The large-scale process of microbial carbonate precipitation for nickel remediation from an industrial soil.

Microbial carbonate precipitation is known as an efficient process for the remediation of heavy metals from contaminated soils. In the present study, a urease positive bacterial isolate, identified as Bacillus cereus NS4 through 16S rDNA sequencing, was utilized on a large scale to remove nickel from industrial soil contaminated by the battery industry. The soil was highly contaminated with an initial total nickel concentration of approximately 900 mg kg-1. The soluble-exchangeable fraction was reduced to 38 mg kg-1 after treatment. The primary objective of metal stabilization was achieved by reducing the bioavailability through immobilizing the nickel in the urease-driven carbonate precipitation. The nickel removal in the soils contributed to the transformation of nickel from mobile species into stable biominerals identified as calcite, vaterite, aragonite and nickelous carbonate when analyzed under XRD. It was proven that during precipitation of calcite, Ni2+ with an ion radius close to Ca2+ was incorporated into the CaCO3 crystal. The biominerals were also characterized by using SEM-EDS to observe the crystal shape and Raman-FTIR spectroscopy to predict responsible bonding during bioremediation with respect to Ni immobilization. The electronic structure and chemical-state information of the detected elements during MICP bioremediation process was studied by XPS. This is the first study in which microbial carbonate precipitation was used for the large-scale remediation of metal-contaminated industrial soil.

Biosequestration of copper by bacteria isolated from an abandoned mine by using microbially induced calcite precipitation.

Abandoned mine sites are frequently polluted with high concentrations of heavy metals. In this study, 25 calcite-forming bacteria were newly isolated from the soil of an abandoned metal mine in Korea. Based on their urease activity, calcite production, and resistance to copper toxicity, four isolates were selected and further identified by 16S rRNA gene sequencing. Among the isolates, Sporosarcina soli B-22 was selected for subsequent copper biosequestration studies, using the sand impermeability test by production of calcite and extracellular polymeric substance. High removal rates (61.8%) of copper were obtained when the sand samples were analyzed using an inductively coupled plasma-optical emission spectrometer following 72 h of incubation. Scanning electron microscopy showed that the copper carbonate precipitates had a diameter of approximately 5-10 µm. X-ray diffraction further confirmed the presence of copper carbonate and calcium carbonate crystals.

Zeta potential-assisted sorption of uranyl tricarbonate complex from aqueous solution by polyamidoxime-functionalized colloidal particles.

Uranium(vi) is one of the main sources in nuclear energy but can cause severe effects to human health and the environment, therefore it is important to develop a new method and materials for uranium capture. A novel approach is reported here for efficient uranium sorption by polyamidoxime-functionalized colloids with zeta potential-assistance. Specifically, colloidal particles were prepared via emulsion polymerization with (3-acrylamidopropyl)trimethyl-ammonium chloride (MAPTAC). The zeta potential of the colloids could be controlled by the concentration of MAPTAC. The effects of pH, the sorbent dose and competing ions on uranium(vi) sorption were investigated. The sorption process followed a pseudo-second-order kinetics and could reach equilibrium within 3.5 h at pH 7.8. The colloidal particles with high zeta potentials showed higher selectivity, faster kinetics and larger capacity for the sorption of uranium(vi) in comparison with that of negative zeta potential particles. This work may provide a new method for efficient uranium(vi) capture from aqueous solution through zeta potential-assisted sorption.

Upgrading the rice husk char obtained by flash pyrolysis for the production of amorphous silica and high quality activated carbon.

The overall valorization of rice husk char obtained by flash pyrolysis in a conical spouted bed reactor (CSBR) has been studied in a two-step process. Thus, silica has been recovered in a first step and the remaining carbon material has been subjected to steam activation. The char samples used in this study have been obtained by continuous flash pyrolysis in a conical spouted bed reactor at 500°C. Extraction with Na2CO3 allows recovering 88% of the silica contained in the rice husk char. Activation of the silica-free rice husk char has been carried out in a fixed bed reactor at 800°C using steam as activating agent. The porous structure of the activated carbons produced includes a combination of micropores and mesopores, with a BET surface area of up to 1365m(2)g(-1) at the end of 15min.

Evaluating specificity of sequential extraction for chemical forms of lead in artificially-contaminated and field-contaminated soils.

In the present study, we evaluated a commonly employed modified Bureau Communautaire de Référence (BCR test) 3-step sequential extraction procedure for its ability to distinguish forms of solid-phase Pb in soils with different sources and histories of contamination. When the modified BCR test was applied to mineral soils spiked with three forms of Pb (pyromorphite, hydrocerussite and nitrate salt), the added Pb was highly susceptible to dissolution in the operationally-defined "reducible" or "oxide" fraction regardless of form. When three different materials (mineral soil, organic soil and goethite) were spiked with soluble Pb nitrate, the BCR sequential extraction profiles revealed that soil organic matter was capable of retaining Pb in more stable and acid-resistant forms than silicate clay minerals or goethite. However, the BCR sequential extraction for field-collected soils with known and different sources of Pb contamination was not sufficiently discriminatory in the dissolution of soil Pb phases to allow soil Pb forms to be "fingerprinted" by this method. It is concluded that standard sequential extraction procedures are probably not very useful in predicting lability and bioavailability of Pb in contaminated soils.

