisite for the risk assessment and remedial activity management of contaminated soil. To better understand the intrinsic reactivity of Pb and Zn, nine heavily and poorly contaminated soils were investigated using the combined approaches of chemical extractions, multi-element stable isotopic dilution (ID) method, and multi-surface modelling. The ID results show that 0.1-38% of total Pb and 3-45% of total Zn in the studied soils are isotopically exchangeable after a 3-day equilibration. The intercomparison between experimental and modelling results evidences that single extraction with 0.43 M HNO3 solubilizes part of non-isotopically exchangeable fraction of Pb and Zn in the studied soils, and cannot be used as a surrogate for ID to assess labile Pb and Zn pools in soil. Both selective sequential extraction (SSE) and modelling reveal that Mn oxides are the predominant sorption surface for Pb in the studied soils; while Zn is predicted to be mainly associated with soil organic matter in the soil with low pH and Fe/Mn oxides in the soils with high pH. Multi-surface modelling can provide a reasonable prediction of Pb and Zn adsorption onto different soil constituents for the most of the studied soils. The modelling could be a promising tool to decipher the underlying mechanism that controls metal reactivity in soil, but the submodel for Mn oxides should be incorporated and the model parameters, especially for the 2-pK diffuse layer model for Mn oxides, should be updated in the further studies.

Lead distribution in soils impacted by a secondary lead smelter: Experimental and modelling approaches.

Smelting activities are one of the most common sources of trace elements in the environment. The aim of this study was to determine the lead distribution in upper horizons (0-5 and 5-10cm) of acidic soils in the vicinity of a lead-acid battery recycling plant in northern France. The combination of chemical methods (sequential extractions), physical methods (Raman microspectroscopy and scanning electron microscopy with an energy dispersive spectrometer) and multi-surface complexation modelling enabled an assessment of the behaviour of Pb. Regardless of the studied soil, none of the Pb-bearing phases commonly identified in similarly polluted environments (e.g., anglesite) were observed. Lead was mainly associated with organic matter and manganese oxides. The association of Pb with these soil constituents can be interpreted as evidence of Pb redistribution in the studied soils following smelter particle deposition.

Influence of dissolved organic matter and manganese oxides on metal speciation in soil solution: A modelling approach.

Trace element (TE) speciation modelling in soil solution is controlled by the assumptions made about the soil solution composition. To evaluate this influence, different assumptions using Visual MINTEQ were tested and compared to measurements of free TE concentrations. The soil column Donnan membrane technique (SC-DMT) was used to estimate the free TE (Cd, Cu, Ni, Pb and Zn) concentrations in six acidic soil solutions. A batch technique using DAX-8 resin was used to fractionate the dissolved organic matter (DOM) into four fractions: humic acids (HA), fulvic acids (FA), hydrophilic acids (Hy) and hydrophobic neutral organic matter (HON). To model TE speciation, particular attention was focused on the hydrous manganese oxides (HMO) and the Hy fraction, ligands not considered in most of the TE speciation modelling studies in soil solution. In this work, the model predictions of free ion activities agree with the experimental results. The knowledge of the FA fraction seems to be very useful, especially in the case of high DOM content, for more accurately representing experimental data. Finally, the role of the manganese oxides and of the Hy fraction on TE speciation was identified and, depending on the physicochemical conditions of the soil solution, should be considered in future studies.

Eu(III)-Fulvic Acid Complexation: Evidence of Fulvic Acid Concentration Dependent Interactions by Time-Resolved Luminescence Spectroscopy.

Europium speciation is investigated by time-resolved luminescence spectroscopy (TRLS) in the presence of Suwannee River fulvic acid (SRFA). From complexation isotherms built at different total Eu(III) concentrations, pH values, ionic strength, and SRFA concentrations, it appears that two luminescence behaviors of Eu(III) are occurring. The first part, at the lowest CSRFA values, is showing the typical luminescence evolution of Eu(III) complexed by humic substances--that is, the increase of the asymmetry ratio between the (5)D0 → (7)F2 and (5)D0 → (7)F1 transitions up to a plateau--, and the occurrence of a biexponential decay--the first decay being faster than free Eu(3+). At higher CSRFA, a second luminescence mode is detected as the asymmetry ratio is increasing again after the previous plateau, and could correspond to the formation of another type of complex, and/or it can reflect a different spatial organization of complexed europium within the SRFA structure. The luminescence decay keeps on evolving but link to hydration number is not straightforward due to quenching mechanisms. The Eu(III) chemical environment evolution with CSRFA is also ionic strength dependent. These observations suggest that in addition to short-range interactions--intraparticulate complexation--, there might be interactions at longer range--interparticulate repulsion--between particles that are complexing Eu(III) at high CSRFA. These interactions are not yet accounted by the different complexation models.

