Biogeochemical and mineralogical effects of Fe-P-S dynamics in sediments of continental shelf sea: Impact of salinity, oxygen conditions, and catchment area characteristics.

In this study, we investigate how salinity, oxygen concentration and catchment area characteristics impact the dynamics of Fe-P-S cycling in the continental shelf sea sediments. Samples were collected from three sites representing different environmental conditions: Gdansk Deep (southern Baltic Sea), Gotland Deep (central Baltic Sea) and Bothnian Sea (northern Baltic Sea). Sediments were analysed for their mineral composition and speciation of iron and phosphorus. The main groups of Prokaryota involved in Fe-P-S cycling in sediments were indicated. Concentrations of sulphate, hydrogen sulphide, alkalinity, chloride, calcium, phosphate and iron were measured in pore waters. We demonstrated that in the eutrophicated southern region with moderate salinity and oxygen deficit in bottom water, sediments had high potential for retaining Fe and releasing P as indicated by high concentrations of pyrite and labile forms of phosphorus, respectively. Strong salinity stratification and intermittent pelagic redoxcline in the central Baltic Sea resulted in a clearly higher rate of pyrite deposition. Sediment was enriched with Mn due to the formation of Ca-Mn carbonates driven by intensive Mn redox cycling and sulphate reduction. Because of high availability of Mn oxides connected with episodic inflows of oxic seawater from the North Sea, sulphate was present in the entire profile of the studied sediments in the Gotland Deep. Sediments in the well-oxygenated, virtually fresh and rich in land-derived iron northern Baltic Sea retained significant amounts of P in authigenic minerals. Organic matter mineralisation in the surface sediment of this area was dominated by iron reduction. The variability of environmental conditions and consequent availability of electron acceptors were the cause of regional differences in the composition of Prokaryota communities - the number of sulphate reducers in the Gdansk and Gotland Deeps was greater than in the Bothnian Sea, where there were more Fe reducers and bacteria that oxidise Fe and S.

Effect of a Sulfur Precursor on the Hydrothermal Synthesis of Cu2MnSnS4.

Cu2MnSnS4 (CMTS) is acknowledged as an alternative to traditional semiconductors. The structure and microstructure of synthetic CMTS depend on, among other things, the types of sulfur sources used. Traditionally obtained CMTS mostly has a tetragonal structure. In this study, the effect of using thiourea (Tu) or Na2S as a sulfur source on the product structure was compared using hydrothermal synthesis at 190 °C for 7 days (ethylene glycol with water in the presence of poly(vinylpyrollidone) was used as a solvent). When Tu was used, CMTS precipitated in the form of concentric microspheres, 1-1.5 µm in size, consisting of hexagonal (in the cores) and tetragonal (the rims) forms. Most probably, the rapidly formed hexagonal nucleus was later surrounded by a slower-forming rim with a tetragonal structure. In contrast, when Na2S was used as a precursor, microspheres were not formed and a fine crystalline material with a homogeneous tetragonal structure was obtained. This allowed for the choice of micromorphology and product structure during synthesis.

Origin, distribution, and perspective health benefits of particulate matter in the air of underground salt mine: a case study from Bochnia, Poland.

