Feroxyhyte - from synthesis and characterization to application.

Feroxyhyte (δ-FeOOH) was synthesized and characterized using X-ray diffractometry (XRD), simultaneous thermal analysis (STA), scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDS), and low-temperature nitrogen adsorption-desorption measurements. Its potential application as adsorbent of an anionic and cationic dyes such as C.I. Acid Violet 1 (AV1) and C.I. Basic Blue 3 (BB3) was investigated by determining the adsorption capacities based on the Langmuir (36.6 mg/g for AV1 and 187 mg/g for BB3), Freundlich and Dubinin-Radushkevich isotherm models. Adsorption of AV1 and BB3 by δ-FeOOH drops with the presence of additives such as cationic and anionic surfactants (CTAB, SDS) and ionic polymers (PAA, PEI). The surface and electrokinetic properties of examined suspensions were also described. They include determination of the solid surface charge density and the zeta potential, as well as values of point of zero charge and isoelectric point of feroxyhyte particles without and with adsorbed layers of organic substances. Their analysis made possible to propose the most probable structure of electrical double layer formed at the iron mineral/aqueous solution interface.

Reduction of bioavailability and phytotoxicity effect of cadmium in soil by microbial-induced carbonate precipitation using metabolites of ureolytic bacterium Ochrobactrum sp. POC9.

The application of ureolytic bacteria for bioremediation of soil contaminated with heavy metals, including cadmium (Cd), allows for the efficient immobilization of heavy metals by precipitation or coprecipitation with carbonates. Microbially-induced carbonate precipitation process may be useful also in the case of the cultivation of crop plants in various agricultural soils with trace but legally permissible Cd concentrations, which may be still uptaken by plants. This study aimed to investigate the influence of soil supplementation with metabolites containing carbonates (MCC) produced by the ureolytic bacterium Ochrobactrum sp. POC9 on the Cd mobility in the soil as well as on the Cd uptake efficiency and general condition of crop plants (Petroselinum crispum). In the frame of the conducted studies (i) carbonate productivity of the POC9 strain, (ii) the efficiency of Cd immobilization in soil supplemented with MCC, (iii) crystallization of cadmium carbonate in the soil enriched with MCC, (iv) the effect of MCC on the physico-chemical and microbiological properties of soil, and (v) the effect of changes in soil properties on the morphology, growth rate, and Cd-uptake efficiency of crop plants were investigated. The experiments were conducted in soil contaminated with a low concentration of Cd to simulate the natural environmental conditions. Soil supplementation with MCC significantly reduced the bioavailability of Cd in soil with regard to control variants by about 27-65% (depending on the volume of MCC) and reduced the Cd uptake by plants by about 86% and 74% in shoots and roots, respectively. Furthermore, due to the decrease in soil toxicity and improvement of soil nutrition with other metabolites produced during the urea degradation (MCC), some microbiological properties of soil (quantity and activity of soil microorganisms), as well as the general condition of plants, were also significantly improved. Soil supplementation with MCC enabled efficient Cd stabilization and significantly reduced its toxicity for soil microbiota and plants. Thus, MCC produced by POC9 strain may be used not only as an effective Cd immobilizer in soil but also as a microbe and plant stimulators.

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.

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.

Behavior of Ag species in presence of aquatic sediment minerals - In context of aquatic environmental safety.

