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1.
J Hazard Mater ; 440: 129739, 2022 10 15.
Article in English | MEDLINE | ID: mdl-35986942

ABSTRACT

Our study has thoroughly investigated the complete mineralization of toluene in water via heat-activated peroxydisulfate (PDS) by: (1) monitoring concentrations/peak areas of various intermediates and CO2 throughout the reaction period and (2) identifying water-soluble and methanol-soluble intermediates, including trimers, dimers, and organo-sulfur compounds, via non-target screening using high-resolution mass spectrometry. Increased temperature and PDS dosage enhanced toluene removal/mineralization kinetics and increased the rate/extent of benzaldehyde formation and its further transformation. Artificial groundwater and phosphate buffer minimally impacted toluene removal but significantly decreased benzaldehyde formation, indicating a shift in transformation pathways. The stoichiometric PDS dose (18 mM at 40 °C) was adequate to completely mineralize toluene (1 mM), with < 10% PDS needed to transform toluene to intermediates. Toluene transformation to intermediates occurred in 47 h (kobs,toluene = 0.594 h-1) whereas 564 h were required for complete mineralization (kobs,CO2 = 0.0038 h-1). O2 accumulated once mineralization neared completion. A carbon mass balance, including quantification of nine intermediates and CO2 throughout the transformation period, showed that unquantified/unknown intermediates (including yellowish-white precipitates) reached as high as 80% of total carbon before transformation to CO2. Possible toluene transformation pathways via hydroxylation, sulfate addition, and oxidative coupling are proposed.


Subject(s)
Toluene , Water Pollutants, Chemical , Benzaldehydes , Carbon , Carbon Dioxide/analysis , Hot Temperature , Methanol , Oxidation-Reduction , Phosphates , Sulfates/chemistry , Toluene/chemistry , Water/chemistry , Water Pollutants, Chemical/chemistry
2.
Talanta ; 240: 123170, 2022 Apr 01.
Article in English | MEDLINE | ID: mdl-35007773

ABSTRACT

Frequent use of persulfates as oxidants, for in situ chemical oxidation and advanced oxidation processes, warrants the need for developing a fast and efficient method for measuring persulfate concentrations in aqueous samples in the lab and on site. Here, we propose a modified method, based on Liang et al.'s (2008) spectrophotometric method, for measuring both peroxydisulfate (PDS) and peroxymonosulfate (PMS) in the aqueous samples. Our method involves a deep 96-well plate, multi-channel pipettes, a small orbital shaker, and a microplate reader; allowing the preparation and analysis of up to 96 samples in one run. Our proposed method shortens the time by 10 folds, consumes only ∼2% of the original reagents, and generates only ∼2% of the liquid waste compared to the Liang et al.'s method, thus, making our method high-throughput, time-efficient, and cost-effective with reduced environmental impact. The presented microplate reader method is validated in terms of linearity, LOD, LOQ, accuracy, precision, robustness, and selectivity. All the parameters satisfied the acceptance criteria, according to ICH guidelines. The linearity of calibration curves was evaluated by performing the F-test. In general, our method has linear ranges from 20 to 42,000 and 5 to 40,960 µM for PDS and PMS, respectively. Accuracy (% recovery) results suggested that the LOD and LOQ based on the standard deviation of y-intercepts of the regression lines were the most reliable. The LOD/LOQ values for PDS and PMS were 14.7/44.1 and 4.6/14.4 µM, respectively. The proposed method was also modified to work with a standard cuvette spectrophotometer and was validated. A comparison with the UHPLC analysis of PDS showed that our microplate reader method performed equivalently or even outperformed the UHPLC method, in the presence of common groundwater constituents and organic contaminants.