Zn Isotope Fractionation during Sorption onto Kaolinite.

In this study, we quantify zinc isotope fractionation during its sorption onto kaolinite, by performing experiments under various pH, ionic strength, and total Zn concentrations. A systematic enrichment in heavy Zn isotopes on the surface of kaolinite was measured, with Δ(66)Znadsorbed-solution ranging from 0.11‰ at low pH and low ionic strength to 0.49‰ at high pH and high ionic strength. Both the measured Zn concentration and its isotopic ratio are correctly described using a thermodynamic sorption model that considers two binding sites: external basal surfaces and edge sites. Based on this modeling approach, two distinct Zn isotopic fractionation factors were calculated: Δ(66)Znadsorbed-solution = 0.18 ± 0.06‰ for ion exchange onto basal sites, and Δ(66)Znadsorbed-solution = 0.49 ± 0.06‰ for specific complexation onto edge sites. These two distinct factors indicate that Zn isotope fractionation is dominantly controlled by the chemical composition of the solution (pH, ionic strength).

The Fate of Polyol-Made ZnO and CdS Nanoparticles in Seine River Water (Paris, France).

This study aims to characterize nanoparticles with different compositions and structures as well as seeing their evolutions over time in a natural environment such as Seine river water (Paris, France). Face centered cubic (fcc) and hexagonal (hcp) CdS as well as hexagonal (hcp) ZnO nanoparticles were synthesized by the Polyol method. CdS nanoparticles (i) cfc structure: are agglomerated, present 100 nm length with heterogeneous diameter and 10 m2 g(-1) specific surface area (S(g)) from Brunauer Emett and Teller (BET) measurements; (ii) hcp structure: 20 nm and S(g) = 67 m2 g(-1). ZnO hcp nanoparticles presents 50 nm length and 15 nm diameter and S(g) = 54 m2 g(-1). These results are in agreement with X-ray diffraction (XRD), and small angle X-ray scattering (SAXs). After 48 h interaction with Seine river water, cryo-TEM analysis showed that ZnO nanoparticles form spherical agglomerates with 300 nm diameter; CdS nanoparticles (fcc) are agglomerated presenting large diameters (> 500 nm); and CdS nanoparticles (hcp) are not agglomerated and present the same characteristics of the starting material. After 168h of contact with Seine river water, CdS (fcc) presents only 14% of dissolution, CdS (hcp) presents both 60% dissolution and 30% reprecipitation in a cadmium carbonate form and finally almost 90% of ZnO nanoparticles are dissolved.

In-Situ Investigation of Interactions between Magnesium Ion and Natural Organic Matter.

Natural organic matter (NOM) generated in all niches of the environment constitutes a large fraction of the global pool of organic carbon while magnesium is one of the most abundant elements that has multiple roles in both biotic and abiotic processes. Although interactions between Mg(2+) and NOM have been recognized to affect many environmental processes, little is understood about relevant mechanisms and equilibria. This study addressed this deficiency and quantified Mg(2+)-NOM interactions using differential absorbance spectroscopy (DAS) in combination with the NICA-Donnan speciation model. DAS data were obtained for varying total Mg concentrations, pHs from 5.0 to 11.0 and ionic strengths from 0.001 to 0.3 mol L(-1). DAS results demonstrated the existence of strong interactions between magnesium and NOM at all examined conditions and demonstrated that the binding of Mg(2+) by NOM was accompanied by the replacement of protons in the protonation-active phenolic and carboxylic groups. The slope of the log-transformed absorbance spectra of NOM in the range of wavelength 350-400 nm was found to be indicative of the extent of Mg(2+)-NOM binding. The differential and absolute values of the spectral slopes were strongly correlated with the amount of NOM-bound Mg(2+) ions and with the concentrations of NOM-bound protons.

Chemical signature of magnetotactic bacteria.

There are longstanding and ongoing controversies about the abiotic or biological origin of nanocrystals of magnetite. On Earth, magnetotactic bacteria perform biomineralization of intracellular magnetite nanoparticles under a controlled pathway. These bacteria are ubiquitous in modern natural environments. However, their identification in ancient geological material remains challenging. Together with physical and mineralogical properties, the chemical composition of magnetite was proposed as a promising tracer for bacterial magnetofossil identification, but this had never been explored quantitatively and systematically for many trace elements. Here, we determine the incorporation of 34 trace elements in magnetite in both cases of abiotic aqueous precipitation and of production by the magnetotactic bacterium Magnetospirillum magneticum strain AMB-1. We show that, in biomagnetite, most elements are at least 100 times less concentrated than in abiotic magnetite and we provide a quantitative pattern of this depletion. Furthermore, we propose a previously unidentified method based on strontium and calcium incorporation to identify magnetite produced by magnetotactic bacteria in the geological record.