In recent years, there has been a growth in the number of products containing Ag nanoparticles (AgNPs) in many areas and their use suggests that the water-soil environment may be exposed to the contaminant with different Ag species. Therefore, the sorption of two Ag forms (i.e. Ag(I) ions and nanoparticles - AgNPs) on clay minerals (montmorillonite and kaolinite) and iron (oxyhydr)oxides (ferrihydrite) as a function of solution:mineral ratio (100:1, 250:1, 500:1), solution pH (3.0, 5.5 and 7.0) and initial Ag concentration (0.1-100 mg/dm3) was studied using batch method. In addition the binding strength/mobility of the bonded Ag species was researched. The results show a great sorption potential of clay minerals for both Ag forms and lower sorption capacity of ferrihydrite, in particular for Ag(I) ions. The maximum sorption capacities of montmorillonite, kaolinite and ferrihydrite estimated from three-parameter isotherm model of Sips were 94.39 mg/g, 117.8 mg/g and 26.48 mg/g for AgNPs and 17.92 mg/g, 21.14 mg/g and 3.072 mg/g for Ag(I) ions, respectively. Aggregation process plays an important role in sorption and mobility of AgNPs. The sequential extraction study indicated different binding mechanisms of the Ag forms onto the clay minerals and ferrihydrite, which depended on the active sites of minerals as well as the Ag species nature in the solution. Ag(I) was weakly bound by clay minerals but presence of iron (oxyhydr)oxides decreased the Ag(I) mobility and bioavailability. On the other hand, AgNPs bound with the active centers of minerals in a very strong way and were not able to release into water. The study of the binding of Ag forms by clay minerals and (oxyhydr)oxides allows to determine the influence of their physicochemical and structural properties, including e.g. pore size on Ag sorption. These results allow these properties to be taken into account in the study of environmental samples, including waters and soils. Moreover, the results showed that in the study of behavior of Ag forms in contact with the minerals, in addition to the sorption capacity, the susceptibility to their release is very important. Studies on sorption/desorption of AgNPs and Ag(I) ions as a form of oxidation of AgNPs is important for understanding the transport and fate of the Ag species in soil, sediments and surface water because of different their behavior in contact with the minerals.

Genomic and Biotechnological Characterization of the Heavy-Metal Resistant, Arsenic-Oxidizing Bacterium Ensifer sp. M14.

Ensifer (Sinorhizobium) sp. M14 is an efficient arsenic-oxidizing bacterium (AOB) that displays high resistance to numerous metals and various stressors. Here, we report the draft genome sequence and genome-guided characterization of Ensifer sp. M14, and we describe a pilot-scale installation applying the M14 strain for remediation of arsenic-contaminated waters. The M14 genome contains 6874 protein coding sequences, including hundreds not found in related strains. Nearly all unique genes that are associated with metal resistance and arsenic oxidation are localized within the pSinA and pSinB megaplasmids. Comparative genomics revealed that multiple copies of high-affinity phosphate transport systems are common in AOBs, possibly as an As-resistance mechanism. Genome and antibiotic sensitivity analyses further suggested that the use of Ensifer sp. M14 in biotechnology does not pose serious biosafety risks. Therefore, a novel two-stage installation for remediation of arsenic-contaminated waters was developed. It consists of a microbiological module, where M14 oxidizes As(III) to As(V) ion, followed by an adsorption module for As(V) removal using granulated bog iron ores. During a 40-day pilot-scale test in an abandoned gold mine in Zloty Stok (Poland), water leaving the microbiological module generally contained trace amounts of As(III), and dramatic decreases in total arsenic concentrations were observed after passage through the adsorption module. These results demonstrate the usefulness of Ensifer sp. M14 in arsenic removal performed in environmental settings.

Granulated Bog Iron Ores as Sorbents in Passive (Bio)Remediation Systems for Arsenic Removal.