Subject(s)
Groundwater , Peroxides , Cost-Benefit Analysis , Oxidants
3.
Water Res ; 174: 115594, 2020 May 01.
Article in English | MEDLINE | ID: mdl-32092544

ABSTRACT

Sulfidated nano zerovalent iron (S-nZVI), stabilized with carboxymethyl cellulose (CMC), was successfully synthesized on site and injected into the subsurface at a site contaminated with a broad range of chlorinated volatile organic compounds (cVOCs). Transport of CMC-S-nZVI to the monitoring wells, both downgradient and upgradient, resulted in a significant decrease in concentrations of aqueous-phase cVOCs. Short-term (0-17 days) total boron and chloride measurements indicated dilution and displacement in these wells. Importantly however, compound specific isotope analysis (CSIA), changes in concentrations of intermediates, and increase in ethene concentrations confirmed dechlorination of cVOCs. Dissolution from the DNAPL pool into the aqueous phase at the deepest levels (4.0-4.5 m bgs) was identifiable from the increased cVOCs concentrations during long-term monitoring. However, at the uppermost levels (∼1.5 m above the source zone) a contrasting trend was observed indicating successful dechlorination. Changes in cVOCs concentrations and CSIA data suggest both sequential hydrogenolysis as well as reductive ß-elimination as the possible transformation mechanisms during the short-term abiotic and long-term biotic dechlorination. One of the most positive outcomes of this CMC-S-nZVI field treatment is the non-accumulation of lower chlorinated VOCs, particularly vinyl chloride. Post-treatment soil cores also revealed significant decreases in cVOCs concentrations throughout the targeted treatment zones. Results from this field study show that sulfidation is a suitable amendment for developing more efficient nZVI-based in situ remediation technologies.


Subject(s)
Groundwater , Water Pollutants, Chemical , Carboxymethylcellulose Sodium , Halogenation , Iron , Solvents , Water Wells
4.
Water Res ; 170: 115319, 2020 Mar 01.
Article in English | MEDLINE | ID: mdl-31790885

ABSTRACT

Treatment of nano zerovalent iron (nZVI) with lower valent forms of sulfur compounds (sulfidation) has the potential to increase the selectivity and reactivity of nZVI with target contaminants and to decrease inter-particle aggregation for improving its mobility. These developments help in addressing some of the long-standing challenges associated with nZVI-based remediation treatments and are of great interest for in situ applications. Herein we report results from a field-scale project conducted at a contaminated site. Sulfidated nZVI (S-nZVI) was prepared on site by first synthesizing carboxymethyl cellulose (CMC) stabilized nZVI with sodium borohydride as a reductant and then sulfidating the nZVI suspension by adding sodium dithionite. Transmission electron microscopy (TEM) coupled with energy dispersive X-ray spectroscopy (EDS) of CMC-S-nZVI, from synthesis barrels, confirms the presence of both discrete spherical nZVI-like particles (∼90 nm) as well as larger irregular structures (∼500 nm) comprising of iron sulfides. This CMC-S-nZVI suspension was gravity fed into a sandy material and monitored through multiple multi-level monitoring wells. Samples collected from upstream and downstream wells suggest very good radial and vertical iron distribution. TEM-EDS analysis from the recovered well samples also indicates the presence of both nZVI-like particles as well as the larger flake-like structures, similar to those found in the injected CMC-S-nZVI suspension. This study shows that S-nZVI stabilized with CMC can be safely synthesized on site and is highly mobile and stable in the subsurface, demonstrating for the first time the field applicability of S-nZVI.


Subject(s)
Iron , Metal Nanoparticles , Carboxymethylcellulose Sodium , Water Wells
5.
Environ Sci Technol ; 50(14): 7658-70, 2016 07 19.
Article in English | MEDLINE | ID: mdl-27305345

ABSTRACT

Nanoscale zerovalent iron (nZVI) is an emerging technology for the remediation of contaminated sites. However, there are concerns related to the impact of nZVI on in situ microbial communities. In this study, the microbial community composition at a contaminated site was monitored over two years following the injection of nZVI stabilized with carboxymethyl cellulose (nZVI-CMC). Enhanced dechlorination of chlorinated ethenes to nontoxic ethene was observed long after the expected nZVI oxidation. The abundance of Dehalococcoides (Dhc) and vinyl chloride reductase (vcrA) genes, monitored using qPCR, increased by over an order of magnitude in nZVI-CMC-impacted wells. The entire microbial community was tracked using 16S rRNA gene amplicon pyrosequencing. Following nZVI-CMC injection, a clear shift in microbial community was observed, with most notable increases in the dechlorinating genera Dehalococcoides and Dehalogenimonas. This study suggests that coupled abiotic degradation (i.e., from reaction with nZVI) and biotic degradation fueled by CMC led to the long-term degradation of chlorinated ethenes at this field site. Furthermore, nZVI-CMC addition stimulated dehalogenator growth (e.g., Dehalococcoides) and biotic degradation of chlorinated ethenes.