The composition and distribution of airborne particles in different locations in a salt mine were determined in terms of their origin, the distance from the air inlet, and the adaptation of post-mining chambers and corridors for tourists and general audience. The composition of aerosols in air was also evaluated from the perspective of human health. Air samples were collected on filters by using portable air pumps, in a historical underground salt mine in Bochnia (Poland), which is currently a touristic and recreation attraction and sanatorium. The particulate matter (PM) concentration was determined using the gravimetric method by weighing quartz filters. The content of carbon, water-soluble constituents, trace elements, and minerals was also determined. A genetic classification of the suspended matter was proposed and comprised three groups: geogenic (fragments of rock salt and associated minerals from the deposit), anthropogenic (carbon-bearing particles from tourist traffic and small amounts of fly ash, soot, and rust), and biogenic particles (occasional pollen). The total PM concentration in air varied between 21 and 79 µg/m3 (with PM4 constituting 4-24 µg/m3). The amount of atmospheric dust components coming from the surface was low and decreased with the distance from the intake shaft, thus indicating the self-cleaning process. NaCl dominated the water-soluble constituents, while Fe, Al, Ag, Mn, and Zn dominated the trace elements, with the concentration of majority of them below 30 ng/m3. These metals are released into air from both natural sources and the wear or/and corrosion of mining and tourists facilities in the underground functional space. No potentially toxic elements or constituents were detected. The presence of salt particles and salty spray in the atmosphere of salt mine, which may have anti-inflammatory and antiallergic properties, is beneficial to human health. This study will allow for a broader look at the potential of halotherapy in underground salt mines from a medical and regulatory point of view.

Synthesis and Characterization of Cu2FeSnS4-Cu2MnSnS4 Solid Solution Microspheres.

In this study, we used a hydrothermal method to synthesize microspheres of Cu2(Mn1-xFex)SnS4 solid solution (X = 1, 0.8, 0.6, 0.4, 0.2, 0). The process was optimized to improve the crystallinity, morphology, and purity of the obtained materials. All samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), Raman spectroscopy, and Fourier transform infrared (FTIR) spectroscopy. The following conditions were optimized: A mixture of water and ethylene glycol at the ratio of 1:7 as the reaction medium, polyvinylpyrrolidone (PVP) as the surface ligand, and reaction temperature of 195 °C for 7 days. The product of synthesis precipitated in the form of aggregates of nanocrystals, which form homogeneous, often concentric microspheres with a diameter of 1-1.5 µm. The chemical composition of the product can be well controlled by the chemical composition of the reactants. The compound Cu2(Mn1-xFex)SnS4 forms a continuous series of solid solutions.

Thermal Stability and Decomposition Products of P-Doped Ferrihydrite.

This work aimed to determine the effect of various amounts of P admixtures in synthetic ferrihydrite on its thermal stability, transformation processes, and the properties of the products, at a broad range of temperatures up to 1000 °C. A detailed study was conducted using a series of synthetic ferrihydrites Fe5HO8·4H2O doped with phosphates at P/Fe molar ratios of 0.2, 0.5, and 1.0. Ferrihydrite was synthesized by a reaction of Fe2(SO4)3 with 1 M KOH at room temperature in the presence of K2HPO4 at pH 8.2. The products of the synthesis and the products of heating were characterized at various stages of transformation by using differential thermal analysis accompanied with X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy-energy dispersive X-ray spectroscopy. Coprecipitation of P with ferrihydrite results in the formation of P-doped 2-line ferrihydrite. A high P content reduces crystallinity. Phosphate significantly inhibits the thermal transformation processes. The temperature of thermal transformation increases from below 550 to 710-750 °C. Formation of intermediate maghemite and Fe-phosphates, is observed. The product of heating up to 1000 °C contains hematite associated with rodolicoite FePO4 and grattarolaite Fe3PO7. Higher P content greatly increases the thermal stability and transformation temperature of rodolicoite as well.

The Early Stages of Mimetite Dissolution in EDTA Studied with Atomic Force Microscopy and Scanning Electron Microscopy.