The main element of PbRS (passive (bio)remediation systems) are sorbents, which act as natural filters retaining heavy metals and carriers of microorganisms involved in water treatment. Thus, the effectiveness of PbRS is determined by the quality of the (ad)sorbents, which should be stable under various environmental conditions, have a wide range of applications and be non-toxic to (micro)organisms used in these systems. Our previous studies showed that bog iron ores (BIOs) meet these requirements. However, further investigation of the physical and chemical parameters of BIOs under environmental conditions is required before their large-scale application in PbRS. The aim of this study was (i) to investigate the ability of granulated BIOs (gBIOs) to remove arsenic from various types of contaminated waters, and (ii) to estimate the application potential of gBIOs in technologies dedicated to water treatment. These studies were conducted on synthetic solutions of arsenic and environmental samples of arsenic contaminated water using a set of adsorption columns filled with gBIOs. The experiments performed in a static system revealed that gBIOs are appropriate arsenic and zinc adsorbent. Dynamic adsorption studies confirmed these results and showed, that the actual sorption efficiency of gBIOs depends on the adsorbate concentration and is directly proportional to them. Desorption analysis showed that As-loaded gBIOs are characterized by high chemical stability and they may be reused for the (ad)sorption of other elements, i.e., zinc. It was also shown that gBIOs may be used for remediation of both highly oxygenated waters and groundwater or settling ponds, where the oxygen level is low, as both forms of inorganic arsenic (arsenate and arsenite) were effectively removed. Arsenic concentration after treatment was <100 µg/L, which is below the limit for industrial water.

The influence of thermal treatment on bioweathering and arsenic sorption capacity of a natural iron (oxyhydr)oxide-based adsorbent.

Adsorption plays a significant role in remediation of waters contaminated with arsenic, but the efficiency of the process varies depending on the sorbent properties. Bog iron ores (BIOs), characterized by high sorption capacity and widespread availability, seem to be an optimal sorbent of arsenic. However, the use of BIOs for arsenic removal from waters may be limited by the high amount of organic matter, which may stimulate microbial activity, and thus decomposition of the sorbent. The aim of this study was to determine the effect of organic matter removal by thermal transformation (roasting) on the bioavailability of BIOs and their arsenic sorption capacity. For this purpose, the influence of bacterial growth and activity on untreated and treated BIOs, unloaded and loaded with arsenic, was studied. Moreover, the chemical and physical properties (including FTIR and desorption of arsenic) of BIOs were investigated as well. The results show that the removal of organic matter increases the stability of BIOs, and thus reduces the bioavailability of the immobilized arsenic.

Composition of weathering crusts on sandstones from natural outcrops and architectonic elements in an urban environment.

This work presents mineralogical and chemical characteristics of weathering crusts developed on sandstones exposed to various air pollution conditions. The samples have been collected from sandstone tors in the Carpathian Foothill and from buildings in Kraków. It has been stated that these crusts differ in both fabric and composition. The sandstone black crust from tors is rich in organic matter and composed of amorphous silica. Sulphate incrustations accompanied by dust particles have been only sometimes observed. Beneath the black crust, a zone coloured by iron (oxyhydr)oxides occurs. The enrichment of the surface crust in silica and iron compounds protects the rock interior from atmospheric impact. The sandstones from architectonic details are also covered by a thin carbon-rich black crust, but they are visibly loosened. Numerous salts, mainly gypsum and halite, crystallise here, thus enhancing deterioration of the rock. Moreover, spherical particles originated from industrial emissions are much more common. Gypsum in natural outcrops, forms isolated and well-developed crystals, whilst these found on the architectonic details are finer and densely cover the surface. Such diversity reflects various concentrations of acid air pollutants in solutions.

Utilization of bog iron ores as sorbents of heavy metals.

Sorption properties of bog iron ores with respect to Pb, Cu, Zn, Cr are evaluated at various pH. Maximum sorption determined in the experiments equals to 97.0, 25.2, 25.5, 55.0mg/g for lead(II), copper(II), zinc(II), and chromium(III), respectively. Chromium(VI) is bound in the amount of up to 10.0mg/g. The values of desorption indicate that most of the metals remain stably bound to the surface of bog iron ores, indicating that the chemisorption process prevails. The metals are sorbed as cations at the pH values from 4 to 9. Within this pH range up to 100% of the initial metal amount is immobilized. 90-100% of Cr(VI) is sorbed at pH between 3 and 5. Such properties, combined with favorable conditions of shallow mining and resultant low costs, may be regarded as an incentive for local utilization of bog iron ores in the environmental protection practice.