Subject(s)
Carboxymethylcellulose Sodium , Iron , Chloroflexi , Halogenation , RNA, Ribosomal, 16S
6.
Environ Sci Technol ; 50(10): 5243-51, 2016 05 17.
Article in English | MEDLINE | ID: mdl-27128632

ABSTRACT

1,2-Dichloroethane (1,2-DCA) is a chlorinated solvent classified as a probable human carcinogen. Due to its extensive use in industrial applications, widespread contamination, and recalcitrance toward abiotic dechlorination, 1,2-DCA remains a challenging compound for the remediation community. Over the past decade, nano zerovalent iron (nZVI) has been efficiently used to treat many of the chlorinated compounds of concern. However, thus far, even nZVI (monometallic or bimetallic) has been unable to dechlorinate 1,2-DCA. Therefore, an alternative treatment coupling nZVI with dithionite to treat 1,2-DCA is proposed in this work. Coupled nZVI-dithionite was able to degrade >90% 1,2-DCA over the course of a year. The effects of dithionite and nZVI loadings, carboxymethyl cellulose (CMC) coating, addition of palladium, and other iron species as metal surfaces on the degradation kinetics were also investigated. Observed pseudo-first-order rate constants (kobs) ranged from 3.8 × 10(-3) to 7.8 × 10(-3) d(-1). Both nucleophilic substitution and reductive dechlorination are the proposed mechanisms for 1,2-DCA degradation by coupled nZVI-dithionite treatment. Characterization analysis of the nZVI-dithionite nanoparticles shows that most of the iron was still preserved in the zerovalent state even after more than one year of reactivity with some iron sulfide (FeS) formation. Scanning electron microscopy (SEM) analysis shows that the nanosized spherical particles were still present along with the FeS platelets. This novel treatment represents the first nZVI-based formulation to achieve nearly complete degradation of 1,2-DCA.


Subject(s)
Dithionite , Iron , Halogenation , Palladium , Sulfides
7.
J Hazard Mater ; 308: 106-12, 2016 May 05.
Article in English | MEDLINE | ID: mdl-26808236

ABSTRACT

Nanoscale zero valent iron (nZVI) and organochlorine respiring bacteria (ORB) are two technologies used to detoxify chlorinated aliphatic hydrocarbons (CAHs). nZVI can rapidly detoxify high CAH concentrations, but is quickly oxidised and unable to degrade certain CAHs (e.g., 1,2-dichlorothane). In contrast, ORB can dechlorinate CAHs resistant to nZVI (e.g., 1,2-dichlorothane) but are inhibited by other CAHs of concern degradable by nZVI (e.g., chloroform and carbon tetrachloride). Combining the two was proposed as a unique treatment train to overcome each technology's shortcomings. In this study, this combined remedy was investigated using a mixture of 1,2-dichloroethane, degradable by ORB but not nZVI, and 1,1,2-trichloroethane, susceptible to both. Results indicated that nZVI rapidly dechlorinated 1,1,2-trichloroethane when supplied above 0.5 g/L, however ORB were inhibited and unable to dechlorinate 1,2-dichloroethane. pH increase and ionic species associated with nZVI did not significantly impact ORB, pinpointing Fe(0) particles as responsible for ORB inhibition. Below 0.05 g/L nZVI, ORB activity was stimulated. Results suggest that combining ORB and nZVI at appropriate doses can potentially treat a wider range of CAHs than each individual remedy. At field sites where nZVI was applied, it is likely that in situ nZVI concentrations were below the threshold of negative consequences.