A mineral, mimetite Pb5(AsO4)3Cl, is one of the most insoluble minerals and continues to be considered a viable remedial strategy for immobilization of Pb and As from contaminated soils. It has been recognized that many well-known, naturally-occurring, and synthetic chelators strongly influence dissolution processes in near-surface geological environments. In this study, crystals of mimetite were observed in scanning electron microscopy (SEM) and atomic force microscopy (AFM) before and after dissolution in EDTA (ethylene diamine tetra-acetic acid) solution. Direct in situ observations at room temperature made in an AFM fluid cell revealed that the grain surface roughness has increased due to development of etch pits. Both hexagonal and prismatic walls developed dissolution features between 0.6 and 1.2 µm, respectively, during duration of the experiment. AFM observations suggest surface-controlled dissolution dominated step retrieval on both prismatic and hexagonal surfaces. SEM observations showed the development of rounded edges on hexagonal walls and elongated, oval etch pits on the prismatic wall. These results, representing early dissolution patterns on mimetite surfaces, might suggest that low pH conditions in soils containing organic acids similar to EDTA might contribute to remobilization of Pb and As from mimetite when applied to stabilization of these toxic metals in contaminated soils.

Raman and Fourier transform infrared spectroscopic study of pyromorphite-vanadinite solid solutions.

Due to the great range of the application fields for apatites, there is a strong need to complete the data set determining the properties of these minerals. In this study, Raman and Infrared spectra of the phases from pyromorphite Pb5(PO4)3Cl - vanadinite Pb5(VO4)3Cl series were investigated. Totally, 9 samples (2 end-members and 7 solid solutions of the series) were synthesized at 25°C and pH=3.5, and analyzed. In the Raman and Infrared spectra of the studied Pb-apatites, the bands typical for the vibrations in the PO4 and the VO4 tetrahedra appeared. The bands attributed to the stretching vibrations (ν1, ν3) occurred in the 1050-910cm-1 and 830-720cm-1 regions, whereas the bending vibrations (ν2, ν4) were visible at the 580-540cm-1, 430-380cm-1 and 370-290cm-1 range. The position of the bands depended on the P/(P+V) ratio in the analyzed solid, since there are differences in the ionic radii and the atomic mass of P5+ and V5+, which affect the bong lengths, bond forces and the banding energies of the substituting tetrahedra. The analysis allowed observing gradual shifts of the bands caused by the replacement of phosphorous with vanadium in the studied phases. The positions and the intensities of selected bands are proposed to serve as a semi-quantitative estimation of the chemical composition of the phases from the pyromorphite - vanadinite series.

Solubilization of Pb-bearing apatite Pb5(PO4)3Cl by bacteria isolated from polluted environment.

The main purpose of this study was to test if microorganisms isolated from heavily polluted environments can enhance dissolution of Pb-apatite (pyromorphite) resulting in remobilization of lead. Three bacterial strains belonging to the genus Pseudomonas isolated from underground mines in SW Poland were used in batch experiments of pyromorphite solubilization carried out in phosphate reach and phosphate poor media. Bacteria growth and evolution of Pb and phosphate concentrations as well as pH were determined. Additionally the concentration of bacterial siderophores in leaching solution was assayed. All bacterial strains were able to grow in both media in the presence of pyromorphite. The number of bacterial cells was from one to two orders of magnitude higher in the phosphate rich media. In the phosphate poor media the only source of P was the dissolving lead apatite. Bacteria enhanced the solubility of pyromorphite resulting in elevated Pb concentrations, up to 853 µg L-1 in phosphate-rich medium and 6112 µg L-1 in phosphate-poor medium, compared to less than 100 µg L-1 in an abiotic control sample. Production of siderophores was characteristic for each culture and was much lower (10-1000 fold) in the phosphate-poor medium. This study demonstrates for the first time that indigenous bacteria can directly and indirectly promote the mobilization of lead from pyromorphite. This phenomenon should be considered in long term risk assessment of Pb contaminated soils after reclamation processes because bacteria can play a significant role in the efficiency of clean-up efforts and overall geochemical cycling of Pb.

Mimetite Formation from Goethite-Adsorbed Ions.

