Enhanced anaerobic dechlorination of polychlorinated biphenyl in sediments by bioanode stimulation

International Nuclear Information System (INIS)

Yu, Hui; Feng, Chunhua; Liu, Xiaoping; Yi, Xiaoyun; Ren, Yuan; Wei, Chaohai

2016-01-01

The application of a low-voltage electric field as an electron donor or acceptor to promote the bioremediation of chlorinated organic compounds represents a promising technology meeting the demand of developing an efficient and cost-effective strategy for in situ treatment of PCB-contaminated sediments. Here, we reported that bioanode stimulation with an anodic potential markedly enhanced dechlorination of 2,3,4,5-tetrachlorobiphenyl (PCB 61) contained in the sediment at an electronic waste recycling site of Qingyuan, Guangdong, China. The 110-day incubation of the bioanode with a potential poised at 0.2 V relative to saturated calomel electrode enabled 58% transformation of the total PCB 61 at the initial concentration of 100 μmol kg"−"1, while only 23% was reduced in the open-circuit reference experiment. The introduction of acetate to the bioelectrochemical reactor (BER) further improved PCB 61 transformation to 82%. Analysis of the bacterial composition showed significant community shifts in response to variations in treatment. At phylum level, the bioanode stimulation resulted in substantially increased abundance of Actinobacteria, Bacteroidetes, and Chloroflexi either capable of PCB dechlorination, or detected in the PCB-contaminated environment. At genus level, the BER contained two types of microorganisms: electrochemically active bacteria (EAB) represented by Geobacter, Ignavibacterium, and Dysgonomonas, and dechlorinating bacteria including Hydrogenophaga, Alcanivorax, Sedimentibacter, Dehalogenimonas, Comamonas and Vibrio. These results suggest that the presence of EAB can promote the population of dechlorinating bacteria which are responsible for PCB 61 transformation. - Highlights: • A bioelectrochemical reactor (BER) was constructed for anaerobic PCB dechlorination. • Bioanode stimulation substantially enhanced dechlorination of PCB 61. • Electrochemically active bacteria and dechlorinating bacteria coexisted in the BER. - Bioanode

Reductive dechlorination of hexachlorocyclohexane (HCH) isomers in soil under anaerobic conditions

NARCIS (Netherlands)

Middeldorp, P.J.M.; Doesburg, van W.C.J.; Schraa, G.; Stams, A.J.M.

2005-01-01

The biological anaerobic reductive dechlorination of -hexachlorocyclohexane under methanogenic conditions was tested in a number of contaminated soil samples from two locations in the Netherlands. Soils from a heavily polluted location showed rapid dechlorination of -hexachlorocyclohexane to benzene

Radiation dechlorination of PCE and PCB in the quarter operation flow apparatus

International Nuclear Information System (INIS)

Mucka, V.; Silber, R.; Pospisil, M.; Camra, M.; Bartonicek, B.

1999-01-01

The aim of this work was to verify practical possibilities of radiation dechlorination of liquid chlorinated substrates [perchloroethylene (PCE) and polychlorinated biphenyls (PCB)] in the quarter operation flow apparatus. In this apparatus may be disposable work over 50 dm 3 of media. Radiation dechlorination of PCE proceeds more effectively as dechlorination of PCB in flow regimes, too. Radiation chemical yield of G(-OH - ) decrease with increasing applied radiation dose and at the dose 5 kGy for PCE it is 200 · 10 -2 eV -1 and for PCB this value is 55 · 10 -2 eV -1 . At increasing original concentration of PCE or PCB the G-values decreases. The radical chain mechanism of dechlorination of PCE and PCB was proposed

Heterogeneous hyporheic zone dechlorination of a TCE groundwater plume discharging to an urban river reach.

Science.gov (United States)

Freitas, Juliana G; Rivett, Michael O; Roche, Rachel S; Durrant Neé Cleverly, Megan; Walker, Caroline; Tellam, John H

2015-02-01

The typically elevated natural attenuation capacity of riverbed-hyporheic zones is expected to decrease chlorinated hydrocarbon (CHC) groundwater plume discharges to river receptors through dechlorination reactions. The aim of this study was to assess physico-chemical processes controlling field-scale variation in riverbed-hyporheic zone dechlorination of a TCE groundwater plume discharge to an urban river reach. The 50-m long pool-riffle-glide reach of the River Tame in Birmingham (UK) studied is a heterogeneous high energy river environment. The shallow riverbed was instrumented with a detailed network of multilevel samplers. Freeze coring revealed a geologically heterogeneous and poorly sorted riverbed. A chlorine number reduction approach provided a quantitative indicator of CHC dechlorination. Three sub-reaches of contrasting behaviour were identified. Greatest dechlorination occurred in the riffle sub-reach that was characterised by hyporheic zone flows, moderate sulphate concentrations and pH, anaerobic conditions, low iron, but elevated manganese concentrations with evidence of sulphate reduction. Transient hyporheic zone flows allowing input to varying riverbed depths of organic matter are anticipated to be a key control. The glide sub-reach displayed negligible dechlorination attributed to the predominant groundwater baseflow discharge condition, absence of hyporheic zone, transition to more oxic conditions and elevated sulphate concentrations expected to locally inhibit dechlorination. The tail-of-pool-riffle sub-reach exhibited patchy dechlorination that was attributed to sub-reach complexities including significant flow bypass of a low permeability, high organic matter, silty unit of high dechlorination potential. A process-based conceptual model of reach-scale dechlorination variability was developed. Key findings of practitioner relevance were: riverbed-hyporheic zone CHC dechlorination may provide only a partial, somewhat patchy barrier to CHC

PALLADIUM-FACILITATED ELECTROLYTIC DECHLORINATION OF 2-CHLOROBIPHENYL USING A GRANULAR-GRAPHITE ELECTRODE.

Science.gov (United States)

Palladium-assisted electrocatalytic dechlorination of 2-chlorobiphenyl (2-Cl BP) in aqueous solutions was conducted in a membrane-separated electrochemical reactor with granular-graphite packed electrodes. The dechlorination took place at a granular-graphite cathode while Pd was ...

Comparison of dechlorination rates for field DNAPL vs synthetic samples: effect of sample matrix

Science.gov (United States)

O'Carroll, D. M.; Sakulchaicharoen, N.; Herrera, J. E.

2015-12-01

Nanometals have received significant attention in recent years due to their ability to rapidly destroy numerous priority source zone contaminants in controlled laboratory studies. This has led to great optimism surrounding nanometal particle injection for insitu remediation. Reported dechlorination rates vary widely among different investigators. These differences have been ascribed to differences in the iron types (granular, micro, or nano-sized iron), matrix solution chemistry and the morphology of the nZVI surface. Among these, the effects of solution chemistry on rates of reductive dechlorination of various chlorinated compounds have been investigated in several short-term laboratory studies. Variables investigated include the effect of anions or groundwater solutes such as SO4-2, Cl-, NO3-, pH, natural organic matters (NOM), surfactant, and humic acid on dechlorination reaction of various chlorinated compounds such as TCE, carbon tetrachloride (CT), and chloroform (CF). These studies have normally centered on the assessment of nZVI reactivity toward dechlorination of an isolated individual contaminant spiked into a ground water sample under ideal conditions, with limited work conducted using real field samples. In this work, the DNAPL used for the dechlorination study was obtained from a contaminatied site. This approach was selected to adequately simulate a condition where the nZVI suspension was in direct contact with DNAPL and to isolate the dechlorination activity shown by the nZVI from the groundwater matrix effects. An ideal system "synthetic DNAPL" composed of a mixture of chlorinated compounds mimicking the composition of the actual DNAPL was also dechlorinated to evaluate the DNAPL "matrix effect" on NZVI dechlorination activity. This approach allowed us to evaluate the effect of the presence of different types of organic compounds (volatile fatty acids and humic acids) found in the actual DNAPL on nZVI dechlorination activity. This presentation will

Rules of thumb for assessing reductive dechlorination pathways of PCDDs in specific systems

International Nuclear Information System (INIS)

Lu Guining; Dang Zhi; Fennell, Donna E.; Huang Weilin; Li Zhong; Liu Congqiang

2010-01-01

This paper reports a theoretical validation and proposition of the reductive dechlorination pathways for polychlorinated dibenzo-p-dioxin (PCDD) congeners. Density functional theory (DFT) calculations were carried out at the B3LYP/6-31G(d) level for all PCDDs and Mulliken atomic charges on chlorine atoms were adopted as the probe of the dechlorination reaction activity. The experimentally substantiated dechlorination pathways of 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD) and its daughter products in the presence of zero-valent zinc were validated and the complete pathway of dechlorination of octachlorodibenzo-p-dioxin (OCDD) was proposed. The proposed pathways were found to be consistent with anaerobic biotransformation of several PCDD congeners. Four rules of thumb arrived from this study include (1) the chlorine atoms in the longitudinal (1,4,6,9) positions are removed in preference to the chlorine atoms on lateral (2,3,7,8) positions; (2) the chlorine atom that has more neighboring chlorine atoms at ortho-, meta- and para-positions is to be eliminated; (3) reductive dechlorination prefers to take place on the benzene ring having more chlorine substitutions; and (4) a chlorine atom on the side of the longitudinal symmetry axis containing more chlorine atoms is preferentially eliminated. These rules of thumb can be conveniently used for rapidly predicting the major dechlorination pathway for a given PCDD in specific systems.

Factors Influencing TCE Anaerobic Dechlorination Investigated via Simulations of Microcosm Experiments

Science.gov (United States)

Mao, X.; Harkness, M.; Lee, M. D.; Mack, E. E.; Dworatzek, S.; Acheson, C.; McCarty, P.; Barry, D. A.; Gerhard, J. I.

2006-12-01

SABRE (Source Area BioREmediation) is a public-private consortium whose charter is to determine if enhanced anaerobic bioremediation can result in effective and quantifiable treatment of chlorinated solvent DNAPL source areas. The focus of this 4-year, $5.7 million research project is a field site in the United Kingdom containing a TCE DNAPL source area. In preparation, a microcosm study was performed to determine the optimal combination of factors to support reductive dechlorination of TCE in site soil and groundwater. The study consisted of 168 bottles distributed between four laboratories (Dupont, GE, SiREM, and Terra Systems) and tested the impact of six carbon substrates (lactate, acetate, methanol, SRS (soybean oil), hexanol, butyl acetate), bioaugmentation with KB-1 bacterial culture, three TCE levels (100 mg/L, 400 mg/L, and 800 mg/L) and two sulphate levels (200 mg/L, >500 mg/L) on TCE dechlorination. This research presents a numerical model designed to simulate the main processes occurring in the microcosms, including substrate fermentation, sequential dechlorination, toxic inhibition, and the influence of sulphate concentration. In calibrating the model to over 60 of the microcosm experiments, lumped parameters were employed to quantify the effect of key factors on the conversion rate of each chlorinated ethene in the TCE degradation sequence. Results quantify the benefit (i.e., increased stepwise dechlorination rate) due to both bioaugmentation and the presence of higher sulphate concentrations. Competitive inhibition is found to increase in significance as TCE concentrations increase; however, inclusion of Haldane inhibition is not supported. Over a wide range of experimental conditions and dechlorination steps, SRS appears to induce relatively little hydrogen limitation, thereby facilitating relatively quick conversion of TCE to ethene. In general, hydrogen limitation is found to increase with increasing TCE concentration and with bioaugmentation, and

Chlorination and dechlorination rates in a forest soil — A combined modelling and experimental approach

Energy Technology Data Exchange (ETDEWEB)

Montelius, Malin, E-mail: malin.montelius@liu.se [Department of Thematic Studies — Environmental Change, Linköping University, 581 83 Linköping (Sweden); Svensson, Teresia [Department of Thematic Studies — Environmental Change, Linköping University, 581 83 Linköping (Sweden); Lourino-Cabana, Beatriz [EDF, Laboratoire National d' Hydraulique et Environnement, 78401 Chatou (France); Thiry, Yves [Andra, Research and Development Division, Parc de la Croix Blanche, 1/7 rue Jean Monnet, 92298 Châtenay-Malabry Cedex (France); Bastviken, David [Department of Thematic Studies — Environmental Change, Linköping University, 581 83 Linköping (Sweden)

2016-06-01

Much of the total pool of chlorine (Cl) in soil consists of naturally produced organic chlorine (Cl{sub org}). The chlorination of bulk organic matter at substantial rates has been experimentally confirmed in various soil types. The subsequent fates of Cl{sub org} are important for ecosystem Cl cycling and residence times. As most previous research into dechlorination in soils has examined either single substances or specific groups of compounds, we lack information about overall bulk dechlorination rates. Here we assessed bulk organic matter chlorination and dechlorination rates in coniferous forest soil based on a radiotracer experiment conducted under various environmental conditions (additional water, labile organic matter, and ammonium nitrate). Experiment results were used to develop a model to estimate specific chlorination (i.e., fraction of Cl{sup −} transformed to Cl{sub org} per time unit) and specific dechlorination (i.e., fraction of Cl{sub org} transformed to Cl{sup −} per time unit) rates. The results indicate that chlorination and dechlorination occurred simultaneously under all tested environmental conditions. Specific chlorination rates ranged from 0.0005 to 0.01 d{sup −1} and were hampered by nitrogen fertilization but were otherwise similar among the treatments. Specific dechlorination rates were 0.01–0.03 d{sup −1} and were similar among all treatments. This study finds that soil Cl{sub org} levels result from a dynamic equilibrium between the chlorination and rapid dechlorination of some Cl{sub org} compounds, while another Cl{sub org} pool is dechlorinated more slowly. Altogether, this study demonstrates a highly active Cl cycling in soils. - Highlights: • Chlorination and dechlorination rates in soil were revealed by a radiotracer method. • Chlorination was hampered by nitrogen addition. • Both Cl{sup −} and many Cl{sub org} compounds are highly reactive in soils. • Some formed Cl{sub org} seem to be refractory.