Subject(s)
Bacteria/metabolism , Ethylene Dichlorides , Iron/chemistry , Metal Nanoparticles/chemistry , Trichloroethanes , Environmental Pollutants/chemistry , Environmental Pollutants/metabolism , Ethylene Dichlorides/chemistry , Ethylene Dichlorides/metabolism , Trichloroethanes/chemistry , Trichloroethanes/metabolism
8.
J Contam Hydrol ; 183: 16-28, 2015 Dec.
Article in English | MEDLINE | ID: mdl-26496622

ABSTRACT

Nano-scale zero valent iron (nZVI) has been used at a number of contaminated sites over the last decade. At most of these sites, significant decreases in contaminant concentrations have resulted from the application of nZVI. However, limited work has been completed investigating nZVI field-scale mobility. In this study, a field test was combined with numerical modeling to examine nZVI reactivity along with transport properties in variably saturated soils. The field test consisted of 142L of carboxymethyle cellulose (CMC) stabilized monometallic nZVI synthesized onsite and injected into a variably saturated zone. Periodic groundwater samples were collected from the injection well, as well as, from two monitoring wells to analyze for chlorinated solvents and other geochemistry indicators. This study showed that CMC stabilized monometallic nZVI was able to decrease tricholorethene (TCE) concentrations in groundwater by more than 99% from the historical TCE concentrations. A three dimensional, three phase, finite difference numerical simulator, (CompSim) was used to further investigate nZVI and polymer transport at the variably saturated site. The model was able to accurately predict the field observed head data without parameter fitting. In addition, the numerical simulator estimated the mass of nZVI delivered to the saturated and unsaturated zones and distinguished the nZVI phase (i.e. aqueous or attached). The simulation results showed that the injected slurry migrated radially outward from the injection well, and therefore nZVI transport was governed by injection velocity and viscosity of the injected solution. A suite of sensitivity analyses was performed to investigate the impact of different injection scenarios (e.g. different volume and injection rate) on nZVI migration. Simulation results showed that injection of a higher nZVI volume delivered more iron particles at a given distance; however, the travel distance was not proportional to the increase in volume. Moreover, simulation results showed that using a 1D transport equation to simulate nZVI migration in the subsurface may overestimate the travel distance. This is because the 1D transport equation assumes a constant velocity while pore water velocity radially decreases from the well during injection. This study suggests that on-site synthesized nZVI particles are mobile in the subsurface and that a numerical simulator can be a valuable tool for optimal design of nZVI field applications.


Subject(s)
Environmental Restoration and Remediation/methods , Iron , Metal Nanoparticles , Water Pollutants, Chemical/analysis , Carboxymethylcellulose Sodium/chemistry , Computer Simulation , Groundwater/analysis , Iron/chemistry , Metal Nanoparticles/chemistry , Models, Theoretical , Ontario , Soil/chemistry , Soil Pollutants/analysis , Soil Pollutants/chemistry , Trichloroethanes/analysis , Trichloroethanes/chemistry , Viscosity , Water Wells
9.
Environ Sci Technol ; 49(14): 8648-56, 2015 Jul 21.
Article in English | MEDLINE | ID: mdl-26090687

ABSTRACT

A pilot scale injection of nanoscale zerovalent iron (nZVI) stabilized with carboxymethyl cellulose (CMC) was performed at an active field site contaminated with a range of chlorinated volatile organic compounds (cVOC). The cVOC concentrations and microbial populations were monitored at the site before and after nZVI injection. The remedial injection successfully reduced parent compound concentrations on site. A period of abiotic degradation was followed by a period of enhanced biotic degradation. Results suggest that the nZVI/CMC injection created conditions that stimulated the native populations of organohalide-respiring microorganisms. The abundance of Dehalococcoides spp. immediately following the nZVI/CMC injection increased by 1 order of magnitude throughout the nZVI/CMC affected area relative to preinjection abundance. Distinctly higher cVOC degradation occurred as a result of the nZVI/CMC injection over a 3 week evaluation period when compared to control wells. This suggests that both abiotic and biotic degradation occurred following injection.


Subject(s)
Carboxymethylcellulose Sodium/chemistry , Environmental Pollution , Environmental Restoration and Remediation/methods , Iron/chemistry , Volatile Organic Compounds , Biodegradation, Environmental , Chloroflexi/genetics , Chloroflexi/isolation & purification , Halogenation , Ontario , Volatile Organic Compounds/analysis , Volatile Organic Compounds/chemistry , Volatile Organic Compounds/metabolism
10.
Environ Sci Technol ; 48(5): 2862-9, 2014.
Article in English | MEDLINE | ID: mdl-24479900