Bioavailability of arsenic in contaminated soils and wastes can be reduced to insignificant levels by precipitation of mimetite Pb5(AsO4)3Cl. The objective of this study is to elucidate mechanisms of the reaction between solution containing lead ions and arsenates adsorbed on synthetic goethite (AsO4-goethite), or arsenate ions in the solution and goethite saturated with adsorbed Pb (Pb-goethite). These reactions, in the presence of Cl, result in rapid crystallization of mimetite. Formation of mimetite is faster than desorption of AsO4 but slower than desorption of Pb from the goethite surface. Slow desorption of arsenates from AsO4-goethite results in heterogeneous precipitation and formation of mimetite incrustation on goethite crystals. Desorption of lead from Pb-goethite is at least as fast as diffusion and advection of AsO4 and Cl in suspension allowing for homogeneous crystallization of mimetite in intergranular solution. Therefore, the mechanism of nucleation is primarily driven by the kinetics of constituent supply to the saturation front, rather than by the thermodynamics of nucleation. The products of the reactions are well documented using microscopy methods such as scanning electron microscopy, electron backscattered diffraction, X-ray diffraction, and Fourier transform infrared spectroscopy.

Arsenate substitution in lead hydroxyl apatites: A Raman spectroscopic study.

A total of seven compounds of the hydroxylpyromorphite Pb10(PO4)6(OH)2 - hydroxylmimetite Pb10(AsO4)6(OH)2 (HPY-HMI) solid solution series were synthesized at 80°C from aqueous solutions and characterized using Raman spectroscopy. The positions of the bands in all spectra of the series depend on the content of arsenates and phosphates shifting to lower wavenumbers with substitution of (AsO4)(3-) for (PO4)(3-). This shift results from the decreasing bond strength of X-O (where X=P, As) and higher atomic mass of As than P. The position and intensity of major (PO4)(3-) and (AsO4)(3-) bands in Raman spectra exhibit linear correlation with As content, while the ratio of the intensities of these peaks shows exponential correlation. This results due to different polarizability of (PO4)(3-) and (AsO4)(3-) molecules. A small carbonate band develops with increasing As content indicating that hydroxyl lead apatites adopt the (CO3)(2-) ions, particularly at the arsenate end of the series.

Petrophysical examination of CO2-brine-rock interactions-results of the first stage of long-term experiments in the potential Zaosie Anticline reservoir (central Poland) for CO2 storage.

The objective of the study was determination of experiment-induced alterations and changes in the properties of reservoir rocks and sealing rocks sampled from potential reservoir for CO2. In the experiment, rocks submerged in brine in specially constructed reactors were subjected to CO2 pressure of 6 MPa for 20 months at room temperature. Samples of Lower Jurassic reservoir rocks and sealing rocks (sandstones, claystones, and mudstones) from the Zaosie Anticline (central Poland) were analysed for their petrophysical properties (specific surface area, porosity, pore size and distribution) before and after the experiment. Comparison of the ionic composition the brines before and after the experiment demonstrated an increase in total dissolved solids as well as the concentration of sulphates and calcium ions. This indicates partial dissolution of the rock matrix and the cements. As a result of the reaction, the properties of reservoir rocks did not changed significantly and should not affect the process of CO2 storage. In the case of the sealing rocks, however, the porosity, the framework density, as well as the average capillary and threshold diameter increased. Also, the pore distribution in the pore space changed in favour of larger pores. The reasons for these changes could not be explained by petrographic characteristics and should be thoroughly investigated.

Pb remobilization by bacterially mediated dissolution of pyromorphite Pb5(PO4)3Cl in presence of phosphate-solubilizing Pseudomonas putida.