Adsorption of phosphorus on sediments from the Three-Gorges Reservoir (China) and the relation with sediment compositions.

The adsorption of phosphorus (P) on four sediment samples (CunTan, XiaoJiang, DaNing and XiangXi) from the Three-Gorges Reservoir on the Yangtze River in China was studied systematically in batch experiments. A sequential chemical extraction experiment was conducted to clarify the effect of sediment composition on P adsorption. The results showed that P adsorption on four sediment samples mainly occurred within 6h. P adsorption kinetics can be satisfactorily fitted by both power function and simple Elovich model. A modified Langmuir model may describe well the P adsorption on all the samples in our study. Theoretically, the maximum adsorption amount (Q(max)) was 0.402mg-P/g for XiaoJiang sediment, 0.358mg-P/g for DaNing sediment, 0.165mg-P/g for CunTan sediment, and 0.15mg-P/g for XiangXi sediment. The sediment compositions such as organic matter, metal hydroxides, calcium and clay content showed influences on the P adsorption. Wherein, organic matter and metal hydroxides were the main factors affecting the P adsorption. The maximum P adsorption capacity (Q(max)) enhanced with the increase of the content of (Fe+Al+Ca). Compared the zero-equilibrium P concentration (EPC(0)) values obtained by the modified Langmuir models with actual P concentrations in water, all the sediments studied in this paper except for XiaoJiang showed a trend of releasing P as a source role, which could enhance the risk of eutrophication occurrence in the Three-Gorges Reservoir.

The impact of toxicity of metals on the activity of ureolytic mixed culture during the precipitation of calcium.

In this article, the inhibitory impact of metals on substrate utilization and microbial carbonate precipitation (MCP) by ureolytic mixed cultures (UMC) was investigated with glucose and mineral medium under batch conditions. The IC(50) (toxicant concentration eliciting 50% inhibitory effect) values were determined from the BOD values of samples. Inhibition, expressed as the value of 50% inhibitory effect (IC(50)), was evaluated by the decrease in substrate removal using BOD tests. The effect of toxicity of metals on substrate degradation, IC(50) values, was found to increase in the following order: Cd(II)>Cu(II)>Pb(II)>Cr(VI)>Ni(II)>Zn(II). Nitrification a possible phenomenon in the biocatalytic process was observed in several samples and this inhibited the precipitation of soluble calcium. During the removal of calcium from industrial calcium-rich wastewater, toxicity of metal at higher metal concentrations and possibility of nitrification at higher sludge ages should be considered.

Evidence of different stoichiometries for the limiting carbonate complexes across the lanthanide(III) series: a capillary electrophoresis-mass spectrometry study.

The electrophoretic mobilities (mu ep,Ln) of twelve lanthanides (not Ce, Pr and Yb) were measured by CE-ICP-MS in 0.15 and 0.5 mol L(-1) Alk2 CO3 aqueous solutions for Alk+ = Li+, Na+, K+ and Cs+. In 0.5 mol L(-1) solutions, two different mu ep,Ln values were found for the light (La to Nd) and the heavy (Dy to Tm) lanthanides, which suggests two different stoichiometries for the carbonate limiting complexes. These results are consistent with a solubility study that attests the Ln(CO3)3(3-) and Ln(CO3)4(5-) stoichiometries for the heavy (small) and the light (big) lanthanides, respectively. The Alk+ counterions influence the mu ep,Ln Alk2 CO3 values, but not the overall shape of the mu ep,Ln Alk2 CO3 plots as a function of the lanthanide atomic numbers: the counterions do not modify the stoichiometries of the inner sphere complexes. The influence of the Alk+ counterions decreases in the Li+ > Na+ >> K+ > Cs+ series. The K3,Ln stepwise formation constants of the Ln(CO3)3(3-) complexes slightly increase with the atomic numbers of the lanthanides while K4,Ln, the stepwise formation constants of Ln(CO3)4(5-) complexes, slightly decrease from La to Tb, and is no longer measurable for heavier lanthanides.

Investigation of gas production and entrapment in granular iron medium.

