Miroslav Černík

Application of nanoscale zero valent iron (NZVI) for groundwater remediation in Europe

PurposeNanoscale zero valent iron (NZVI) is emerging as a new option for the treatment of contaminated soil and groundwater targeting mainly chlorinated organic contaminants (e.g., solvents, pesticides) and inorganic anions or metals. The purpose of this article is to give a short overview of the practical experience with NZVI applications in Europe and to present a comparison to the situation in the USA. Furthermore, the reasons for the difference in technology use are discussed.MethodThe results in this article are based on an extensive literature review and structured discussions in an expert workshop with experts from Europe and the USA. The evaluation of the experiences was based on a SWOT (strength, weakness, opportunity, threat) analysis.ResultThere are significant differences in the extent and type of technology used between NZVI applications in Europe and the USA. In Europe, only three full-scale remediations with NZVI have been carried out so far, while NZVI is an established treatment method in the USA. Bimetallic particles and emulsified NZVI, which are extensively used in the USA, have not yet been applied in Europe. Economic constraints and the precautionary attitude in Europe raise questions regarding whether NZVI is a cost-effective method for aquifer remediation. Challenges to the commercialization of NZVI include mainly non-technical aspects such as the possibility of a public backlash, the fact that the technology is largely unknown to consultants, governments and site owners as well as the lack of long-term experiences.ConclusionDespite these concerns, the results of the current field applications with respect to contaminant reduction are promising, and no major adverse impacts on the environment have been reported so far. It is thus expected that these trials will contribute to promoting the technology in Europe.

Green synthesis of copper oxide nanoparticles using gum karaya as a biotemplate and their antibacterial application

Background Copper oxide (CuO) nanoparticles have attracted huge attention due to catalytic, electric, optical, photonic, textile, nanofluid, and antibacterial activity depending on the size, shape, and neighboring medium. In the present paper, we synthesized CuO nanoparticles using gum karaya, a natural nontoxic hydrocolloid, by green technology and explored its potential antibacterial application. Methods The CuO nanoparticles were synthesized by a colloid-thermal synthesis process. The mixture contained various concentrations of CuCl2 • 2H2O (1 mM, 2 mM, and 3 mM) and gum karaya (10 mg/mL) and was kept at 75°C at 250 rpm for 1 hour in an orbital shaker. The synthesized CuO was purified and dried to obtain different sizes of the CuO nanoparticles. The well diffusion method was used to study the antibacterial activity of the synthesized CuO nanoparticles. The zone of inhibition, minimum inhibitory concentration, and minimum bactericidal concentration were determined by the broth microdilution method recommended by the Clinical and Laboratory Standards Institute. Results Scanning electron microscopy analysis showed CuO nanoparticles evenly distributed on the surface of the gum matrix. X-ray diffraction of the synthesized nanoparticles indicates the formation of single-phase CuO with a monoclinic structure. The Fourier transform infrared spectroscopy peak at 525 cm−1 should be a stretching of CuO, which matches up to the B2u mode. The peaks at 525 cm−1 and 580 cm−1 indicated the formation of CuO nanostructure. Transmission electron microscope analyses revealed CuO nanoparticles of 4.8 ± 1.6 nm, 5.5 ± 2.5 nm, and 7.8 ± 2.3 nm sizes were synthesized with various concentrations of CuCl2 • 2H2O (1 mM, 2 mM, and 3 mM). X-ray photoelectron spectroscopy profiles indicated that the O 1s and Cu 2p peak corresponding to the CuO nanoparticles were observed. The antibacterial activity of the synthesized nanoparticles was tested against Gram-negative and positive cultures. Conclusion The formed CuO nanoparticles are small in size (4.8 ± 1.6 nm), highly stable, and have significant antibacterial action on both the Gram classes of bacteria compared to larger sizes of synthesized CuO (7.8 ± 2.3 nm) nanoparticles. The smaller size of the CuO nanoparticles (4.8 ± 1.6 nm) was found to be yielding a maximum zone of inhibition compared to the larger size of synthesized CuO nanoparticles (7.8 ± 2.3 nm). The results also indicate that increase in precursor concentration enhances an increase in particle size, as well as the morphology of synthesized CuO nanoparticles.

Zero-valent iron nanoparticles in treatment of acid mine water from in situ uranium leaching.

Acid mine water from in situ chemical leaching of uranium (Straz pod Ralskem, Czech Republic) was treated in laboratory scale experiments by zero-valent iron nanoparticles (nZVI). For the first time, nZVI were applied for the treatment of the real acid water system containing the miscellaneous mixture of pollutants, where the various removal mechanisms occur simultaneously. Toxicity of the treated saline acid water is caused by major contaminants represented by aluminum and sulphates in a high concentration, as well as by microcontaminants like As, Be, Cd, Cr, Cu, Ni, U, V, and Zn. Laboratory batch experiments proved a significant decrease in concentrations of all the monitored pollutants due to an increase in pH and a decrease in oxidation-reduction potential related to an application of nZVI. The assumed mechanisms of contaminants removal include precipitation of cations in a lower oxidation state, precipitation caused by a simple pH increase and co-precipitation with the formed iron oxyhydroxides. The possibility to control the reaction kinetics through the nature of the surface stabilizing shell (polymer vs. FeO nanolayer) is discussed as an important practical aspect.

Dynamics of an Oligotrophic Bacterial Aquifer Community during Contact with a Groundwater Plume Contaminated with Benzene, Toluene, Ethylbenzene, and Xylenes: an In Situ Mesocosm Study

ABSTRACT An in situ mesocosm system was designed to monitor the in situ dynamics of the microbial community in polluted aquifers. The mesocosm system consists of a permeable membrane pocket filled with aquifer material and placed within a polypropylene holder, which is inserted below groundwater level in a monitoring well. After a specific time period, the microcosm is recovered from the well and its bacterial community is analyzed. Using this system, we examined the effect of benzene, toluene, ethylbenzene, and xylene (BTEX) contamination on the response of an aquifer bacterial community by denaturing gradient gel electrophoresis analysis of PCR-amplified 16S rRNA genes and PCR detection of BTEX degradation genes. Mesocosms were filled with nonsterile or sterile aquifer material derived from an uncontaminated area and positioned in a well located in either the uncontaminated area or a nearby contaminated area. In the contaminated area, the bacterial community in the microcosms rapidly evolved into a stable community identical to that in the adjacent aquifer but different from that in the uncontaminated area. At the contaminated location, bacteria with tmoA- and xylM/xylE1-like BTEX catabolic genotypes colonized the aquifer, while at the uncontaminated location only tmoA-like genotypes were detected. The communities in the mesocosms and in the aquifer adjacent to the wells in the contaminated area consisted mainly of Proteobacteria. At the uncontaminated location, Actinobacteria and Proteobacteria were found. Our results indicate that communities with long-term stability in their structures follow the contamination plume and rapidly colonize downstream areas upon contamination.

DDT degradation efficiency and ecotoxicological effects of two types of nano-sized zero-valent iron (nZVI) in water and soil.

Nano-scale zero-valent iron (nZVI) has been conceived for cost-efficient degradation of chlorinated pollutants in soil as an alternative to e.g permeable reactive barriers or excavation. Little is however known about its efficiency in degradation of the ubiquitous environmental pollutant DDT and its secondary effects on organisms. Here, two types of nZVI (type B made using precipitation with borohydride, and type T produced by gas phase reduction of iron oxides under H2) were compared for efficiency in degradation of DDT in water and in a historically (>45 years) contaminated soil (24 mg kg(-1) DDT). Further, the ecotoxicity of soil and water was tested on plants (barley and flax), earthworms (Eisenia fetida), ostracods (Heterocypris incongruens), and bacteria (Escherichia coli). Both types of nZVI effectively degraded DDT in water, but showed lower degradation of aged DDT in soil. Both types of nZVI had negative impact on the tested organisms, with nZVI-T giving least adverse effects. Negative effects were mostly due to oxidation of nZVI, resulting in O2 consumption and excess Fe(II) in water and soil.

Cation transport in natural porous media on laboratory scale: multicomponent effects

Abstract Multicomponent transport experiments were performed with four major cations, Na + , K + , Ca 2+ and Mg 2+ , in laboratory columns packed with a non-calcereous soil. The breakthrough curves are explained quantitatively with a box model including cation exchange. We use a single set of selectivity coefficients, an independently verified value of the cation-exchange capacity (CEC), and an adjusted value of the Peclet number. This Peclet number is smaller than the value determined from independent tracer experiments. The model is able to predict all experimentally observed breakthrough curves quite well. The selectivity coefficients determined from binary exchange experiments prove unreliable for the prediction of multicomponent experiments. We propose to estimate the selectivity coefficients by directly fitting the multicomponent breakthrough curves. Their shape is a very sensitive function of the values of these coefficients. Concepts from non-linear chromatography can be used in order to interpret several qualitative features of the breakthrough curves.

Combined nano-biotechnology for in-situ remediation of mixed contamination of groundwater by hexavalent chromium and chlorinated solvents

The present report describes a 13month pilot remediation study that consists of a combination of Cr(VI) (4.4 to 57mg/l) geofixation and dechlorination of chlorinated ethenes (400 to 6526μg/l), achieved by the sequential use of nanoscale zerovalent iron (nZVI) particles and in situ biotic reduction supported by whey injection. The remediation process was monitored using numerous techniques, including physical-chemical analyses and molecular biology approaches which enabled both the characterization of the mechanisms involved in pollutant transformation and the description of the overall background processes of the treatment. The results revealed that nZVI was efficient toward Cr(VI) by itself and completely removed it from the groundwater (LOQ 0.05mg/l) and the subsequent application of whey resulted in a high removal of chlorinated ethenes (97 to 99%). The persistence of the reducing conditions, even after the depletion of the organic substrates, indicated a complementarity between nZVI and the whey phases in the combined technology as the subsequent application of whey phase partially assisted the microbial regeneration of the spent nZVI by promoting its reduction into Fe(II), which further supported remediation conditions at the site. Illumina sequencing and the detection of functional vcrA and bvcA genes documented a development in the reducing microbes (iron-reducing, sulfate-reducing and chlororespiring bacteria) that benefited under the conditions of the site and that was probably responsible for the high dechlorination and/or Cr(VI) reduction. The results of this study demonstrate the feasibility and high efficiency of the combined nano-biotechnological approach of nZVI and whey application in-situ for the removal of Cr(VI) and chlorinated ethenes from the groundwater of the contaminated site.

Poly (vinyl alcohol)/gum karaya electrospun plasma treated membrane for the removal of nanoparticles (Au, Ag, Pt, CuO and Fe3O4) from aqueous solutions.

In the present work, nanofibre membranes composed of polyvinyl alcohol (PVA) and a natural gum karaya (GK) hydrocolloid were prepared using electrospinning. The electrospun membranes of PVA/GK were cross-linked with heat treatment and later methane plasma was used to obtain a hydrophobic membrane. The morphology, characterization and adsorption ability of P-NFM was assessed using scanning electron microscopy, UV-vis spectroscopy, ATR-FTIR techniques, water contact angle and ICP-MS analytical methods. The membrane was employed for the extraction of nanoparticles (Ag, Au, Pt, CuO and Fe3O4) from water. The nanoparticle extraction kinetic and adsorption isotherm perform the pseudo-second-order model and Langmuir isotherm model, respectively. The adsorption capacities of the membrane for the removal of NPs from water diverge in the order Pt>Au>Ag>CuO>Fe3O4. The high adsorption efficiency for the removal of NPs from water was compared with an untreated membrane. Physisorption, functional group interactions, complexation reactions between metal/metal oxide nanoparticles with various functional groups present in NFM and modified surface properties such as the balance of hydrophilicity/hydrophobicity, surface free energy, and the high surface area of the plasma treated membrane were possible mechanisms of NPs adsorption onto NFM. The regeneration and reusability were tested in five consecutive adsorption/desorption cycles.

Simple spectrophotometric determination of monopersulfate.

A simple, sensitive and accurate spectrophotometric method has been developed and validated for the determination of monopersulfate (MPS) which is an active part of potassium monopersulfate triple salt that has the commercial name - Oxone. This work proposes a spectrophotometric determination of monopersulfate based on modification of the iodometric titration method. The analysis of absorption spectra was made for the concentration range from 1.35 to 13.01 ppm of MPS (with a detection and quantification limit of 0.41 and 1.35 ppm, respectively) and different pH values. The influence of several anions on the measurement was also investigated. Furthermore, the absorbance of iron and cobalt (often used as free radical initiators) proved to have no effect on the measurement of MPS concentrations. On the basis of the conducted studies, we propose 395 nm as an optimal wavelength for the determination of MPS concentrations.

Dodecenylsuccinic Anhydride Derivatives of Gum Karaya (Sterculia urens): Preparation, Characterization, and Their Antibacterial Properties

Esterifications of the tree-based gum, gum karaya (GK), using dodecenylsuccinic anhydride (DDSA) were carried out in aqueous solutions. GK was deacetylated using alkali treatment to obtain deacetylated gum karaya (DGK). The DGK and its DDSA derivative were characterized using gel permeation chromatography/multiangle laser light scattering (GPC/MALLS), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM), proton nuclear magnetic resonance spectroscopy ((1)H NMR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) analysis, and rheological studies. The degree of substitution was found to be 10.25% for DGK using (1)H NMR spectroscopy. The critical aggregation concentration of DDSA-DGK was determined using dye solubilization and surface tension methods. The antibacterial activity of the DDSA-DGK derivative was then investigated against Gram-negative Escherichia coli and Pseudomonas aeruginosa and Gram-positive Staphylococcus aureus. The DDSA-DGK derivative has the potential for use as a stabilizing agent in food and nonfood applications. It can also be developed as an antibacterial agent.