Remediation of lead (Pb)-contaminated sites with phosphate amendments is one of the best studied and cost-effective methods for in situ immobilization. In this treatment, a very stable mineral, pyromorphite Pb5(PO4)3Cl, is formed. Several studies propose to improve this treatment method with the addition of phosphate-solubilizing bacteria (PSB). The effect of bacteria on solubilization of pyromorphite is unknown. In this study, the effect of the soil microorganisms on the stability of pyromorphite Pb5(PO4)3Cl has been investigated in a set of batch solution experiments. The mineral was reacted with Pseudomonas putida, a common soil microorganism. Dissolution of pyromorphite was enhanced by the presence of P. putida, resulting in an elevated Pb concentration in the solution. This occurred even when the bacteria were provided with an additional source of phosphate in the solution. Pyromorphite has been shown to be a potential source of nutrient phosphorus for common soil bacteria. Thus, the use of PSB in remediation treatments of Pb contaminated sites may have adverse long-term impacts on Pb immobilization. Conscious phosphate management is suggested for long-term sustainability of the in situ Pb immobilization by pyromorphite formation.

A comparative study of the most effective amendment for Pb, Zn and Cd immobilization in contaminated soils.

The problem of an extensive contamination of soils with metals can be resolved using an in situ chemical immobilization technology. Five substances (natural zeolite, bog iron ore, "Polifoska 15" fertilizer, triple superphosphate, diammonium phosphate) were tested to determine their efficiency to immobilize Zn, Pb and Cd in smelter-contaminated soil in the Upper Silesia region. Soil samples were collected at three sites located in the vincity of a Pb-Zn smelter and a sludge landfill near the town of Bukowno. Effective reduction of leachable and fitoavailable Zn, Pb and Cd concentrations in soil was observed after addition of diammonium phosphate, "Polifoska 15" fertilizer and bog iron ore amendments. Additional test proved that immobilization effect gained by these amendments sustains at low-temperature conditions. It was noticed that phosphate addition resulted in lowering pH and mobilization of As(V) in soils. Good immobilization effectiveness and lack of major adverse effects of bog iron application suggest that this is the method of choice.

Synchrotron-based X-ray diffraction of the lead apatite series Pb(10)(PO(4))(6)Cl(2)-Pb(10)(AsO(4))(6)Cl(2).

A number of compounds of the pyromorphite-mimetite solid solution series were synthesized at room temperature and analyzed with infrared spectroscopy and powder X-ray diffraction. High-resolution high-quality powder diffraction data were obtained by means of the state-of-the-art instrument at the 11-BM beamline of the Advanced Photon Source at Argonne National Laboratory, Argonne, IL, USA. The unit-cell dimensions, atomic position and atomic displacement parameters, as well as site occupancy for analyzed phases, were refined by the Rietveld method and reported herein for the first time. The results of this study indicate that the pyromorphite-mimetite series is continuous in near-Earth-surface environments. Detailed structural changes caused by P(5+)-As(5+) substitutions in minerals from the pyromorphite-mimetite solid solution series are reported.

Immobilization of aqueous cadmium by addition of phosphates.

In situ immobilization of heavy metals in polluted soils using phosphates leads to formation of products which are highly insoluble and thermodynamically stable over a broad pH and Eh range. In this research effectivity of Cd ions immobilization (initial [Cdaq]-4.800 mM) from aqueous solutions by different phosphorus compounds (K2HPO4, NH4H2PO4 and "Polifoska 15" fertilizer) was compared at pH in the range 4.00-9.00 and for reaction times 2-1440 h. The highest reduction of cadmium concentration (>99%), owing due to the formation of cadmium phosphates, was observed for all used phosphorus sources within pH range of 6.75-9.00. Uptake of cadmium for pH< or =5.00 did not exceed 80% and was lowest in the reaction with "Polifoska 15" fertilizer (28.25%). Identification of phases formed in the reactions using XRD, FTIR and SEM-EDS-EBSD was carried out. It was noticed that crystallinity of formed solid decreased with pH increase. Formation of Cd5H2(PO4)4.4H2O was observed in acidic conditions (pH< or =5.00), at pH approximately 7.00 mixture of following cadmium phosphates Cd(H2PO4)2, Cd3(PO4)2 and Cd5H2(PO4)4.4H2O was formed. Amorphic cadmium phosphates were noticed in alkaline conditions (pH>8.50).