A method for measuring gas entrapment in granular iron (Fe0) was developed and used to estimate the impact of gas production on porosity loss during the treatment of a high NO3- groundwater (up to approximately 10 mM). Over the 400-d study period the trapped gas in laboratory columns was small, with a maximum measured at 1.3% pore volume. Low levels of dissolved H2(g) were measured (up to 0.07+/-0.02 M). Free moving gas bubbles were not observed. Thus, porosity loss, which was determined by tracer tests to be 25-30%, is not accounted for by residual gas trapped in the iron. The removal of aqueous species (i.e., NO3-, Ca, and carbonate alkalinity) indicates that mineral precipitation contributed more significantly to porosity loss than did the trapped gases. Using the stoichiometric reactions between Fe0 and NO3-, an average corrosion rate of 1.7 mmol kg-1 d-1 was derived for the test granular iron. This rate is 10 times greater than Fe0 oxidation by H2O alone, based on H2 gas production. NO3- ion rather than H2O was the major oxidant in the groundwater in the absence of molecular O2. The N-mass balance [e.g., N2g and NH4+ and NO3-] suggests that abiotic reduction of NO3- dominated at the start of Fe0 treatment, whereas N2 production became more important once the microbial activity began. These laboratory results closely predict N2 gas production in a separated large column experiment that was operated for approximately 2 yr in the field, where a maximum of approximately 600 ml d-1 gas volumes was detected, of which 99.5% (v/v) was N2. We conclude that NO3- suppressed the production of H2(g) by competing with water for Fe0 oxidation, especially at the beginning of water treatment when Fe0 is highly reactive. Depends on the groundwater composition, gas venting may be necessary in maintaining PRB performance in the field.

A novel method for preparation of cobalt(II) and lead(II) carbonates.

Cobalt(II) carbonate, CoCO3.4H2O and lead(II) carbonate, PbCO3.2H2O were synthesis by a new simple method during the reaction of aqueous solutions of CoX2 (X=Cl-, NO3- and CH3COO-) and PbX2 (X=NO3- or CH3COO-), respectively, with urea at approximately 85 degrees C for 2 h. The infrared spectra of the reaction products clearly indicates the absence of the bands due to coordinated urea, but show the characteristic bands of ionic carbonate. A general mechanisms describing the formation of cobalt and lead carbonates are suggested.

A cyclic carbonate and related polyketides from a marine-derived fungus of the genus Phoma.

Two metabolites, phomoxin and phomoxide, as well as the previously synthesized antibiotic eupenoxide, have been isolated from the fermentation broth of a marine-derived fungus of the genus Phoma (strain CNC-651). The new compounds are highly oxygenated polyketides of a new structural class. Phomoxin contains an unusual cyclic carbonate functionality that is rare among natural products. The structures of the new metabolites were assigned by spectroscopic methods that relied heavily on 2D NMR spectroscopic analysis.

Bacterial Ca2+ metabolism as the key to microbial carbonate precipitation.

Ca2+ -ATPase enzymes facilitate active trans-membrane transport of Ca2+ in micro-organisms. This study investigates the hypothesis that active calcium metabolism under conditions of alkaline stress is a key element of microbial carbonate precipitation, and that the latter plays an integral part in survival of bacteria under alkaline conditions.

Masking as a mechanism for evaporative loss of trace analyte, especially after solid-phase extraction.

Using a Pasteur pipette plugged with silanized glass wool and packed with C18-silica particles, we attempted to remove K2CO3 from an aqueous acetonitrile solution. In spite of extensive washing of the column with water after the sample was applied, elution with acetonitrile followed by evaporation gave a visible, white residue. It was found that the residue was derived from both the sample and the packing, including particles from the latter. Substitution of a plastic column/polyethylene frit for the Pasteur pipette/glass wool gave a more consistent residue, apparently because this improved the retention of particles. Subsequent experiments were conducted in the plastic hardware. The amount of the residue was observed to vary as much as 19-fold when C18-silica particles were tested from different manufacturers, and the residue could be reduced in amount as much as 9-fold when a column was prepared in the laboratory vs. the use of a comparable, pre-packed column. The water itself contributed some of the residue: even the "purest" water routinely available left a visible residue when 1.0 ml was appropriately evaporated (e.g. on Saran Wrap in a microwave oven). The recovery of an arbitrary trace analyte and internal standard (pentafluorobenzylated nucleobases at the low pg level) was 32% less when they were evaporated in acetonitrile that had been passed through an acetonitrile and water-washed cartridge containing C18-Si vs. evaporation in untreated acetonitrile. Collectively these results reveal that an evaporation can risk some loss of an analyte from masking by even subtle solvent contaminants.(ABSTRACT TRUNCATED AT 250 WORDS)

The nature of bone carbonate.

Models of the bone salt and its synthetic analogues have been strenuously, and sometimes emotionally debated since the late nineteenth century. The main protagonist in the drama is the ubiquitous CO3=ion whose role has never been clearly understood. Initially regarded as an essential part of the calcium phosphate crystal complex, it came to be dubiously designated as a separate phase CaCO3, as an adsorbed ion, or even as a mere contaminant. More recent studies provide evidence that the original impression may be more nearly correct. Of particular interest in defining the role of CO3= in bone are the reactions involved in the formation of CO3-apatite under conditions approximating the physiological. These observations suggest that the synthesis of bone mineral involves hydrolysis of an initial acidic calcium phosphate precipitate to octacalcium phosphate, which is then converted to octacalcium phosphate carbonate (OCPC) by virtue of the replacement of PO4 identical to (HPO4=) by CO3=. OCPC satisfies many criteria for a satisfactory definition of the nature of the bone mineral. It can explain its solubility behavior and the intrinsic relationship between PO4 identical to (HPO4=) and CO3=, the normal variations in bone composition, the sequence of events in bone mineral maturation, and the loss of CO3= under normal and pathological conditions.