ABSTRACT

Nanoscale zerovalent iron (nZVI) particles were injected into a contaminated sandy subsurface area in Sarnia, Ontario. The nZVI was synthesized on site, creating a slurry of 1 g/L nanoparticles using the chemical precipitation method with sodium borohydride (NaBH4) as the reductant in the presence of 0.8% wt. sodium carboxymethylcellulose (CMC) polymer to form a stable suspension. Individual nZVI particles formed during synthesis had a transmission electron microscopy (TEM) quantified particle size of 86.0 nm and dynamic light scattering (DLS) quantified hydrodynamic diameter for the CMC and nZVI of 624.8 nm. The nZVI was delivered to the subsurface via gravity injection. Peak normalized total Fe breakthrough of 71% was observed 1m from the injection well and remained above 50% for the 24 h injection period. Samples collected from a monitoring well 1 m from the injection contained nanoparticles with TEM-measured particle diameter of 80.2 nm and hydrodynamic diameter of 562.9 nm. No morphological changes were discernible between the injected nanoparticles and nanoparticles recovered from the monitoring well. Energy dispersive X-ray spectroscopy (EDS) was used to confirm the elemental composition of the iron nanoparticles sampled from the downstream monitoring well, verifying the successful transport of nZVI particles. This study suggests that CMC stabilized nZVI can be transported at least 1 m to the contaminated source zone at significant Fe(0) concentrations for reaction with target contaminants.


Subject(s)
Iron/chemistry , Metal Nanoparticles/chemistry , Carboxymethylcellulose Sodium/chemistry , Soil Pollutants/chemistry , Time and Motion Studies , Water Purification/methods
11.
Environ Sci Pollut Res Int ; 20(9): 6210-21, 2013 Sep.
Article in English | MEDLINE | ID: mdl-23589245

ABSTRACT

Nano zerovalent iron (nZVI) is an effective remediant for removing various organic and inorganic pollutants from contaminated water sources. Batch experiments were conducted to characterize the nZVI surface and to investigate the effects of various solution properties such as pH, initial cadmium concentration, sorbent dosage, ionic strength, and competitive ions on cadmium removal by nZVI. Energy-dispersive X-ray and X-ray photoelectron spectroscopy results confirmed removal of Cd(2+) ions by nZVI through adsorption. Cd(2+) adsorption decreased in the presence of competitive cations in the order: Zn(2+) > Co(2+) > Mg(2+) > Mn(2+) = Cu(2+) > Ca(2+) > Na(2+) = K(+). Higher concentrations of Cl(-) significantly decreased the adsorption. Cadmium removal increased with solution pH and reached a maximum at pH 8.0. The effects of various solution properties indicated Cd(2+) adsorption on nZVI to be a chemisorption (inner-sphere complexation) process. The three surface complexation models (diffuse layer model, constant capacitance model, and triple layer model) fitted well to the adsorption edge experimental data indicating the formation of nZVI-Cd bidentate inner-sphere surface complexes. Our results suggest that nZVI can be effectively used for the removal of cadmium from contaminated water sources with varying chemical conditions.


Subject(s)
Cadmium/chemistry , Iron/chemistry , Water Pollutants, Chemical/chemistry , Water Purification/methods , Adsorption , Microscopy, Electron, Scanning , Models, Theoretical , Surface Properties
12.
J Hazard Mater ; 186(1): 458-65, 2011 Feb 15.
Article in English | MEDLINE | ID: mdl-21130566

ABSTRACT

Nano zerovalent iron (nZVI) is an effective adsorbent for removing various organic and inorganic contaminants. In this study, nZVI particles were used to investigate the removal of Cd(2+) in the concentration range of 25-450 mg L(-1). The effect of temperature on kinetics and equilibrium of cadmium sorption on nZVI particles was thoroughly examined. Consistent with an endothermic reaction, an increase in the temperature resulted in increasing cadmium adsorption rate. The adsorption kinetics well fitted using a pseudo second-order kinetic model. The calculated activation energy for adsorption was 54.8 kJ mol(-1), indicating the adsorption process to be chemisorption. The intraparticle diffusion model described that the intraparticle diffusion was not the only rate-limiting step. The adsorption isotherm data could be well described by the Langmuir as well as Temkin equations. The maximum adsorption capacity of nZVI for Cd(2+) was found to be 769.2 mg g(-1) at 297 K. Thermodynamic parameters (i.e., change in the free energy (ΔG(o)), the enthalpy (ΔH(o)), and the entropy (ΔS(o))) were also evaluated. The overall adsorption process was endothermic and spontaneous in nature. EDX analysis indicated the presence of cadmium ions on the nZVI surface. These results suggest that nZVI could be employed as an efficient adsorbent for the removal of cadmium from contaminated water sources.


Subject(s)
Cadmium/isolation & purification , Adsorption , Diffusion , Kinetics , Microscopy, Electron, Scanning , Thermodynamics
13.
Chemosphere ; 79(8): 865-72, 2010 May.
Article in English | MEDLINE | ID: mdl-20226494

ABSTRACT

Zerovalent iron barriers have become a viable treatment for field-scale cleanup of various ground water contaminants. While contact with the iron surface is important for contaminant destruction, the interstitial pore water within and near the iron barrier will be laden with aqueous, adsorbed and precipitated Fe(II) phases. These freshly precipitated iron minerals could play an important role in transforming high explosives (HE). Our objective was to determine the transformation of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), and TNT (2,4,6-trinitrotoluene) by freshly precipitated iron Fe(II)/Fe(III) minerals. This was accomplished by quantifying the effects of initial Fe(II) concentration, pH, and the presence of aquifer solids (Fe(III) phases) on HE transformation rates. Results showed that at pH 8.2, freshly precipitated iron minerals transformed RDX, HMX, and TNT with reaction rates increasing with increasing Fe(II) concentrations. RDX and HMX transformations in these solutions also increased with increasing pH (5.8-8.55). By contrast, TNT transformation was not influenced by pH (6.85-8.55) except at pH values <6.35. Transformations observed via LC/MS included a variety of nitroso products (RDX, HMX) and amino degradation products (TNT). XRD analysis identified green rust and magnetite as the dominant iron solid phases that precipitated from the aqueous Fe(II) during HE treatment under anaerobic conditions. Geochemical modeling also predicted Fe(II) activity would likely be controlled by green rust and magnetite. These results illustrate the important role freshly precipitated Fe(II)/Fe(III) minerals in aqueous Fe(II) solutions play in the transformation of high explosives.


Subject(s)
Azocines/chemistry , Environmental Restoration and Remediation/methods , Explosive Agents/chemistry , Iron/chemistry , Triazines/chemistry , Trinitrotoluene/chemistry , Cations/chemistry , Hydrogen-Ion Concentration , Models, Chemical
14.
Environ Sci Technol ; 40(9): 3043-9, 2006 May 01.
Article in English | MEDLINE | ID: mdl-16719109

ABSTRACT

The prevalent use of chloroacetanilide herbicides has resulted in nonpoint contamination of some groundwater and surface water. We determined the efficacy of dithionite-treated sediment and soils to transform chloroacetanilides. When used alone, dithionite rapidly dechlorinates chloroacetanilides in water, with the following order of reactivity: propachlor > alachlor > acetochlor > metolachlor. Stoichiometric release of chloride occurs during reaction with dithionite, and thiosulfate herbicide derivatives are produced. Treating aquifer sediment with dithionite reduces native Fe(lII), creating a redox barrier of Fe(ll)-bearing minerals and surface-bound Fe(ll). Washing the reduced sediment (buffered with citrate-bicarbonate) with oxygen-free water removed Fe(ll) and excess dithionite and no alachlor transformation was observed. In contrast, a dithionite-treated surface soil, rich in clay and iron, effectively dechlorinated alachlor after washing. Exposing alachlor to aquifer sediment treated with dithionite in potassium carbonate buffer (pH 8.5-9.0) produced dechlorinated alachlor as the major degradation product. Our results provide proof-of-concept that dechlorination of chloroacetanilide herbicides by dithionite and dithionite-treated aquifer sediment and soil is a remediation option in natural environments where iron-bearing minerals are abundant.


Subject(s)
Acetamides/chemistry , Dithionite/pharmacology , Herbicides/chemistry , Soil Pollutants/analysis , Acetamides/analysis , Adsorption , Buffers , Carbonates/chemistry , Chlorine/chemistry , Hydrogen-Ion Concentration , Kinetics , Models, Chemical , Oxidation-Reduction , Potassium/chemistry , Water Pollutants
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