Effects of bioaugmentation on enhanced reductive dechlorination of 1,1,1-trichloroethane in groundwater - a comparison of three sites

DEFF Research Database (Denmark)

Scheutz, Charlotte; Durant, Neal D.; Broholm, Mette Martina

2014-01-01

, microcosms were amended with various concentrations of chloroethanes (TCA or monochloroethane [CA]) and/or chloroethenes (tetrachloroethene [PCE], trichloroethene [TCE], or 1,1-dichloroethene [1,1-DCE]). Results showed that combined electron donor addition and bioaugmentation stimulated dechlorination of TCA...... and 1,1-dichloroethane (1,1-DCA) to CA, and dechlorination of PCE, TCE, 1,1-DCE and cDCE to ethane. Dechlorination of CA was not observed. Bioaugmentation improved the rate and extent of TCA and 1,1-DCA dechlorination at two sites, but did not accelerate dechlorination at a third site where geochemical...... conditions were reducing and Dhc and Dhb were indigenous. TCA at initial concentrations of 5 mg/L inhibited (i.e., slowed the rate of) TCA dechlorination, TCE dechlorination, donor fermentation, and methanogenesis. 1 mg/L TCA did not inhibit dechlorination of TCA, TCE or cDCE. Moreover, complete...

Effects of different electron donor feeding patterns on TCE reductive dechlorination performance.

Science.gov (United States)

Panagiotakis, I; Antoniou, K; Mamais, D; Pantazidou, M

2015-03-01

This study investigates how the feeding pattern of e(-) donors might affect the efficiency of enhanced in situ bioremediation in TCE-contaminated aquifers. A series of lab-scale batch experiments were conducted using butyrate or hydrogen gas (H2) as e(-) donor and a TCE-dechlorinating microbial consortium dominated by Dehalococcoides spp. The results of these experiments demonstrate that butyrate is similarly efficient for TCE dechlorination whether it is injected once or in doses. Moreover, the present work indicates that the addition of butyrate in great excess cannot be avoided, since it most likely provide, even indirectly, significant part of the H2 required. Furthermore, methanogenesis appears to be the major ultimate e(-) accepting process in all experiments, regardless the e(-) donor used and the feeding pattern. Finally, the timing of injection of H2 seems to significantly affect dechlorination performance, since the injection during the early stages improves VC-to-ETH dechlorination and reduce methanogenic activity.

IDENTIFICATION OF CHLOROMETHANE FORMATION PATHS DURING ELECTROCHEMICAL DECHLORINATION OF TCE USING GRAPHITE ELECTRODES

Science.gov (United States)

The purpose of this research is to investigate the formation of chloromethane during TCE dechlorination in a mixed electrochemical reactor using graphite electrodes. Chloromethane was the major chlorinated organic compound detected in previous dechlorination experiments. In order...

IDENTIFICATION OF CHLOROMETHANE FROMATION PATHS DURING ELECTROCHEMICAL DECHLORINATION OF TCE USING GRAPHITE ELECTRODES

Science.gov (United States)

The purpose of this research is to investigate the formation of chloromethane during TCE dechlorination in a mixed electrochemical reactor using graphite electrodes. Chloromethane was the major chlorinated organic compound detected in previous dechlorination experiments. In order...

Dechlorinating ability of TCE-fed microcosms with different electron donors

International Nuclear Information System (INIS)

Panagiotakis, Iraklis; Mamais, Daniel; Pantazidou, Marina; Marneri, Matina; Parapouli, Maria; Hatziloukas, Efstathios; Tandoi, Valter

2007-01-01

The main objective of the work presented herein is to assess the effect of different electron donors (butyric acid and methanol) on the dechlorinating activity of two microbial cultures where active methanogenic populations are present, in an effort to evaluate the importance of the electron donor selection process. The ability of each anaerobic culture to dechlorinate TCE, when enriched with either butyric acid or methanol, was verified based on the results of gas chromatography. In addition, the fluorescent in situ hybridization (FISH) and the polymerase chain reaction (PCR) methods gave positive results for the presence of Dehalococcoides spp. According to results of the batch tests conducted in this study, it appears that the selection of the electron donor for stimulating TCE dechlorination depends on microbial culture composition; therefore, the decision on the appropriate electron donor should be based on site-specific microcosm studies

Reductive dechlorination of organochlorine pesticides in soils from an abandoned manufacturing facility by zero-valent iron

International Nuclear Information System (INIS)

Cong, Xin; Xue, Nandong; Wang, Shijie; Li, Keji; Li, Fasheng

2010-01-01

Several experiments and a model were constructed using conventional granular zero-valent iron (ZVI) particles as the reducing agent to study the reductive dechlorination characteristics of hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethane (DDTs) in soils from a former pesticide-manufacturing site. The results showed that ZVI had good ability for the reductive dechlorination for both HCHs and DDTs. The reductive dechlorination of HCHs and DDTs proceeded at different rates. The pseudo first-order constants of HCHs were greater than those of DDTs. The reductive dechlorination rates in a descending order were γ-HCH > δ-HCH > β-HCH > α-HCH > o,p'-DDT > p,p'-DDT > p,p'-DDE. To discuss the major influential factors over the reductive dechlorination rates of HCHs and DDTs by ZVI, 22 quantum chemical descriptors were computed with the density functional theory at B3LYP/6-31G * level, which characterizes different molecular structures and physicochemical properties of HCHs and DDTs. A polyparameter linear free energy relationship (LFER) model was established, which correlates the reductive dechlorination properties of pollutants with their structural descriptors. Using the partial least squares (PLS) analysis, an optimal two-parameter LFER model was established. q + and q Cl - were more important factors in determining the dechlorination rate of OCPs in the chemical reductive reaction. This optimal model was stable and had good predictability. The model study also showed that the coefficient value of q + was 0.511, which positively correlated with the reductive dechlorination rate constant, whereas q Cl - was negatively correlated with it. The reductive dechlorination rate of pollutants appears to be limited mainly by the rate of dissolution in the aqueous phase. This model can be used to explain the degradation potential of organochlorine pesticides (OCPs) and the trend of residues changing during the soil remediation. Therefore, the study is of

[Effect of composting organic fertilizer supplies on hexachlorobenzene dechlorination in paddy soils].

Science.gov (United States)

Liu, Cui-Ying; Jiang, Xin

2013-04-01

A rice pot experiment was conducted in two soils, Hydragric Acrisols (Ac) and Gleyi-Stagnic Anthrosols (An). Three treatments including control and additions of 1% or 2% composting organic fertilizer were designed for each soil. The objective of this research was to evaluate the reductive dechlorination of hexachlorobenzene (HCB) as affected by organic fertilizer supplies in planted paddy soils, and to analyze the relationship between methane production and HCB dechlorination. The results showed that the HCB residues were decreased by 28.6%-30.1% of the initial amounts in Ac, and 47.3% -61.0% in An after 18 weeks of experiment. The amount of HCB and its metabolite uptake by rice plants was only a few thousandths of the initial HCB amount in soils. The main product of HCB dechlorination was pentachlorobenzene (PeCB). The rates of HCB dechlorination in An were higher than those in Ac, which was mainly attributed to the higher pH and dissolved organic carbon (DOC) content of An. The applications of both 1% and 2% composting organic fertilizer showed significant inhibition on PeCB production after the 6th and 10th week in Ac and An, respectively. In both tested soils, no significant difference of PeCB production rates was observed between the applications of 1% and 2% composting organic fertilizer. The role of methanogenic bacteria in HCB dechlorination was condition-dependent.

Radiation dechlorination of PCE in aqueous solutions under various conditions

International Nuclear Information System (INIS)

Mucka, V.; Lizalova, B.; Pospisil, M.; Silber, R.; Polakova, D.

2002-01-01

Complete text of publication follows. Radiation technology of water purification from chlorinated compounds seems to be one of the promising method (Getoff, 1996), analogously as it was shown (Mueka et al., 2000) with radiation degradation of polychlorinated biphenyls (PCBs). A systematic study of dechlorination of tetrachloroethylene (PCE) in aqueous solutions (initial concentrations ranging from 9.2 x 10 -6 to 2.5 x 10 -4 mol dm -3 ), initiated by γ-rays of 60 Co or by accelerated electrons (EB, 4.5 MeV) in presence of various modifiers (atmospheric oxygen, N 2 O-oxide, HCO 3 - - and NO 3 - - ions as well as various pH-values), was the aim of this paper. The studies showed that both actual concentration c of PCE and radiation yield G(Cl - ) decreased rapidly with increasing dose up to the dose of 2 kGy and the degree of dechlorination raised sharply in this dose-interval. The dechlorination was slightly promoted by atmospheric oxygen. Similarly, a promotion effect was detected in the case of the PCE-solutions saturated, prior to their irradiation, with the N 2 O-oxide. On the other hand, a presence of NO 3 - - or HCO 3 - -ions in irradiated samples led to an inhibiting effect. The inhibiting effect increased markedly with increasing concentration of both at above-mentioned ions up to the concentration of about 100 mg dm -3 . A pronounced inhibition of γ-radiation dechlorination of PCE was observed in alkaline aqueous solutions. The results obtained in this paper support the idea that the radiation dechlorination of PCE in aqueous solutions proceeds via an oxidative mechanism in which the γ-irradiation was found to be more effective than the EB-irradiation

Reductive dechlorination of tetrachlorobisphenol A by Pd/Fe bimetallic catalysts

International Nuclear Information System (INIS)

Huang, Qiang; Liu, Wen; Peng, Ping’an; Huang, Weilin

2013-01-01

Highlights: • TCBPA can be rapidly and completely dechlorinated by Pd/Fe bimetallic catalysts. • The observed rate constants are functions of dosages, initial concentration, Pd coverage and solution pH. • Pd dosage is the major factor in the observed rates of the reaction. • This is the first report investigating the dechlorination of TCBPA by Pd/Fe catalysts. -- Abstract: The Pd/Fe bimetallic catalysts of micron sizes were synthesized and the rates of tetrachlorobisphenol A (TCBPA) degradation were measured under various conditions using a batch reactor system. The results showed that TCBPA was rapidly dechlorinated to tri-, di- and mono-chlorobisphenol A and to bisphenol A (BPA). The observed rate constants (k obs ) were found to increase as functions of the Pd coverage on the Fe particles and the dosages of the catalysts within the reactors. The k obs value decreased as the initial TCBPA concentration increased, suggesting that the TCBPA dechlorination may follow a surface-site limiting Langmuir–Hinshelwood rate model. The weakly acidic solution, especially at or near pH 6.0, also favored the dechlorination of TCBPA. At pH 6.0, Pd coverage of 0.044 wt% and catalyst dosage of 5 g L −1 , TCBPA with an initial concentration of 20 μM was completely transformed within 60 min, and BPA was detected as the major product through the reaction time. Meanwhile, the k obs values measured at constant solution pH correlated linearly with the mass of particle-bound Pd introduced to the reactors, regardless of Pd/Fe catalyst dosage or Pd surface coverage. This study suggested that Pd/Fe catalysts could be potentially employed to rapidly degrade TCBPA in the contaminated environment

Dechlorination of chlorinated phenols by subnanoscale Pd 0 /Fe 0 intercalated in smectite: pathway, reactivity, and selectivity.

Science.gov (United States)

Jia, Hanzhong; Wang, Chuanyi

2015-12-30

Smectite clay was employed as templated matrix to prepare subnanoscale Pd(0)/Fe(0) particles, and their components as well as intercalated architectures were well characterized by X-ray energy dispersive spectroscopy (X-EDS) and X-ray diffraction (XRD). Furthermore, as-prepared Pd(0)/Fe(0) subnanoscale nanoparticles were evaluated for their dechlorination effect using chlorinated phenols as model molecules. As a result, pentachlorophenol (PCP) is selectively transformed to phenol in a stepwise dechlorination pathway within 6h, and the dechlorination rate constants show linearly relationship with contents of Pd as its loadings <0.065%. Comparing with PCP, other chlorinated phenols display similar degradation pattern but within much shorter time frame. The dechlorination rate of chlorinated phenols increases with decreasing in number of -Cl attached to aromatic ring, which can be predicted by the total charge of the aromatic ring, exhibiting an inversely linear relationship with the dechlorination rates. While the selectivity of dechlorination depends on the charges associated with the individual aromatic carbon. Chloro-functional groups at the ortho-position are easier to be dechlorinated than that at meta- and para- positions yielding primarily 3,4,5-TCP as intermediate from PCP, further to phenol. The effective dechlorination warrants their potential utilizations in development of in-situ remediation technologies for organic pollutants in contaminated water. Copyright © 2015 Elsevier B.V. All rights reserved.

Forensic Analysis of Polychlorinated Dibenzo-p-Dioxin and Furan Fingerprints to Elucidate Dechlorination Pathways.

Science.gov (United States)

Rodenburg, Lisa A; Dewani, Yashika; Häggblom, Max M; Kerkhof, Lee J; Fennell, Donna E

2017-09-19

Polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) are persistent organic pollutants whose main removal process in the environment is due to biodegradation, and particularly anaerobic reductive dechlorination. Since PCDD/F congeners that are substituted in the lateral 2, 3, 7, and 8 positions are the most toxic, removal of these chlorines is advantageous, but previous studies have only demonstrated their removal under laboratory conditions. We evaluated a concentration data set of PCDD/F congeners with four or more chlorines along with all 209 polychlorinated biphenyl (PCB) congeners in surface water, treated and untreated wastewater, landfill leachate, and biosolids (NY CARP data set) to determine whether peri and peri/lateral dechlorination of PCDD/Fs occurs in these environments. Positive Matrix Factorization (PMF) applied to the data set revealed a factor indicative of the microbial dechlorination of PCBs, and this factor also contained a variety of non-2,3,7,8 substituted PCDD/F congeners. These results suggest that dechlorination of PCDD/Fs at the lateral positions is facile if not preferred in these environments. The relative lack of tetra- and penta-chlorinated PCDD/Fs suggested that dechlorination proceeds to PCDD/F congeners with less than four chlorines. The PMF results were confirmed by examining three samples that contained >90% PCB dechlorination products from the Fresh Kills Landfill and the Hudson River. Even without factor analysis, these samples demonstrated almost identical PCDD/F congener patterns. This study suggests that PCDD/Fs are reductively dechlorinated to nontoxic non-2,3,7,8 PCDD/F congeners in sewers and landfills as well as in the sediment of the Upper Hudson River.

Dechlorination of chlorinated phenols by subnanoscale Pd{sup 0}/Fe{sup 0} intercalated in smectite: pathway, reactivity, and selectivity

Energy Technology Data Exchange (ETDEWEB)

Jia, Hanzhong; Wang, Chuanyi, E-mail: jiahz0143@aliyun.com

2015-12-30

Graphical abstract: Dechlorination process of pentachlorophenol (PCP) by smectite-templated Pd{sup 0}/Fe{sup 0}. - Highlights: • Smectite was employed as templated matrix to prepare subnanoscale Pd{sup 0}/Fe{sup 0} particles. • Dechlorination rate depends linearly on the Pd content as its loadings <0.065 wt.%. • Dechlorination rates correlate with the total charge of C on chlorinated phenols. • The dechlorination selectivity relies on charges of individual C in aromatic ring. - Abstract: Smectite clay was employed as templated matrix to prepare subnanoscale Pd{sup 0}/Fe{sup 0} particles, and their components as well as intercalated architectures were well characterized by X-ray energy dispersive spectroscopy (X-EDS) and X-ray diffraction (XRD). Furthermore, as-prepared Pd{sup 0}/Fe{sup 0} subnanoscale nanoparticles were evaluated for their dechlorination effect using chlorinated phenols as model molecules. As a result, pentachlorophenol (PCP) is selectively transformed to phenol in a stepwise dechlorination pathway within 6 h, and the dechlorination rate constants show linearly relationship with contents of Pd as its loadings <0.065%. Comparing with PCP, other chlorinated phenols display similar degradation pattern but within much shorter time frame. The dechlorination rate of chlorinated phenols increases with decreasing in number of -Cl attached to aromatic ring, which can be predicted by the total charge of the aromatic ring, exhibiting an inversely linear relationship with the dechlorination rates. While the selectivity of dechlorination depends on the charges associated with the individual aromatic carbon. Chloro-functional groups at the ortho-position are easier to be dechlorinated than that at meta- and para- positions yielding primarily 3,4,5-TCP as intermediate from PCP, further to phenol. The effective dechlorination warrants their potential utilizations in development of in-situ remediation technologies for organic pollutants in contaminated

Use of carbon stable isotope to investigate chloromethane formation in the electrolytic dechlorination of trichloroethylene

International Nuclear Information System (INIS)

Fang Yuanxiang; Al-Abed, Souhail R.

2007-01-01

Carbon stable isotope trichloroethylene ( 13 C TCE) was used to investigate the formation of chloromethane (CM) during the electrolytic dechlorination of trichloroethylene (TCE) at a granular-graphite packed cathode. A method was developed to use a conventional GC/MS to analyze and quantify regular and 13 C TCE and their dechlorination products. The concentration of a 13 C compound can be calculated, based on the concentration of its regular counterpart, from the response ratio of two fragments of different mass per charge values from the compounds in a sample and two characteristic MS spectrum ratios: one is the response ratio of the two fragments of the regular compound, and the other is the response ratio of the corresponding fragments of the regular and 13 C compounds at the same concentrations. The method was used to analyze the regular and 13 C compounds observed in an experiment of dechlorination in an ammonium acetate solution that contained both regular TCE and 13 C TCE. Results of analysis confirmed that CM was not a direct product of TCE dechlorination at the granular graphite cathode that cis-DCE was an intermediate product of TCE dechlorination, and that 1,1-DCE was not a dechlorination product

Use of carbon stable isotope to investigate chloromethane formation in the electrolytic dechlorination of trichloroethylene

Energy Technology Data Exchange (ETDEWEB)

Fang Yuanxiang [National Risk Management Research Laboratory, USEPA 26 W. Martin Luther King Dr. Cincinnati, OH 45268 (United States); Al-Abed, Souhail R. [National Risk Management Research Laboratory, USEPA 26 W. Martin Luther King Dr. Cincinnati, OH 45268 (United States)]. E-mail: Al-Abed.Souhail@epa.gov

2007-03-22

Carbon stable isotope trichloroethylene ({sup 13}C TCE) was used to investigate the formation of chloromethane (CM) during the electrolytic dechlorination of trichloroethylene (TCE) at a granular-graphite packed cathode. A method was developed to use a conventional GC/MS to analyze and quantify regular and {sup 13}C TCE and their dechlorination products. The concentration of a {sup 13}C compound can be calculated, based on the concentration of its regular counterpart, from the response ratio of two fragments of different mass per charge values from the compounds in a sample and two characteristic MS spectrum ratios: one is the response ratio of the two fragments of the regular compound, and the other is the response ratio of the corresponding fragments of the regular and {sup 13}C compounds at the same concentrations. The method was used to analyze the regular and {sup 13}C compounds observed in an experiment of dechlorination in an ammonium acetate solution that contained both regular TCE and {sup 13}C TCE. Results of analysis confirmed that CM was not a direct product of TCE dechlorination at the granular graphite cathode that cis-DCE was an intermediate product of TCE dechlorination, and that 1,1-DCE was not a dechlorination product.

Effects of Aqueous Film-Forming Foams (AFFFs) on Trichloroethene (TCE) Dechlorination by a Dehalococcoides mccartyi-Containing Microbial Community.

Science.gov (United States)

Harding-Marjanovic, Katie C; Yi, Shan; Weathers, Tess S; Sharp, Jonathan O; Sedlak, David L; Alvarez-Cohen, Lisa

2016-04-05

The application of aqueous film-forming foams (AFFFs) to extinguish chlorinated solvent-fueled fires has led to the co-contamination of poly- and perfluoroalkyl substances (PFASs) and trichloroethene (TCE) in groundwater and soil. Although reductive dechlorination of TCE by Dehalococcoides mccartyi is a frequently used remediation strategy, the effects of AFFF and PFASs on TCE dechlorination are not well-understood. Various AFFF formulations, PFASs, and ethylene glycols were amended to the growth medium of a D. mccartyi-containing enrichment culture to determine the impact on dechlorination, fermentation, and methanogenesis. The community was capable of fermenting organics (e.g., diethylene glycol butyl ether) in all AFFF formulations to hydrogen and acetate, but the product concentrations varied significantly according to formulation. TCE was dechlorinated in the presence of an AFFF formulation manufactured by 3M but was not dechlorinated in the presence of formulations from two other manufacturers. Experiments amended with AFFF-derived PFASs and perfluoroalkyl acids (PFAAs) indicated that dechlorination could be inhibited by PFASs but that the inhibition depends on surfactant concentration and structure. This study revealed that the fermentable components of AFFF can stimulate TCE dechlorination, while some of the fluorinated compounds in certain AFFF formulations can inhibit dechlorination.

Contributions of Fe Minerals to Abiotic Dechlorination

Science.gov (United States)

Most applications of enhanced in situ bioremediation are based on biological reductive dechlorination. Anaerobic metabolism can also produce reactive minerals that allow for in situ biogeochemical transformation of chlorinated organic contaminants such as PCE, TCE, and cis-DCE. ...

Hexachlorobenzene dechlorination as affected by organic fertilizer and urea applications in two rice planted paddy soils in a pot experiment

International Nuclear Information System (INIS)

Liu, C.Y.; Jiang, X.; Yang, X.L.; Song, Y.

2010-01-01

Reductive dechlorination is a crucial pathway for HCB degradation, the applications of organic materials and nitrogen can alter microbial activity and redox potential of soils, thus probably influence HCB dechlorination. To evaluate hexachlorobenzene (HCB) dechlorination as affected by organic fertilizer (OF) and urea applications in planted paddy soils, a pot experiment was conducted in two types of soils, Hydragric Acrisols (Ac) and Gleyi-Stagnic Anthrosols (An). After 18 weeks of experiment, HCB residues decreased by 28.2-37.5% of the initial amounts in Ac, and 42.1-70.9% in An. The amounts of HCB metabolites showed that dechlorination rates in An were higher than in Ac, which was mainly attributed to the higher pH and dissolved organic carbon (DOC) content of An. Both in Ac and An, the additions of 1% and 2% OF had negative effect on HCB dechlorination, which was probably because excessive nitrogen in OF decreased degraders' activity and the degradation of organic carbon in OF accepted electrons. The application of 0.03% urea could enhance HCB dechlorination rates slightly, while 0.06% urea accelerated HCB dechlorination significantly both in Ac and An. It could be assumed that urea served as an electron donor and stimulated degraders to dechlorinate HCB. In addition, the methanogenic bacteria were involved in dechlorination process, and reductive dechlorination in planted paddy soil might be impeded for the aerenchyma and O 2 supply into the rhizosphere. Results indicated that soil types, rice root system, methanogenic bacteria, OF and urea applications all had great effects on dechlorination process.

Graphene oxide-mediated rapid dechlorination of carbon tetrachloride by green rust

DEFF Research Database (Denmark)

Huang, Li-Zhi; Hansen, Hans Christian B.; Daasbjerg, Kim

2017-01-01

Graphene-based nanomaterials can mediate environmentally relevant abiotic redox reactions of chlorinated aliphatic hydrocarbons. In this study as low amounts as ∼0.007 % of graphene oxide (GO) was found to catalyze the reduction of carbon tetrachloride by layered Fe(II)-Fe(III) hydroxide (Green R....... This study indicates that traces of graphene oxide can affect reaction pathways as well as kinetics for dechlorination processes in anoxic sediments by facilitating a partial dechlorination....

Chain dechlorination of organic chlorinated compounds in alcohol solutions by 60Co gamma-rays, (1)

International Nuclear Information System (INIS)

Sawai, Takeshi; Shimokawa, Toshinari; Sawai, Teruko; Hosoda, Ieji; Kondo, Masaharu.

1975-01-01

A study was made on radiolytic dechlorination of pentachlorobenzene in alkaline alcohol solutions. The dechlorination yield (G(Cl - )) was found to depend on the alcohols used as solvent and the concentrations of the chlorinated benzene and hydroxide ion. The high yields obtained in alkaline 2-propanol, sec-butanol and ethanol indicate a chain process in the dechlorination reaction. The value of G(Cl - ) was highest in 2-propanol, and the principal products generated were potassium chloride, acetone and the lower chlorinated benzenes, while a decrease was seen in the hydroxide ion concentration. The concentrations produced of potassium chloride and acetone, as well as the decrease in hydroxide ion concentration, are all roughly equal at all doses. With increasing irradiation dose, pentachlorobenzene was dechlorinated to tetra, tri, di and monochlorobenzene. 1,2,4,5-tetrachlorobenzene, 1,2,4-trichlorobenzene and 1,4-dichlorobenzene were main products. A discussion is given of the detailed mechanism of the dechlorination in alkaline alcohols and the effect of alcohols on G(Cl - ). (auth.)

Desorption, partitioning, and dechlorination characteristics of PCBs in sediments in interaction with reactive activated carbon.

Science.gov (United States)

Choi, Hyeok; Lawal, Wasiu; Al-Abed, Souhail R

2015-04-28

Sediment (WHS) in Waukegan Harbor, Illinois, heavily contaminated and aged with polychlorinated biphenyls (PCBs), was treated with reactive activated carbon (RAC) impregnated with palladized iron nanoparticles. Lab test proceeded in a direct mixing configuration of RAC and WHS. A compartment configuration, where RAC was physically separated from WHS, was also designed to trace the sequential transport and fate of PCBs, including desorption, adsorption, dechlorination, and re-partitioning. PCBs, once desorbed from WHS, were immediately sequestrated to RAC and subject to dechlorination. Direct mixing of WHS with RAC was one-order of magnitude more effective for dechlorination than compartment configuration. Compared to their desorption-followed by-adsorption route, direct physical contact of RAC with PCBs bound to WHS exhibited negligible contribution to the availability of PCBs for dechlorination reaction. Addition of RAC even in compartment configuration facilitated PCBs desorption from WHS. However, slow desorption of PCBs limited overall performance, resulting in a five-order of magnitude lower dechlorination yield when compared with treatment of purely aqueous PCBs. The low dechlorination yield reflected real world complexities in treating 3.19% organic carbon-containing WHS aged with PCBs for 40 years. These observations were further supported when compared with results on clean Cesar Creek sediment spiked with 2-chlorinated biphenyls. Copyright © 2015 Elsevier B.V. All rights reserved.

Field-scale modeling of acidity production and remediation efficiency during in situ reductive dechlorination

Science.gov (United States)

Brovelli, A.; Robinson, C. E.; Barry, D. A.; Gerhard, J.

2009-12-01

Enhanced reductive dechlorination is a viable technology for in situ remediation of chlorinated solvent DNAPL source areas. Although in recent years increased understanding of this technology has led to more rapid dechlorination rates, complete dechlorination can be hindered by unfavorable conditions. Hydrochloric acid produced from dechlorination and organic acids generated from electron donor fermentation can lead to significant groundwater acidification. Adverse pH conditions can inhibit the activity of dehalogenating microorganisms and thus slow or stall the remediation process. The extent of acidification likely to occur at a contaminated site depends on a number of factors including (1) the extent of dechlorination, (2) the pH-sensitivity of dechlorinating bacteria, and (3) the geochemical composition of the soil and water, in particular the soil’s natural buffering capacity. The substantial mass of solvents available for dechlorination when treating DNAPL source zones means that these applications are particularly susceptible to acidification. In this study a reactive transport biogeochemical model was developed to investigate the chemical and physical parameters that control the build-up of acidity and subsequent remediation efficiency. The model accounts for the site water chemistry, mineral precipitation and dissolution kinetics, electron donor fermentation, gas phase formation, competing electron-accepting processes (e.g., sulfate and iron reduction) and the sensitivity of microbial processes to pH. Confidence in the model was achieved by simulating a well-documented field study, for which the 2-D field scale model was able to reproduce long-term variations of pH, and the concurrent build up of reaction products. Sensitivity analyses indicated the groundwater flow velocity is able to reduce acidity build-up when the rate of advection is comparable or larger than the rate of dechlorination. The extent of pH change is highly dependent on the presence of

Reductive Dechlorination of Polychlorinated Biphenyls in Marine Sediments

National Research Council Canada - National Science Library

Sowers, Kevin

1999-01-01

... Community by Comparative Sequence Analysis of Genes Coding for 16S rRNA, Microbial Reductive Dechlorination of Aroclor 1260 in Anaerobic Slurries of Estuarine Sediments, Differential RFLP patterns of PCR...

Reductive Dechlorination of Carbon Tetrachloride by Soil With Ferrous and Bisulfide

Science.gov (United States)

Choi, K.; Lee, W.

2008-12-01

Batch and column experiments were conducted to investigate the effect of concentration of reductants, contact time to activate reductive capacity, and pH on reductive dechlorination by soil with Fe(II) and HS- in this study. Carbon tetrachloride (CT) was used as a representative target organic compound. Sorption kinetic and isotherm tests were performed to investigate the influence of adsorption on the soil surface. Target compound in the soil suspension reached sorption equilibrium in 4 hours and the type of isotherm was well fitted by a linear type isotherm. In batch experiment, kinetic rate constants for the reductive dechlorination of CT increased with increasing the concentration of the reductants (Fe(II) and HS-). However, Fe(II) was a much more effective reductant, producing higher k values than those of HS-. The contact time of one day for the soil with HS- and that of four hours with Fe(II) showed the highest reaction rates. Additionally, the rate constants increased with the increase of pH in soil suspension with Fe(II) (5.2~8) and HS- (8.3~10.3), respectively. In column experiment, the soil column with Fe(II) showed larger bed volumes (13.76) to reach a column breakthrough than that with HS- indicating the treatment of Fe(II) is more effective for the reductive dechlorination of CT. To enhance reductive capacity of soil column under an acidic condition, CaO addition to the column treated with Fe(II) showed better results for the reductive dechlorination of CT than that of HS-. Fe(II) showed better CT dechlorination than HS- in batch and column reactors therefore, it can be used as an effective reducing agent for the treatment of soil contaminated with chlorinated organic compounds.

Dechlorination and decomposition of chloroform induced by glow discharge plasma in an aqueous solution

Energy Technology Data Exchange (ETDEWEB)

Liu, Yongjun, E-mail: lyjglow@sohu.com [College of Environmental Science & Engineering, Dalian Maritime University, Dalian 116026 (China); Brook Byers Institute for Sustainable Systems, Georgia Institute of Technology, Atlanta 30332 (United States); Crittenden, John C. [Brook Byers Institute for Sustainable Systems, Georgia Institute of Technology, Atlanta 30332 (United States); Wang, Lei [College of Environmental Science & Engineering, Xiamen University of Technology, Xiamen 361024 (China); Liu, Panliang [Brook Byers Institute for Sustainable Systems, Georgia Institute of Technology, Atlanta 30332 (United States)

2016-05-05

Highlights: • Hydrated electrons played an important role for chloroform decomposition. • Oxygen enhanced hydrolyses are critical for the chloroform mineralization. • Energy efficiency of GDP is higher than those of the typical competitive processes. - Abstract: In this study, efficient dechlorination and decomposition of chloroform (CF) induced by glow discharge plasma (GDP) in contact with a sodium sulfate solution was investigated. Intermediate byproducts were determined by ionic chromatography and headspace gas chromatography, respectively. Results showed that CF can be effectively dechlorinated and decomposed under the action of GDP. Both removal and dechlorination of CF increased with increasing pH and with addition of hydroxyl radical scavengers to the solution. Addition of H{sub 2}O{sub 2} to the solution slightly decreased the CF removal. Formic acid, oxalic acid and dichloromethane were determined as the major intermediate byproducts. Final products were carbon dioxide and hydrochloric acid. Hydrated electrons were the most likely active species responsible for initiation of the dechlorination, and hydroxyl radicals may be the ones for the oxidation of the organic intermediate byproducts. Hydrolyses of the chloromethyl radicals contributed much in the mineralization of the organic chlorine. Reaction mechanism was proposed based on the dechlorination kinetics and the distribution of intermediate byproducts.

16S rRNA gene-based detection of tetrachloroethene-dechlorinating Desulfuromonas and Dehalococcoides species

Energy Technology Data Exchange (ETDEWEB)

Loeffler, F.E.; Sun, Q.; Li, J.; Tiedje, J.M.

2000-03-01

Members of the genera Desulfuromonas and Dehalococcoides reductively dechlorinate tetrachloroethene (PCE) and trichloroethene. Two primer pairs specific to hypervariable regions of the 16S rRNA genes of the Dehalococcoides group (comprising Dehalococcoides ethenogenes and Dehalococcoides sp. strain FL2) and the acetate-oxidizing, PCE-dechlorinating Desulfuromonas group (comprising Desulfuromonas sp. strain BB1 and Desulfuromonas chloroethenica) were designed. The detection threshold of a nested PCR approach using universal bacterial primers followed by a second PCR with the Desulfuromonas dechlorinator-targeted primer pair was 1 x 10{sup 3} BB1 cells added per gram (wet weight) of sandy aquifer material. Total community DNA isolated from sediments of three Michigan rivers and six different chloroethene-contaminated aquifer samples was used as template in nested PCR. All river sediment samples yielded positive signals with the BB1- and the Dehalococcoides-targeted primers. One chloroethene-contaminated aquifer tested positive with the Dehalococcoides-targeted primers, and another contaminated aquifer tested positive with the Desulfuromonas dechlorinator-targeted primer pair. Restriction fragment analysis of the amplicons could discriminate strain BB1 from other known Desulfuromonas species. Microcosm studies confirmed the presence of PCE-dechlorinating, acetate-oxidizing Desulfuromonas and hydrogenotrophic Dehalococcoides species in samples yielding positive PCR signals with the specific primers.

Dechlorination and decomposition of chloroform induced by glow discharge plasma in an aqueous solution

International Nuclear Information System (INIS)

Liu, Yongjun; Crittenden, John C.; Wang, Lei; Liu, Panliang

2016-01-01

Highlights: • Hydrated electrons played an important role for chloroform decomposition. • Oxygen enhanced hydrolyses are critical for the chloroform mineralization. • Energy efficiency of GDP is higher than those of the typical competitive processes. - Abstract: In this study, efficient dechlorination and decomposition of chloroform (CF) induced by glow discharge plasma (GDP) in contact with a sodium sulfate solution was investigated. Intermediate byproducts were determined by ionic chromatography and headspace gas chromatography, respectively. Results showed that CF can be effectively dechlorinated and decomposed under the action of GDP. Both removal and dechlorination of CF increased with increasing pH and with addition of hydroxyl radical scavengers to the solution. Addition of H_2O_2 to the solution slightly decreased the CF removal. Formic acid, oxalic acid and dichloromethane were determined as the major intermediate byproducts. Final products were carbon dioxide and hydrochloric acid. Hydrated electrons were the most likely active species responsible for initiation of the dechlorination, and hydroxyl radicals may be the ones for the oxidation of the organic intermediate byproducts. Hydrolyses of the chloromethyl radicals contributed much in the mineralization of the organic chlorine. Reaction mechanism was proposed based on the dechlorination kinetics and the distribution of intermediate byproducts.

Effect of a base-catalyzed dechlorination process on the genotoxicity of PCB-contaminated soil

Energy Technology Data Exchange (ETDEWEB)

DeMarini, D.M.; Houk, V.S.; Kornel, A.; Rogers, C.J.

1992-01-01

We evaluated the genotoxicity of dichloromethane (DCM) extracts of PCB-contaminated soil before and after the soil had been treated by a base-catalyzed dechlorination process, which involved heating a mixture of the soil, polyethylene glycol, and sodium hydroxide to 250-350 C. This dechlorination process reduced by over 99% the PCB concentration in the soil, which was initially 2,200 ppm. The DCM extracts of both control and treated soils were not mutagenic in strain TA100 of Salmonella, but they were mutagenic in strain TA98. The base-catalyzed dechlorination process reduced the mutagenic potency of the soil by approximately one-half. The DCM extracts of the soils before and after treatment were equally genotoxic in a prophage-induction assay in E. coli, which detects some chlorinated organic carcinogens that were not detected by the Salmonella mutagenicity assay. These results show that treatment of PCB-contaminated soil by this base-catalyzed dechlorination process did not increase the genotoxicity of the soil.

Dechlorination of Hexachloroethane in Water Using Iron Shavings and Amended Iron Shavings: Kinetics and Pathways

Directory of Open Access Journals (Sweden)

D. L. Wu

2014-01-01

Full Text Available In contrast to previous studies which employed zero-valent iron powder, this paper investigated reductive dechlorination of hexachloroethane (HCA using iron shavings and bimetallic iron shavings modified with Cu, Ag, or Pd. Results clearly show that iron shavings offer superior reductive dechlorination of HCA. In addition, surface-normalized pseudo first-order dechlorination rates of 0.0073 L·m−2·h−1, 0.0136 L·m−2·h−1, 0.0189 L·m−2·h−1, and 0.0084 L·m−2·h−1 were observed in the presence of iron shavings (Fe0 and the bimetallic iron shavings Cu/Fe, Ag/Fe, and Pd/Fe, respectively. Bimetallic iron shavings consisting of Cu/Fe and Ag/Fe could greatly enhance the reductive reaction rate; Pd/Fe was used to achieve complete dechlorination of HCA within 5 hours. The additives of Ag and Pd shifted product distributions, and the reductive dechlorination of HCA occurred via β reductive elimination and sequential hydrogenolysis in the presence of all iron shavings. This study consequently designed a reaction pathway diagram which reflected the reaction pathway and most prevalent dechlorination products. Iron shavings are a common byproduct of mechanical processing plants. While the purity of such Fe metals may be low, these shavings are readily available at low costs and could potentially be used in engineering applications such as contamination control technologies.

Review of reactive kinetic models describing reductive dechlorination of chlorinated ethenes in soil and groundwater

DEFF Research Database (Denmark)

Chambon, Julie Claire Claudia; Bjerg, Poul Løgstrup; Scheutz, Charlotte

2013-01-01

Reductive dechlorination is a major degradation pathway of chlorinated ethenes in anaerobic subsurface environments, and reactive kinetic models describing the degradation process are needed in fate and transport models of these contaminants. However, reductive dechlorination is a complex biologi...

Kinetics of 2-chlorobiphenyl Reductive Dechlorination by Pd-fe0 Nanoparticles

Directory of Open Access Journals (Sweden)

Jiang Junrong

2016-01-01

Full Text Available Kinetics of 2-chlorobiphenyl (2-Cl BP catalytic reductive dechlorination by Pd-Fe0 nanoparticles were investigated. Experimental results showed that ultrafine bimetallic Pd-Fe0e nanoparticles were synthesized in the presence of 40 kHz ultrasound in order to enhance disparity and avoid agglomeration. The application of ultrasonic irradiation during the synthesis of Pd-Fe0 nanoparticles further accelerated the dechlorinated removal ratio of 2-Cl BP. Up to 95.0% of 2-Cl BP was removed after 300 min reaction with the following experimental conditions: initial 2-Cl BP concentration 10 mg L-1, Pd content 0.8 wt. %, bimetallic Pd-Fe0 nanoparticles prepared in the presence of ultrasound available dosage 7g L-1, initial pH value in aqueous solution 3.0, and reaction temperature 25°C. The catalytic reductive dechlorination of 2-Cl BP followed pseudo-first-order kinetics and the apparent pseudo-first-order kinetics constant was 0.0143 min-1.

The kinetics of the radiation-induced chain dechlorination of hexachloroethane in alcohols

International Nuclear Information System (INIS)

Sawai, Takeshi; Ohara, Naoki; Shimokawa, Toshinari

1978-01-01

The kinetics of the radiation-induced dechlorination of hexachloroethane was investigated in deoxygenated alcohol solutions. The major products were hydrogen chloride, pentachloroethane, 1,1,2,2-tetrachloroethane, tetrachloroethylene, and aldehydes or acetone. No 1,1,1,2-tetrachloroethane was observed. The radiation-chemical yields of these products and the disappearance of hexachloroethane were quite high; these facts indicate that a chain reaction is involved in these processes. After the hexachloroethane had effectively dechlorinated down to tetrachloro compounds, there were no marked changes in the lower chlorinated compound upon continuous irradiation. Tetrachloroethane was formed via pentachloroethane, but tetrachloroethylene was produced by means of C 2 Cl 5 →C 2 Cl 4 + cl reaction and the yield was particularly high in methanol compared with the other alcohols. The chain length of the dechlorination from hexachloroethane to pentachloroethane and from pentachloroethane to tetrachloroethane increased in the order of 2-propanol>ethanol>methanol. The G(-C 2 Cl 6 ) and G(products) were proportional to (dose rate)sup(-1/2), and the ratio of G(C 2 HCl 5 ) to G(C 2 Cl 4 ) was a constant in each alcohol solution, regardless of the dose rate. The α-hydroxy alkyl radical is the chain carrier for the dechlorination reaction of hexachloroethane in alcohol solutions. The relative rates of the dechlorination were found to be 1, 3, and 14 for C*H 2 OH (*: radical), CH 3 C*HOH (*: radical), and (CH 3 ) 2 C*OH (*: radical), respectively. The order in the rate is in agreement with that of the redox potential of these radicals. The effect of the irradiation temperature on the products yields was also examined. (auth.)

Influential factors of 2-chlorobiphenyl reductive dechlorination by highly dispersed bimetallic nanoparticles

Directory of Open Access Journals (Sweden)

Jiang Junrong

2016-01-01

Full Text Available Highly dispersed Pd-Fe0 bimetallic nanoparticles were prepared in the presence of 40 kHz ultrasonic irradiation in order to enhance disparity and reactivity, and simultaneously avoid agglomeration. Influential factors of 2-chlorobiphenyl (2-Cl BP reductive dechlorination by highly dispersed Pd-Fe0 nanoparticles were investigated. Experimental results showed that highly dispersed Pd-Fe0 nanoparticles prepared in the in the presence of ultrasound could further improve the dechlorination efficiency of 2-Cl BP, meanwhile the biphenyl (BP formation rates increased obviously and increased from 47.4% (in the absence of ultrasound to 95.3% (in the presence of ultrasound within 300 min. The catalytic reductive dechlorination effciency of 2-Cl BP was dependent on Pd-Fe0 nanoparticles prepared methods, Pd-Fe0 nanoparticles dosage, Pd loading percentage over Fe0 and initial pH values

INFLUENCES OF PH AND CURRENT ON ELECTROLYTIC DECHLORINATION OF TRICHLOROETHYLENE AT A GRANULAR-GRAPHITE PACKED ELECTRODE

Science.gov (United States)

Electrolytic dechlorination using a granular-graphite packed cathode is an alternative method for the remediation of chlorinated organic compounds. Its effectiveness under various conditions needs experimental investigation. Dechlorination of trichloroethylene (TCE) was conducted...

Enhanced abiotic and biotic contributions to dechlorination of pentachlorophenol during Fe(III) reduction by an iron-reducing bacterium Clostridium beijerinckii Z

Energy Technology Data Exchange (ETDEWEB)

Xu, Yan [College of Environmental and Natural Resource Sciences, Zhejiang Provincial Key Laboratory of Subtropical Soil and Plant Nutrition, Zhejiang University, Hangzhou 310058 (China); He, Yan, E-mail: yhe2006@zju.edu.cn [College of Environmental and Natural Resource Sciences, Zhejiang Provincial Key Laboratory of Subtropical Soil and Plant Nutrition, Zhejiang University, Hangzhou 310058 (China); Feng, Xiaoli [College of Environmental and Natural Resource Sciences, Zhejiang Provincial Key Laboratory of Subtropical Soil and Plant Nutrition, Zhejiang University, Hangzhou 310058 (China); Liang, Luyi [Experiment Teaching Center for Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Xu, Jianming, E-mail: jmxu@zju.edu.cn [College of Environmental and Natural Resource Sciences, Zhejiang Provincial Key Laboratory of Subtropical Soil and Plant Nutrition, Zhejiang University, Hangzhou 310058 (China); Brookes, Philip C.; Wu, Jianjun [College of Environmental and Natural Resource Sciences, Zhejiang Provincial Key Laboratory of Subtropical Soil and Plant Nutrition, Zhejiang University, Hangzhou 310058 (China)

2014-03-01

A novel Fe(III) reducing bacterium, Clostridium beijerinckii Z, was isolated from glucose amended paddy slurries, and shown to dechlorinate pentachlorophenol (PCP). Fifty percent of added PCP was removed by C. beijerinckii Z alone, which increased to 83% in the presence of both C. beijerinckii Z and ferrihydrite after 11 days of incubation. Without C. beijerinckii Z, the surface-bound Fe(II) also abiotically dechlorinated more than 40% of the added PCP. This indicated that the biotic dechlorination by C. beijerinckii Z is a dominant process causing PCP transformation through anaerobic dechlorination, and that the dechlorination rates can be accelerated by simultaneous reduction of Fe(III). A biochemical electron transfer coupling process between sorbed Fe(II) produced by C. beijerinckii Z and reductive dehalogenation is a possible mechanism. This finding increases our knowledge of the role of Fe(III) reducing genera of Clostridium in dechlorinating halogenated organic pollutants, such as PCP, in anaerobic paddy soils. - Highlights: • A novel Fe(III) reducing bacterium Clostridium beijerinckii Z was isolated and could dechlorinate pentachlorophenol. • Anaerobic transformation of PCP by C. beijerinckii Z could be accelerated by simultaneous reduction of Fe(III). • Biochemical electron transfer coupling between Fe redox cycling and reductive dechlorination was the mechanism involved. • The finding increases our knowledge of Clostridium sp. regarding their multiple functions for dechlorinating pollutants.

Enhanced abiotic and biotic contributions to dechlorination of pentachlorophenol during Fe(III) reduction by an iron-reducing bacterium Clostridium beijerinckii Z

International Nuclear Information System (INIS)

Xu, Yan; He, Yan; Feng, Xiaoli; Liang, Luyi; Xu, Jianming; Brookes, Philip C.; Wu, Jianjun

2014-01-01

A novel Fe(III) reducing bacterium, Clostridium beijerinckii Z, was isolated from glucose amended paddy slurries, and shown to dechlorinate pentachlorophenol (PCP). Fifty percent of added PCP was removed by C. beijerinckii Z alone, which increased to 83% in the presence of both C. beijerinckii Z and ferrihydrite after 11 days of incubation. Without C. beijerinckii Z, the surface-bound Fe(II) also abiotically dechlorinated more than 40% of the added PCP. This indicated that the biotic dechlorination by C. beijerinckii Z is a dominant process causing PCP transformation through anaerobic dechlorination, and that the dechlorination rates can be accelerated by simultaneous reduction of Fe(III). A biochemical electron transfer coupling process between sorbed Fe(II) produced by C. beijerinckii Z and reductive dehalogenation is a possible mechanism. This finding increases our knowledge of the role of Fe(III) reducing genera of Clostridium in dechlorinating halogenated organic pollutants, such as PCP, in anaerobic paddy soils. - Highlights: • A novel Fe(III) reducing bacterium Clostridium beijerinckii Z was isolated and could dechlorinate pentachlorophenol. • Anaerobic transformation of PCP by C. beijerinckii Z could be accelerated by simultaneous reduction of Fe(III). • Biochemical electron transfer coupling between Fe redox cycling and reductive dechlorination was the mechanism involved. • The finding increases our knowledge of Clostridium sp. regarding their multiple functions for dechlorinating pollutants

Performance and Mechanism of Piezo-Catalytic Degradation of 4-Chlorophenol: Finding of Effective Piezo-Dechlorination.

Science.gov (United States)

Lan, Shenyu; Feng, Jinxi; Xiong, Ya; Tian, Shuanghong; Liu, Shengwei; Kong, Lingjun

2017-06-06

Piezo-catalysis was first used to degrade a nondye pollutant, 4-chlorophenol (4-CP). In this process, hydrothermally synthesized tetragonal BaTiO 3 nano/micrometer-sized particles were used as the piezo-catalyst, and the ultrasonic irradiation with low frequency was selected as the vibration energy to cause the deformation of tetragonal BaTiO 3 . It was found that the piezoelectric potential from the deformation could not only successfully degrade 4-chlorophenol but also effectively dechlorinate it at the same time, and five kinds of dechlorinated intermediates, hydroquinone, benzoquinone, phenol, cyclohexanone, and cyclohexanol, were determined. This is the first sample of piezo-dechlorination. Although various active species, including h + , e - , •H, •OH, •O 2 - , 1 O 2 , and H 2 O 2 , were generated in the piezoelectric process, it was confirmed by ESR, scavenger studies, and LC-MS that the degradation and dechlorination were mainly attributed to •OH radicals. These •OH radicals were chiefly derived from the electron reduction of O 2 , partly from the hole oxidation of H 2 O. These results indicated that the piezo-catalysis was an emerging and effective advanced oxidation technology for degradation and dechlorination of organic pollutants.

Modeling multi-component transport and enhanced anaerobic dechlorination processes in a single fracture-clay matrix system

DEFF Research Database (Denmark)

Chambon, Julie Claire Claudia; Broholm, Mette Martina; Binning, Philip John

2010-01-01

Clayey tills contaminated with chlorinated solvents are a threat to groundwater and are difficult to remediate. A numerical model is developed for assessing leaching processes and for simulating the remediation via enhanced anaerobic dechlorination. The model simulates the transport...... to the physical processes, mainly diffusion in the matrix, than to the biogeochemical processes, when dechlorination is assumed to take place in a limited reaction zone only. The inclusion of sequential dechlorination in clay fracture transport models is crucial, as the contaminant flux to the aquifer...

Humic acid and metal ions accelerating the dechlorination of 4-chlorobiphenyl by nanoscale zero-valent iron

Institute of Scientific and Technical Information of China (English)

Yu Wang; Dongmei Zhou; Yujun Wang; Xiangdong Zhu; Shengyang Jin

2011-01-01

Transformation of polychlorinated biphenyls (PCBs) by zero-valent iron represents one of the latest innovative technologies for environmental remediation.The dechlorination of 4-chlorobiphenyl (4-C1BP) by nanoscale zero-valent iron (NZVI) in the presence of humic acid or metal ions was investigated.The results showed that the de chlorination of 4-CIBP by NZVI increased with decreased solution pH.When the initial pH value was 4.0,5.5,6.8,and 9.0,the de chlorination efliciencies of 4-C1BP after 48 hr were 53.8%,47.8%,35.7%,and 35.6%,respectively.The presence of humic acid inhibited the reduction of 4-ClBP in the first 4 hr,and then significantly accelerated the dechlorination by reaching 86.3% in 48 hr.Divalent metal ions,Co2+,Cu2+,and Ni2+,were reduced and formed bimetals with NZVI,thereby enhanced the dechlorination of 4-CIBP.The dechlorination percentages of 4-CIBP in the presence of 0.1 mmol/L Co2+,Cu2+ and Ni2+ were 66.1%,66.0% and 64.6% in 48 hr,and then increased to 67.9%,71.3% and 73.5%,after 96 hr respectively.The dechlorination kinetics of 4-CIBP by the NZVI in all cases followed pseudo-first order model.The results provide a basis for better understanding of the dechlorination mechanisms of PCBs in real environment.

Stable carbon isotope fractionation of chlorinated ethenes by a microbial consortium containing multiple dechlorinating genes.

Science.gov (United States)

Liu, Na; Ding, Longzhen; Li, Haijun; Zhang, Pengpeng; Zheng, Jixing; Weng, Chih-Huang

2018-08-01

The study aimed to determine the possible contribution of specific growth conditions and community structures to variable carbon enrichment factors (Ɛ- carbon ) values for the degradation of chlorinated ethenes (CEs) by a bacterial consortium with multiple dechlorinating genes. Ɛ- carbon values for trichloroethylene, cis-1,2-dichloroethylene, and vinyl chloride were -7.24% ± 0.59%, -14.6% ± 1.71%, and -21.1% ± 1.14%, respectively, during their degradation by a microbial consortium containing multiple dechlorinating genes including tceA and vcrA. The Ɛ- carbon values of all CEs were not greatly affected by changes in growth conditions and community structures, which directly or indirectly affected reductive dechlorination of CEs by this consortium. Stability analysis provided evidence that the presence of multiple dechlorinating genes within a microbial consortium had little effect on carbon isotope fractionation, as long as the genes have definite, non-overlapping functions. Copyright © 2018 Elsevier Ltd. All rights reserved.

Desorption, partitioning, and dechlorination characteristics of PCBs in sediments in interaction with reactive activated carbon

International Nuclear Information System (INIS)

Choi, Hyeok; Lawal, Wasiu; Al-Abed, Souhail R.

2015-01-01

Highlights: • Problematic aged real PCBs-contaminated sediment (WHS) was examined. • Performance of reactive activated carbon (RAC) impregnated with Pd–ZVI was tested. • Fate and transport of PCBs bound to WHS in the presence of RAC was fully traced. • Direct mixing configuration was compared with compartment configuration. • Results reflected real world complexities associated with slow desorption of PCBs. - Abstract: Sediment (WHS) in Waukegan Harbor, Illinois, heavily contaminated and aged with polychlorinated biphenyls (PCBs), was treated with reactive activated carbon (RAC) impregnated with palladized iron nanoparticles. Lab test proceeded in a direct mixing configuration of RAC and WHS. A compartment configuration, where RAC was physically separated from WHS, was also designed to trace the sequential transport and fate of PCBs, including desorption, adsorption, dechlorination, and re-partitioning. PCBs, once desorbed from WHS, were immediately sequestrated to RAC and subject to dechlorination. Direct mixing of WHS with RAC was one-order of magnitude more effective for dechlorination than compartment configuration. Compared to their desorption-followed by-adsorption route, direct physical contact of RAC with PCBs bound to WHS exhibited negligible contribution to the availability of PCBs for dechlorination reaction. Addition of RAC even in compartment configuration facilitated PCBs desorption from WHS. However, slow desorption of PCBs limited overall performance, resulting in a five-order of magnitude lower dechlorination yield when compared with treatment of purely aqueous PCBs. The low dechlorination yield reflected real world complexities in treating 3.19% organic carbon-containing WHS aged with PCBs for 40 years. These observations were further supported when compared with results on clean Cesar Creek sediment spiked with 2-chlorinated biphenyls

Influence of phosphate and copper on reductive dechlorination of thiobencarb in California rice field soils.

Science.gov (United States)

Gunasekara, Amrith S; Tenbrook, Patti L; Palumbo, Amanda J; Johnson, Catherine S; Tjeerdema, Ronald S

2005-12-28

The potential for reductive dechlorination of the herbicide thiobencarb (TB) by microbes and its prevention in saturated anaerobic rice field soils was examined in laboratory microcosms. TB is effective in controlling both annual grasses and broadleaf weeds. In anoxic microcosms, TB was effectively degraded within 30 days to its dechlorinated product, deschlorothiobencarb (DTB), in two Sacramento Valley rice field soils. TB dechlorination, and subsequent degradation, followed pseudo-zero- (lag phase) and first-order (degradation phase) kinetics. Logistic regression analysis (r2 > 0.841) produced a half-life (t(1/2)) in nonsterile soils ranging from 10 to 15 days, which was also observed when microcosms were amended with low concentrations (copper (Cu2+; as the fungicides Cu(OH)2 and CuSO4.5H2O). High Cu2+ concentrations (>40 mg L(-1)) were added to the microcosms to determine if copper toxicity to dechlorinating microbes is concentration dependent within the range used. After 30 days, the low-copper-amended soils closely resembled the nonsterile experiments to which no Cu2+ was added while the high-copper-amended microcosms were similar to the sterile experiment. Microcosms were also separately amended with 5.7 g L(-1) phosphate (PO4(2-); as KH2PO4), a nutrient regularly applied to rice fields. Phosphate-amended experiments also showed TB degradation, but no DTB formation, indicating the phosphate played a role, possibly as a microbial inhibitor or an alternative electron acceptor, in limiting the dechlorination of TB. In summary, TB dechlorination was inhibited at high Cu(OH)2, CuSO4.5H2O, and KH2PO4 concentrations.

Desorption, partitioning, and dechlorination characteristics of PCBs in sediments in interaction with reactive activated carbon

Energy Technology Data Exchange (ETDEWEB)

Choi, Hyeok, E-mail: hchoi@uta.edu [Department of Civil Engineering, The University of Texas at Arlington, 416 Yates Street, Arlington, TX 76019-0308 (United States); Environmental and Earth Sciences Program, The University of Texas at Arlington, 500 Yates Street, Arlington, TX 76019-0049 (United States); Lawal, Wasiu [Environmental and Earth Sciences Program, The University of Texas at Arlington, 500 Yates Street, Arlington, TX 76019-0049 (United States); Al-Abed, Souhail R. [National Risk Management Research Laboratory, U.S. Environmental Protection Agency, 26 W. Martin Luther King Dr., Cincinnati, OH 45268 (United States)

2015-04-28

Highlights: • Problematic aged real PCBs-contaminated sediment (WHS) was examined. • Performance of reactive activated carbon (RAC) impregnated with Pd–ZVI was tested. • Fate and transport of PCBs bound to WHS in the presence of RAC was fully traced. • Direct mixing configuration was compared with compartment configuration. • Results reflected real world complexities associated with slow desorption of PCBs. - Abstract: Sediment (WHS) in Waukegan Harbor, Illinois, heavily contaminated and aged with polychlorinated biphenyls (PCBs), was treated with reactive activated carbon (RAC) impregnated with palladized iron nanoparticles. Lab test proceeded in a direct mixing configuration of RAC and WHS. A compartment configuration, where RAC was physically separated from WHS, was also designed to trace the sequential transport and fate of PCBs, including desorption, adsorption, dechlorination, and re-partitioning. PCBs, once desorbed from WHS, were immediately sequestrated to RAC and subject to dechlorination. Direct mixing of WHS with RAC was one-order of magnitude more effective for dechlorination than compartment configuration. Compared to their desorption-followed by-adsorption route, direct physical contact of RAC with PCBs bound to WHS exhibited negligible contribution to the availability of PCBs for dechlorination reaction. Addition of RAC even in compartment configuration facilitated PCBs desorption from WHS. However, slow desorption of PCBs limited overall performance, resulting in a five-order of magnitude lower dechlorination yield when compared with treatment of purely aqueous PCBs. The low dechlorination yield reflected real world complexities in treating 3.19% organic carbon-containing WHS aged with PCBs for 40 years. These observations were further supported when compared with results on clean Cesar Creek sediment spiked with 2-chlorinated biphenyls.

Identification of Multiple Dehalogenase Genes Involved in Tetrachloroethene-to-Ethene Dechlorination in a Dehalococcoides-Dominated Enrichment Culture

Directory of Open Access Journals (Sweden)

Mohamed Ismaeil

2017-01-01

Full Text Available Chloroethenes (CEs are widespread groundwater toxicants that are reductively dechlorinated to nontoxic ethene (ETH by members of Dehalococcoides. This study established a Dehalococcoides-dominated enrichment culture (designated “YN3” that dechlorinates tetrachloroethene (PCE to ETH with high dechlorination activity, that is, complete dechlorination of 800 μM PCE to ETH within 14 days in the presence of Dehalococcoides species at 5.7±1.9×107 copies of 16S rRNA gene/mL. The metagenome of YN3 harbored 18 rdhA genes (designated YN3rdhA1–18 encoding the catalytic subunit of reductive dehalogenase (RdhA, four of which were suggested to be involved in PCE-to-ETH dechlorination based on significant increases in their transcription in response to CE addition. The predicted proteins for two of these four genes, YN3RdhA8 and YN3RdhA16, showed 94% and 97% of amino acid similarity with PceA and VcrA, which are well known to dechlorinate PCE to trichloroethene (TCE and TCE to ETH, respectively. The other two rdhAs, YN3rdhA6 and YN3rdhA12, which were never proved as rdhA for CEs, showed particularly high transcription upon addition of vinyl chloride (VC, with 75±38 and 16±8.6 mRNA copies per gene, respectively, suggesting their possible functions as novel VC-reductive dehalogenases. Moreover, metagenome data indicated the presence of three coexisting bacterial species, including novel species of the genus Bacteroides, which might promote CE dechlorination by Dehalococcoides.

Complete dechlorination of 2,4-dichlorophenol in aqueous solution on palladium/polymeric pyrrole-cetyl trimethyl ammonium bromide/foam-nickel composite electrode

Energy Technology Data Exchange (ETDEWEB)

Sun, Zhirong, E-mail: zrsun@bjut.edu.cn [College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124 (China); Wei, Xuefeng; Han, Yanbo; Tong, Shan [College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124 (China); Hu, Xiang, E-mail: huxiang99@163.com [College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029 (China)

2013-01-15

Highlights: ► Pd/PPy-CTAB/foam-Ni electrode with high surface area and low Pd content was prepared. ► The composite electrode was applied to dechlorination of 2,4-DCP in aqueous solution. ► Complete dechlorination of 2,4-DCP was achieved with higher current efficiency. ► Removal efficiency kept 100% after 10 times dechlorination on the stable electrode. ► The electrochemically reductive activation energy was 25.8 kJ mol{sup −1} in this system. -- Abstract: The electrochemically reductive dechlorination of 2,4-dichlorophenol (2,4-DCP) in aqueous solution on palladium/polymeric pyrrole-cetyl trimethyl ammonium bromide/foam-nickel electrode (Pd/PPy-CTAB/foam-Ni electrode) was investigated in this paper. Pd/PPy-CTAB/foam-Ni electrode was prepared and characterized by cyclic voltammetry (CV), scanning electron microscope (SEM), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) adsorption and inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The influences of some experimental factors such as the dechlorination current, dechlorination time and the initial pH on the removal efficiency and the current efficiency of 2,4-DCP dechlorination on Pd/PPy-CTAB/foam-Ni electrode were studied. Complete removal of 2,4-DCP was achieved and the current efficiency of 47.4% could be obtained under the conditions of the initial pH of 2.2, the dechlorination current of 5 mA and the dechlorination time of 50 min when the initial 2,4-DCP concentration was 100 mg L{sup −1}. The analysis of high performance liquid chromatography (HPLC) identified that the intermediate products were 2-chlorophenol (2-CP) and 4-chlorophenol (4-CP). The final products were mainly phenol. Its further reduction product cyclohexanone was also detected. The electrocatalytic dechlorination pathways of 2,4-DCP on Pd/PPy-CTAB/foam-Ni electrode were discussed. The stability of the electrode was favorable that it could keep dechlorination efficiency at 100% after having been reused

A remediation performance model for enhanced metabolic reductive dechlorination of chloroethenes in fractured clay till

Science.gov (United States)

Manoli, Gabriele; Chambon, Julie C.; Bjerg, Poul L.; Scheutz, Charlotte; Binning, Philip J.; Broholm, Mette M.

2012-04-01

A numerical model of metabolic reductive dechlorination is used to describe the performance of enhanced bioremediation in fractured clay till. The model is developed to simulate field observations of a full scale bioremediation scheme in a fractured clay till and thereby to assess remediation efficiency and timeframe. A relatively simple approach is used to link the fermentation of the electron donor soybean oil to the sequential dechlorination of trichloroethene (TCE) while considering redox conditions and the heterogeneous clay till system (clay till matrix, fractures and sand stringers). The model is tested on lab batch experiments and applied to describe sediment core samples from a TCE-contaminated site. Model simulations compare favorably to field observations and demonstrate that dechlorination may be limited to narrow bioactive zones in the clay matrix around fractures and sand stringers. Field scale simulations show that the injected donor is expected to be depleted after 5 years, and that without donor re-injection contaminant rebound will occur in the high permeability zones and the mass removal will stall at 18%. Long remediation timeframes, if dechlorination is limited to narrow bioactive zones, and the need for additional donor injections to maintain dechlorination activity may limit the efficiency of ERD in low-permeability media. Future work should address the dynamics of the bioactive zones, which is essential to understand for predictions of long term mass removal.

Pentachlorophenol dechlorination with zero valent iron: a Raman and GCMS study of the complex role of surficial iron oxides.

Science.gov (United States)

Gunawardana, Buddhika; Swedlund, Peter J; Singhal, Naresh; Nieuwoudt, Michel K

2018-04-20

The dechlorination of chlorinated organic pollutants by zero valent iron (ZVI) is an important water treatment process with a complex dependence on many variables. This complexity means that there are reported inconsistencies in terms of dechlorination with ZVI and the effect of ZVI acid treatment, which are significant and are as yet unexplained. This study aims to decipher some of this complexity by combining Raman spectroscopy with gas chromatography-mass spectrometry (GC-MS) to investigate the influence of the mineralogy of the iron oxide phases on the surface of ZVI on the reductive dechlorination of pentachlorophenol (PCP). Two electrolytic iron samples (ZVI-T and ZVI-H) were found to have quite different PCP dechlorination reactivity in batch reactors under anoxic conditions. Raman analysis of the "as-received" ZVI-T indicated the iron was mainly covered with the ferrous oxide (FeO) wustite, which is non-conducting and led to a low rate of PCP dechlorination. In contrast, the dominant oxide on the "as-received" ZVI-H was magnetite which is conducting and, compared to ZVI-T, the ZVI-H rate of PCP dechlorination was four times faster. Treating the ZVI-H sample with 1 N H 2 SO 4 made small change to the composition of the oxide layers and also minute change to the rate of PCP dechlorination. However, treating the ZVI-T sample with H 2 SO 4 led to the loss of wustite so that magnetite became the dominant oxide and the rate of PCP dechlorination increased to that of the ZVI-H material. In conclusion, this study clearly shows that iron oxide mineralogy can be a contributing factor to apparent inconsistencies in the literature related to ZVI performance towards dechlorination and the effect of acid treatment on ZVI reactivity.

PCE dechlorination by non-Dehalococcoides in a microbial electrochemical system.

Science.gov (United States)

Yu, Jaecheul; Park, Younghyun; Nguyen, Van Khanh; Lee, Taeho

2016-08-01

The bioremediation of tetrachloroethene (perchloroethene; PCE) contaminated sites generally requires a supply of some fermentable organic substrates as an electron donor. On the other hand, organic substrates can induce the massive growth of microorganisms around the injection wells, which can foul the contaminated subsurface environment. In this study, PCE dechlorination to ethene was performed in a microbial electrochemical system (MES) using the electrode (a cathode polarized at -500 mV vs. standard hydrogen electrode) as the electron donor. Denaturing gel gradient electrophoresis and pyrosequencing revealed a variety of non-Dehalococcoides bacteria dominant in MES, such as Acinetobacter sp. (25.7 % for AS1 in suspension of M3), Rhodopseudomonas sp. (10.5 % for AE1 and 10.1 % for AE2 in anodic biofilm of M3), Pseudomonas aeruginosa (22.4 % for BS1 in suspension of M4), and Enterobacter sp. (21.7 % for BE1 in anodic biofilm of M4) which are capable of electron transfer, hydrogen production and dechlorination. The Dehalococcoides group, however, was not detected in this system. Therefore, these results suggest that a range of bacterial species outside the Dehalococcoides can play an important role in the microbial electrochemical dechlorination process, which may lead to innovative bioremediation technology.

Dechlorination of PCB by radiation

International Nuclear Information System (INIS)

Shinozaki, Yoshiharu

1978-01-01

On the PCB poisoning accident in Japan occurred in 1968, Tokyo Metropolitan Isotope Research Center started to investigate the decomposition of PCB (polychlorinated biphenyl) on the request of Metropolitan government. The research center has found that if PCB is dissolved or extracted in alkaline 2-propanol solution and then irradiated with γ-ray, PCB is dechlorinated in chain-reactive manner, and biphenyl and salts (KCl or NaCl) are formed. Afterwards, it has been found that photolysis has also similar effect on PCB. Then, the basic design of a disposal pilot plant using ultraviolet ray and its economic evaluation have been performed, which is composed of photolysis reaction process, refining process and waste disposal process. However, its disposal cost only has reached the value three times as high as that of incineration process. If this is conducted by radiolysis, its disposal cost can be reduced to about 1/12 of that of ultraviolet ray system when an electron accelerator is employed. Cs-137 source gives better results than Co-60. Dechlorination process of PCB has been thus established. Further reduction of total cost will be the keypoint of radiolysis system to be adopted. If the application of electron accelerators to sludge treatment in the future, the effective use of recovered products, and the possibility of using Cs-137 large sources are considered, it is expected that the disposal cost of radiolysis process system becomes comparable with the incineration process. (Wakatsuki, Y.)

Dechlorinating reaction of organic chlorides

Energy Technology Data Exchange (ETDEWEB)

Yahata, Taneaki; Kihara, Shinji [Japan Atomic Energy Research Inst., Oarai, Ibaraki (Japan). Oarai Research Establishment; Ohuchi, Misao

1996-06-01

Dechlorination has been examined by the reaction between iron, aluminum powder or CaO and organic chlorides such as C{sub 2}HCl{sub 3} and CH{sub 2}Cl{sub 2}. Progress of the reaction was analyzed with mass spectrometer. The reaction between iron and organic chloride was rapidly occurred at the temperature between 350 and 440degC in an atmosphere of argon. Above 380degC, more than 99.5% of C{sub 2}HCl{sub 3} was decomposed within approximately 100 minutes. At 440degC, approximately 60% of C{sub 2}HCl{sub 3} was decomposed by the reaction with aluminium powder within approximately 100 minutes. At 440degC, reaction between C{sub 2}HCl{sub 3} and CaO powder were occurred rapidly in an atmosphere of argon to form CaCl{sub 2} and free carbon. Also in an atmosphere of air, nearly the same result was obtained. In this reaction, CaCl{sub 2}, CO and CO{sub 2} were formed. CH{sub 2}Cl{sub 2} was also decomposed by the reaction with iron at the temperature between 380 and 440degC. In the reaction, FeCl{sub 2}, carbon and hydrogen were formed. CH{sub 3}{sup +} and CH{sub 4} were observed during the dechlorinating reaction of CH{sub 2}Cl{sub 2}. Variation in particle size of iron powder such as 100, 150 and 250 mesh did not affect the reaction rate. (author)

PCB dechlorination hotspots and reductive dehalogenase genes in sediments from a contaminated wastewater lagoon.

Science.gov (United States)

Mattes, Timothy E; Ewald, Jessica M; Liang, Yi; Martinez, Andres; Awad, Andrew; Richards, Patrick; Hornbuckle, Keri C; Schnoor, Jerald L

2017-08-12

Polychlorinated biphenyls (PCBs) are a class of persistent organic pollutants that are distributed worldwide. Although industrial PCB production has stopped, legacy contamination can be traced to several different commercial mixtures (e.g., Aroclors in the USA). Despite their persistence, PCBs are subject to naturally occurring biodegradation processes, although the microbes and enzymes involved are poorly understood. The biodegradation potential of PCB-contaminated sediments in a wastewater lagoon located in Virginia (USA) was studied. Total PCB concentrations in sediments ranged from 6.34 to 12,700 mg/kg. PCB congener profiles in sediment sample were similar to Aroclor 1248; however, PCB congener profiles at several locations showed evidence of dechlorination. The sediment microbial community structure varied among samples but was dominated by Proteobacteria and Firmicutes. The relative abundance of putative dechlorinating Chloroflexi (including Dehalococcoides sp.) was 0.01-0.19% among the sediment samples, with Dehalococcoides sp. representing 0.6-14.8% of this group. Other possible PCB dechlorinators present included the Clostridia and the Geobacteraceae. A PCR survey for potential PCB reductive dehalogenase genes (RDases) yielded 11 sequences related to RDase genes in PCB-respiring Dehalococcoides mccartyi strain CG5 and PCB-dechlorinating D. mccartyi strain CBDB1. This is the first study to retrieve potential PCB RDase genes from unenriched PCB-contaminated sediments.

Studies on dechlorination of DDT (1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane) using magnesium/palladium bimetallic system

International Nuclear Information System (INIS)

Gautam, Sumit Kumar; Suresh, Sumathi

2007-01-01

The aim of our investigation was to compare the rates of dechlorination of DDT using Mg 0 /Pd 4+ system in two different reaction phases, namely, water-acetone and 0.05% biosurfactant in water. Since palladium is expensive and its toxicity effects are not well known we also examined the reuse efficiency of Pd 0 immobilized on alumina for dechlorinating DDT. Studies on the dechlorination of DDT in water-acetone (1:1, v/v) and 0.05% biosurfactant phases revealed that the reaction followed second order kinetics and rate of reaction is dependent upon both initial concentrations of the target compound and Mg 0 /Pd 4+ . The presence of acid enhanced the rate of reaction by providing protons and preventing passivation of metal that occurs due to deposition of magnesium hydroxide. GC-MS analyses revealed the formation of completely dechlorinated hydrocarbon skeleton of DDT namely, diphenylethane (DPE), as the end product in both reaction phases (water-acetone and 0.05% biosurfactant in water) thereby implying the removal of all five chlorine atoms (three alkyl and two aryl) of DDT. The optimum ratio of water and acetone to facilitate successful dechlorination reaction was found to be 9:1. Results suggested that salt form (K 2 PdCl 6 ) of palladium had higher potential to dechlorinate DDT as compared to pellet (Pd 0 -alumina) form (efficiencies of 95 and 36%, respectively, for 100 ppm initial concentration of DDT). We noted that Pd 0 -alumina pellets could be reused at least four times for successful dechlorination of DDT provided Mg 0 granules are present in sufficient quantity. Technical grade DDT (50 ppm) containing significant amounts of DDD was dechlorinated almost completely by the Mg 0 /Pd 4+ (10 mg/0.2 mg/ml) within 1 h in water-biosurfactant phase. Our studies reveal that Mg/Pd system is a promising option due to its high reactivity and its ability to achieve complete dechlorination of DDT. This bimetallic system may be useful for designing indigenous permeable

Effects Of Aging And Oxidation Of Palladized Iron Embedded In Activated Carbon On The Dechlorination Of 2-Chlorobiphenyl

Science.gov (United States)

Reactive activated carbon (RAC) impregnated with palladized iron has been developed to effectively treat polychlorinated biphenyls (PCBs) in the environment by coupling adsorption and dechlorination of PCBs. In this study, we addressed the dechlorination reactivity and capacity ...

Impact of estuarine gradients on reductive dechlorination of 1,2,3,4-tetrachlorodibenzo-p-dioxin in river sediment enrichment cultures.

Science.gov (United States)

Dam, Hang T; Häggblom, Max M

2017-02-01

Polychlorinated dibenzo-p-dioxins (PCDDs) are among the most persistent organic pollutants. Although the total input of PCDDs into the environment has decreased substantially over the past four decades, their input via non-point sources is still increasing, especially in estuarine metropolitan areas. Here we report on the microbially mediated reductive dechlorination of PCDDs in anaerobic enrichment cultures established from sediments collected from five locations along the Hackensack River, NJ and investigate the impacts of sediment physicochemical characteristics on dechlorination activity. Dechlorination of 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TeCDD) and abundance of Dehalococcoides spp. negatively correlated with salinity and sulfate concentration in sediments used to establish the cultures. 1,2,3,4-TeCDD was dechlorinated to a lesser extent in cultures established from sediments from the tidally influenced estuarine mouth of the river. In cultures established from low salinity sediments, 1,2,3,4-TeCDD was reductively dechlorinated with the accumulation of 2-monochlorodibenzo-p-dioxin as the major product. Sulfate concentrations above 2 mM inhibited 1,2,3,4-TecDD dechlorination activity. Consecutive lateral- and peri- dechlorination took place in enrichment cultures with a minimal accumulation of 2,3-dichlorodibenzo-p-dioxin in active cultures. A Dehalococcoides spp. community was enriched and accounted for up to 64% of Chloroflexi detected in these sediment cultures. Copyright © 2016 Elsevier Ltd. All rights reserved.

DDT, DDD, AND DDE DECHLORINATION BY ZERO-VALENT IRON

Science.gov (United States)

Traditionally, destruction of DDT [1,1,1-trichIoro-2,2-bis(p-chlorophenyl)ethane] for environmental remediation required high-energy processes such as incineration. Here, the capability of powdered zero-valent iron to dechlorinate DDT and related compounds at room tempera...

Phylogenetic analysis of TCE-dechlorinating consortia enriched on a variety of electron donors.

Science.gov (United States)

Freeborn, Ryan A; West, Kimberlee A; Bhupathiraju, Vishvesh K; Chauhan, Sadhana; Rahm, Brian G; Richardson, Ruth E; Alvarez-Cohen, Lisa

2005-11-01

Two rapidly fermented electron donors, lactate and methanol, and two slowly fermented electron donors, propionate and butyrate, were selected for enrichment studies to evaluate the characteristics of anaerobic microbial consortia that reductively dechlorinate TCE to ethene. Each electron donor enrichment subculture demonstrated the ability to dechlorinate TCE to ethene through several serial transfers. Microbial community analyses based upon 16S rDNA, including terminal restriction fragment length polymorphism (T-RFLP) and clone library/sequencing, were performed to assess major changes in microbial community structure associated with electron donors capable of stimulating reductive dechlorination. Results demonstrated that five phylogenic subgroups or genera of bacteria were present in all consortia, including Dehalococcoides sp., low G+C Gram-positives (mostly Clostridium and Eubacterium sp.), Bacteroides sp., Citrobacter sp., and delta Proteobacteria (mostly Desulfovibrio sp.). Phylogenetic association indicates that only minor shifts in the microbial community structure occurred between the four alternate electron donor enrichments and the parent consortium. Inconsistent detection of Dehalococcoides spp. in clone libraries and T-RFLP of enrichment subcultures was resolved using quantitative polymerase chain reaction (Q-PCR). Q-PCR with primers specific to Dehalococcoides 16S rDNA resulted in positive detection of this species in all enrichments. Our results suggest that TCE-dechlorinating consortia can be stably maintained on a variety of electron donors and that quantities of Dehalococcoides cells detected with Dehalococcoides specific 16S rDNA primer/probe sets do not necessarily correlate well with solvent degradation rates.

Dechlorination of Trichloroacetic Acid Using a Noble Metal-Free Graphene-Cu Foam Electrode via Direct Cathodic Reduction and Atomic H.

Science.gov (United States)

Mao, Ran; Li, Ning; Lan, Huachun; Zhao, Xu; Liu, Huijuan; Qu, Jiuhui; Sun, Meng

2016-04-05

A three-dimensional graphene-copper (3D GR-Cu) foam electrode prepared by chemical vapor deposition method exhibited superior electrocatalytic activity toward the dechlorination of trichloroacetic acid (TCAA) as compared to the Cu foam electrode. The cyclic voltammetry and electrochemical impedance spectra analysis confirmed that GR accelerated the electron transfer from the cathode surface to TCAA. With the applied cathode potential of -1.2 V (vs SCE), 95.3% of TCAA (500 μg/L) was removed within 20 min at pH 6.8. TCAA dechlorination at the Cu foam electrode was enhanced at acidic pH, while a slight pH effect was observed at the GR-Cu foam electrode with a significant inhibition for Cu leaching. The electrocatalytic dechlorination of TCAA was accomplished via a combined stepwise and concerted pathway on both electrodes, whereas the concerted pathway was efficiently promoted on the GR-Cu foam electrode. The direct reduction by electrons was responsible for TCAA dechlorination at Cu foam electrode, while at GR-Cu foam electrode, the surface-adsorbed atomic H* also contributed to TCAA dechlorination owing to the chemical storage of hydrogen in the GR structure. Finally, the potential applicability of GR-Cu foam was revealed by its stability in the electrocatalytic dechlorination over 25 cycles.

Abiotic dechlorination in rock matrices impacted by long-term exposure to TCE.

Science.gov (United States)

Schaefer, Charles E; Towne, Rachael M; Lippincott, David R; Lacombe, Pierre J; Bishop, Michael E; Dong, Hailiang

2015-01-01

Field and laboratory tests were performed to evaluate the abiotic reaction of trichloroethene (TCE) in sedimentary rock matrices. Hydraulically conductive fractures, and the rock directly adjacent to the hydraulically conductive fractures, within a historically contaminated TCE bedrock aquifer were used as the basis for this study. These results were compared to previous work using rock that had not been exposed to TCE (Schaefer et al., 2013) to assess the impact of long-term TCE exposure on the abiotic dechlorination reaction, as the longevity of these reactions after long-term exposure to TCE was hitherto unknown. Results showed that potential abiotic TCE degradation products, including ethane, ethene, and acetylene, were present in the conductive fractures. Using minimally disturbed slices of rock core at and near the fracture faces, laboratory testing on the rocks confirmed that abiotic dechlorination reactions between the rock matrix and TCE were occurring. Abiotic daughter products measured in the laboratory under controlled conditions were consistent with those measured in the conductive fractures, except that propane also was observed as a daughter product. TCE degradation measured in the laboratory was well described by a first order rate constant through the 118-d study. Observed bulk first-order TCE degradation rate constants within the rock matrix were 1.3×10(-8) s(-1). These results clearly show that abiotic dechlorination of TCE is occurring within the rock matrix, despite decades of exposure to TCE. Furthermore, these observed rates of TCE dechlorination are expected to have a substantial impact on TCE migration and uptake/release from rock matrices. Copyright © 2014 Elsevier Ltd. All rights reserved.

Microbial community analysis of switchgrass planted and unplanted soil microcosms displaying PCB dechlorination.

Science.gov (United States)

Liang, Yi; Meggo, Richard; Hu, Dingfei; Schnoor, Jerald L; Mattes, Timothy E

2015-08-01

Polychlorinated biphenyls (PCBs) pose potential risks to human and environmental health because they are carcinogenic, persistent, and bioaccumulative. In this study, we investigated bacterial communities in soil microcosms spiked with PCB 52, 77, and 153. Switchgrass (Panicum virgatum) was employed to improve overall PCB removal, and redox cycling (i.e., sequential periods of flooding followed by periods of no flooding) was performed in an effort to promote PCB dechlorination. Lesser chlorinated PCB transformation products were detected in all microcosms, indicating the occurrence of PCB dechlorination. Terminal restriction fragment length polymorphism (T-RFLP) and clone library analysis showed that PCB spiking, switchgrass planting, and redox cycling affected the microbial community structure. Putative organohalide-respiring Chloroflexi populations, which were not found in unflooded microcosms, were enriched after 2 weeks of flooding in the redox-cycled microcosms. Sequences classified as Geobacter sp. were detected in all microcosms and were most abundant in the switchgrass-planted microcosm spiked with PCB congeners. The presence of possible organohalide-respiring bacteria in these soil microcosms suggests that they play a role in PCB dechlorination therein.

Comparison of an assay for Dehalococcoides DNA and a microcosm study in predicting reductive dechlorination of chlorinated ethenes in the field

International Nuclear Information System (INIS)

Lu Xiaoxia; Wilson, John T.; Kampbell, Donald H.

2009-01-01

The study aims to compare the detection of 16S rRNA gene of Dehalococcoides species and the microcosm study for biotransformation in predicting reductive dechlorination of chlorinated ethenes in ground water at hazardous waste sites. A total of 72 ground water samples were collected from 12 PCE or TCE contaminated sites in the United States. The samples were analyzed and used to construct microcosms in the laboratory. The results showed that the presence of Dehalococcoides DNA was well associated with dechlorination to ethene in the field. Nearly half of the wells where Dehalococcoides DNA was detected had ethene as a dechlorination end product. In comparison, for ground water samples of 16 wells where ethene was detected, ethene was produced in 11 of the corresponding microcosms. For most microcosms, during two years of incubation, dechlorination was less extensive than that observed in the field. - Positive results of the assay for Dehalococcoides DNA and the microcosm study may suggest that reductive dechlorination is occurring in the field

Impact of dechlorination processes on the sediment-water exchange of PCDD/F in Passaic river cores

Energy Technology Data Exchange (ETDEWEB)

Adriaens, P.; Khijniak, A. [Civil and Environmental Engineering, Univ. of Michigan, Ann Arbor (United States); Jones, K.; Green, N. [Environmental Science, Lancaster Univ. (United Kingdom); Gruden, C. [Univ. of Toledo, OH (United States)

2004-09-15

The potential for natural dechlorination processes in sediments to impact the biogeochemical cycling of dioxins and furans has been proposed as a possible mechanism to explain the prevalence of lesser halogenated dioxins and furans at the air-water interface. The hypothesis was supported by multiple lines of evidence, but has not been directly demonstrated. Field evidence indicated dynamic air-water exchange of PCDD/Fs in the Raritan Bay/Hudson River Estuary, whereby lesser chlorinated (predominantly diCDD/F) were present in the particle and apparent dissolved phase. Fugacity calculations indicated that the water column served as the source of these homologue groups. Laboratory evidence from Passaic River sediment cores and microbiallymediated dechlorination demonstrated that historic dioxins can undergo extensive dechlorination reactions, culminating in the formation of mono-and diCDD homologues. Similar pathways have been observed with PCDF, resulting in the accumulation of triCDF. The current paper reports on an investigation addressing the hypothesis of whether the lesser chlorinated PCDD/F observed at the air-water interface could be the result of selective dissolution of these congeners or homologues from sediments as they are produced during microbial dechlorination.

Evaluation of biodegradable plastics as solid hydrogen donors for the reductive dechlorination of fthalide by Dehalobacter species.

Science.gov (United States)

Yoshida, Naoko; Ye, Lizhen; Liu, Fengmao; Li, Zhiling; Katayama, Arata

2013-02-01

Biodegradable plastics (BPs) were evaluated for their applicability as sustainable and solid H(2) donors for microbial reductive dechlorination of 4,5,6,7-tetrachlorophthalide (fthalide). After a screening test of several BPs, the starch-based plastic (SP) that produced the highest levels of H(2) was selected for its use as the sole H(2) donor in this reaction. Fthalide dechlorination was successfully accomplished by combining an H(2)-producing SP culture and a KFL culture containing Dehalobacter species, supplemented with 0.13% and 0.5% SP, respectively. The efficiency of H(2) use in dechlorination was evaluated in a combined culture containing the KFL culture and strain Clostridium sp. Ma13, a new isolate that produces H(2) from SP. Results obtained with this culture indicated increased H(2)-fraction for fthalide dechlorination much more in this culture than in compared with a KFL culture supplemented with 20mM lactate, which are 0.75 H(2)·glucose(-1) and 0.015 H(2)·lactate(-1) in mol ratio, respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

Effect of TCE concentration and dissolved groundwater solutes on NZVI-promoted TCE dechlorination and H2 evolution.

Science.gov (United States)

Liu, Yueqiang; Phenrat, Tanapon; Lowry, Gregory V

2007-11-15

Nanoscale zero-valent iron (NZVI) is used to remediate contaminated groundwater plumes and contaminant source zones. The target contaminant concentration and groundwater solutes (NO3-, Cl-, HCO3-, SO4(2-), and HPO4(2-)) should affect the NZVI longevity and reactivity with target contaminants, but these effects are not well understood. This study evaluates the effect of trichloroethylene (TCE) concentration and common dissolved groundwater solutes on the rates of NZVI-promoted TCE dechlorination and H2 evolution in batch reactors. Both model systems and real groundwater are evaluated. The TCE reaction rate constant was unaffected by TCE concentration for [TCE] TCE concentration up to water saturation (8.4 mM). For [TCE] > or = 0.46 mM, acetylene formation increased, and the total amount of H2 evolved at the end of the particle reactive lifetime decreased with increasing [TCE], indicating a higher Fe0 utilization efficiency for TCE dechlorination. Common groundwater anions (5mN) had a minor effect on H2 evolution but inhibited TCE reduction up to 7-fold in increasing order of Cl- TCE reduction but increased acetylene production and decreased H2 evolution. NO3- present at > 3 mM slowed TCE dechlorination due to surface passivation. NO3- present at 5 mM stopped TCE dechlorination and H2 evolution after 3 days. Dissolved solutes accounted for the observed decrease of NZVI reactivity for TCE dechlorination in natural groundwater when the total organic content was small (< 1 mg/L).

Dechlorination of 1,2– dichloroethane by Pseudomonas aeruginosa ...

African Journals Online (AJOL)

As part of our attempt at isolating and stocking some indigenous microbial species, we isolated a bacterium from a waste dumpsite with appreciable dechlorination activity. 16S rDNA profiling revealed the isolate to be a strain of Pseudomonas aeruginosa and the sequence has been deposited in the NCBI nucleotide ...

Accelerated anaerobic dechlorination of DDT in slurry with Hydragric Acrisols using citric acid and anthraquinone-2,6-disulfonate (AQDS).

Science.gov (United States)

Liu, Cuiying; Xu, Xianghua; Fan, Jianling

2015-12-01

The application of electron donor and electron shuttle substances has a vital influence on electron transfer, thus may affect the reductive dechlorination of 1,1,1-trichoro-2,2-bis(p-chlorophenyl)ethane (DDT) in anaerobic reaction systems. To evaluate the roles of citric acid and anthraquinone-2,6-disulfonate (AQDS) in accelerating the reductive dechlorination of DDT in Hydragric Acrisols that contain abundant iron oxide, a batch anaerobic incubation experiment was conducted in a slurry system with four treatments of (1) control, (2) citric acid, (3) AQDS, and (4) citric acid+AQDS. Results showed that DDT residues decreased by 78.93%-92.11% of the initial quantities after 20days of incubation, and 1,1-dichloro-2,2-bis(4-chlorophenyl)-ethane (DDD) was the dominant metabolite. The application of citric acid accelerated DDT dechlorination slightly in the first 8days, while the methanogenesis rate increased quickly, and then the acceleration effect improved after the 8th day while the methanogenesis rate decreased. The amendment by AQDS decreased the Eh value of the reaction system and accelerated microbial reduction of Fe(III) oxides to generate Fe(II), which was an efficient electron donor, thus enhancing the reductive dechlorination rate of DDT. The addition of citric acid+AQDS was most efficient in stimulating DDT dechlorination, but no significant interaction between citric acid and AQDS on DDT dechlorination was observed. The results will be of great significance for developing an efficient in situ remediation strategy for DDT-contaminated sites. