Field application of glycerol to enhance reductive dechlorination of chlorinated ethenes and its impact on microbial community.

Chlorinated ethenes (CEs) are common and persistent contaminants of soil and groundwater. Their degradation is mostly driven by a process of bacterial reductive dechlorination (also called organohalide respiration) in anaerobic conditions. This study summarizes the outcomes of the long-term in-situ application of glycerol for the enhanced reductive dechlorination of CEs on a highly contaminated site. Glycerol injection resulted in an almost immediate increase in the abundance of fermentative Firmicutes, which produce essential sources of carbon (acetate) and electrons (H2) for organohalide-respiring bacteria (OHRB) and change groundwater conditions to be suitable for OHRB growth. The decreased redox potential of groundwater promoted also the proliferation of sulfate-reducing bacteria, which compete for electron donors with OHRB but at the same time support their growth by producing essential corrinoids and acetate. A considerable increase in the abundance of OHRB Dehalococcoides, concurrently with vinyl chloride (VC) reductase gene levels, was revealed by real time polymerase chain reaction (qPCR) method. Consistent with the shifts in bacterial populations, the concentrations of pollutants tetrachloroethylene and trichloroethylene decreased during the monitoring period, with rising levels of cis-1,2-dichloroethylene, VC, and most importantly, the final CE degradation products: ethene and ethane. Our study implies the importance of syntrophic bacterial interactions for successful and complete CE degradation and evaluates glycerol as convenient substrate to enhance reductive dechlorination and as an effective source of electrons for OHRB.

Discovering the potential of an nZVI-biochar composite as a material for the nanobioremediation of chlorinated solvents in groundwater: Degradation efficiency and effect on resident microorganisms.

Abiotic and biotic remediation of chlorinated ethenes (CEs) in groundwater from a real contaminated site was studied using biochar-based composites containing nanoscale zero-valent iron (nZVI/BC) and natural resident microbes/specific CE degraders supported by a whey addition. The material represented by the biochar matrix decorated by isolated iron nanoparticles or their aggregates, along with the added whey, was capable of a stepwise dechlorination of CEs. The tested materials (nZVI/BC and BC) were able to decrease the original TCE concentration by 99% in 30 days. Nevertheless, regarding the transformation products, it was clear that biotic as well as abiotic transformation mechanisms were involved in the transformation process when nonchlorinated volatiles (i.e., methane, ethane, ethene, and acetylene) were detected after the application of nZVI/BC and nZVI/BC with whey. The whey addition caused a massive increase in bacterial biomass in the groundwater samples (monitored by 16S rRNA sequencing and qPCR) that corresponded with the transformation of trichloro- and dichloro-CEs, and this process was accompanied by the formation of less chlorinated products. Moreover, the biostimulation step also eliminated the adverse effect caused by nZVI/BC (decrease in microbial biomass after nZVI/BC addition). The nZVI/BC material or its aging products, and probably together with vinyl chloride-respiring bacteria, were able to continue the further reductive dechlorination of dichlorinated CEs into nonhalogenated volatiles. Overall, the results of the present study demonstrate the potential, feasibility, and environmental safety of this nanobioremediation approach.

Reduction of chlorinated hydrocarbons using nano zero-valent iron supported with an electric field. Characterization of electrochemical processes and thermodynamic stability.

Electric field assisted remediation using nano iron has shown outstanding results as well as economic benefits during pilot applications (Cerníková et al., 2020). This method is based on donating electrons to the zero-valent iron that possess an inherently strong reductive capacity. The reduction of chlorinated hydrocarbons may be characterized by a decrease in contaminants or better still by the evolution of ethene and ethane originating from the reduction of chlorinated ethenes. The evolution of ethene and ethane was observed predominantly in the vicinity of the anode despite reduction processes being expected near the cathode - the electron donor. The reduction near the anode occurred due to dissolved Fe2+ ions, whose presence was suggested by a Pourbaix diagram that combines Eh/pH values to characterize electrochemical stabilities between different species. No products of dechlorination were observed in the area of the cathode due to presence of oxidized Fe in the form of Fe3+ or Fe(OH)4-. The experimental work described in this research provides a deeper view of the processes of electrochemical reductive dechlorination using zero-valent iron and DC. It also showed an increase in the efficiency compared to the method using zero-valent iron only.

Combining nanoscale zero-valent iron with electrokinetic treatment for remediation of chlorinated ethenes and promoting biodegradation: A long-term field study.

Nanoscale zero-valent iron (nZVI) is recognized as a powerful tool for the remediation of groundwater contaminated by chlorinated ethenes (CEs). This long-term field study explored nZVI-driven degradation of CEs supported by electrokinetic (EK) treatment, which positively affects nZVI longevity and migration, and its impact on indigenous bacteria. In particular, the impact of combined nZVI-EK treatment on organohalide-respiring bacteria, ethenotrophs and methanotrophs (all capable of CE degradation) was assessed using molecular genetic markers detecting Dehalococcoides spp., Desulfitobacterium spp., the reductive dehalogenase genes vcrA and bvcA and ethenotroph and methanotroph functional genes. The remediation treatment resulted in a rapid decrease of the major pollutant cis-1,2-dichloroethene (cDCE) by 75% in the affected area, followed by an increase in CE degradation products methane, ethane and ethene. The newly established geochemical conditions in the treated aquifer not only promoted growth of organohalide-respiring bacteria but also allowed for the concurrent presence of vinyl chloride- and cDCE-oxidizing methanotrophs and (especially) ethenotrophs, which proliferated preferentially in the vicinity of an anode where low levels of oxygen were produced. The nZVI treatment resulted in a temporary negative impact on indigenous bacteria in the application well close to the cathode; but even there, the microbiome was restored within 15 days. The nZVI-EK treatment proved highly effective in reducing CE contamination and creating a suitable environment for subsequent biodegradation by changing groundwater conditions, promoting transport of nutrients and improving CE availability to soil and groundwater bacteria.

Combination of nZVI and DC for the in-situ remediation of chlorinated ethenes: An environmental and economic case study.

Over the past two decades, the use of nanoscale zero-valent iron (nZVI) has emerged as a standard method of contaminated groundwater remediation. The effectiveness of this method depends on key intrinsic hydrogeological parameters, which can affect both reactivity of the nanoparticles and their migration in the aquifer. In the case of low hydraulic permeability, the migration of nanoparticles is limited, which negatively influences remediation. An application of nZVI reinforced with a DC electric field led to a significant increase in the efficiency of remediation, as demonstrated by long-term monitoring at a former industrial site in Horice (Czech Republic). For the method testing, a 12 × 9 m polygon was defined around well IS4, where the original contamination was predominantly composed of DCE (7300 µg/l), and with a total concentration of chlorinated ethenes of 8880 µg/l. During the first stage of the activities, 49 kg of nZVI was injected and monitored for two years. Subsequently, the electrodes were installed, and for three years, the synergistic action of nZVI within an applied DC field was monitored. Based on 32 monitoring campaigns performed over the six years, the combined method was compared with an application of the only nZVI in technical, environmental and economic terms. Technically, the method requires annual reinstallation of anodes as a result of their oxidative disintegration. Environmentally, the method provides significantly improved chlorinated ethane reduction, remediation of low permeable zones, and extended efficiency. Economically, the method is five times cheaper when compared to the nZVI used alone.

Electric-field enhanced reactivity and migration of iron nanoparticles with implications for groundwater treatment technologies: Proof of concept.

The extensive use of nanoscale zero-valent iron (nZVI) particles for groundwater treatment has been limited, in part, because of their non-selective reactivity and low mobility in aquatic environments. Herein, we describe and explore progressive changes in the reactivity and migration of aqueous dispersed nZVI particles under an applied DC electric field. Due to the applied electric field with an intensity of about 1 V cm-1, the solution oxidation-reduction potential (ORP) remained as low as -200 mV for at least 32 days, which was in agreement with the persistence of the reduced iron species (mainly Fe(II)), and led to substantially prolonged reactivity of the original nZVI. The treatment of chlorinated ethenes (DCE > PCE > TCE) was markedly faster, individual CHC compounds were eliminated with the same kinetics and no lesser-chlorinated intermediates were accumulated, following thus the direct dechlorination scheme. When nZVI-dispersion flows towards the anode through vertical laboratory columns filled with quartz sand, significant enhancement of nZVI migration was recorded because of lower extent of nanoparticle aggregation and increased repulsion forces between the nanoparticles and the surface of silica dioxide. The results of this study have significant consequences for groundwater remediation, mainly for the treatment of slowly degradable DCE in real CHC contaminated groundwater, where it could improve the reactivity, the longevity and the migration of nZVI particles.

Coupled extensional vibrations of longitudinally polarized piezoceramic strips.

A system of one-dimensional equations for coupled length-extensional, width-stretch, and symmetric width-shear vibrations of piezoceramic strips polarized in the length direction is derived from the two-dimensional, second-order plate equations by averaging the mechanical displacement and the electrostatic potential over the strip thickness. The boundary conditions correspond to the case of electrically forced vibrations. Theoretical values are compared with results of a previous analytical model and with experimental data.

High-frequency extensional vibrations of piezoelectric ceramic bars polarized in the longitudinal direction.

The approximate 1-D governing equations for coupled length-extensional, width-stretch, and symmetric width-shear vibration modes in rectangular finite piezoelectric bars with 6 mm hexagonal symmetry are presented. The bars polarized in the longitudinal direction with electrodes on the faces perpendicular to the length are considered. The system of equations is used to study the frequency spectrum of piezoelectrically forced vibrations of bars made of hard ceramics. The influence of the width-to-thickness ratio on the resonance frequency is discussed. The computed values are compared with experimental data. The material constants used for numerical simulations of resonant frequencies were obtained from the measurements on APC 841 PZT ceramics samples.

Determination of the electromechanical coupling factor of gallium orthophosphate (GaPO4) and its influence on resonance-frequency temperature dependencies.

The quartz homeotype gallium orthophosphate (GaPO4) is a representative of piezoelectric single crystals of large electromechanical coupling factor. It is known that its coupling factor kappa26 associated with the resonators vibrating in the thickness-shear mode is approximately two times greater than that of quartz. This property increases the spacing between the series and parallel resonance frequencies of resonators, as well as the difference between the resonance frequency temperature dependencies of the fundamental and harmonic resonance frequencies of resonators vibrating in the thickness-shear mode. In this paper, the methods for determination of the coupling factor kappa26 are presented, and the computed values are compared with the measured ones. The influence of the coupling factor to the resonance-frequency temperature dependencies of the fundamental and third harmonics of selected rotated Y-cut GaPO4 resonators vibrating in the thickness-shear mode is presented. The purely elastic case for a laterally unbounded plate, which corresponds closely to the limiting case of high harmonic resonance frequency-temperature behavior was assumed for the calculations. The computed temperature coefficients for the Y-cut orientation and calculated turnover point temperatures TTP for different (YX1) orientations are presented.

Contribution to the electromechanical and nonlinear properties of GaPO4 crystals.

In the last decade, much attention has been given to piezoelectric crystals with large electromechanical coupling coefficient. The quartz homeotypes berlinite and gallium orthophosphate (GaPO4), along with the calcium gallo-germanates such as langasite are representative of these crystals. The coupling coefficient k26 associated with thickness-shear mode resonators is two times greater than that of quartz, increasing the spacing between the series and parallel resonance frequencies of resonators suitable for the frequency range from 1 to 100 MHz. This is important for some types of crystal oscillators and monolithic filters. The large electromechanical coupling coefficient also increases the difference between the temperature dependencies of the fundamental resonance frequency and its harmonics. In this paper, measured resonance frequency-temperature characteristics of the fundamental and third harmonics of selected rotated Y-cut GaPO4 resonators vibrating in the thickness-shear mode are presented. Further attention is given to the measurement of some nonlinear properties of rotated Y-cut GaPO4 resonators. Knowledge of such nonlinear interactions is important for the analysis of intermodulation phenomena in resonators, and for the application of GaPO4 resonators in crystal oscillators, filters and other electronic devices.

A precise measurement of some nonlinear effects and its application to the evaluation of nonlinear elastic constants of quartz and GaPO4.

This paper deals with a precise measurement of amplitude frequency and intermodulation effects, and its application to the evaluation of nonlinear elastic constants of quartz and gallium orthophosphate (GaPO4). An evaluation is based on the methods used previously concerning determination of the higher-order material constants in the quartz. Using a measurement of the intermodulation products and measurement of drive level dependence of resonant frequency of quartz resonators, we have determined some effective elastic constants of fourth order. The computer-based method of solution of the set of equations gives an access to obtain a number of effective nonlinear stiffnesses of fourth order. The measurements and computer solutions are performed on different Y-cuts resonators, both for quartz and gallium orthophosphate resonators, vibrating in fundamental thickness shear mode. The experimental results are discussed.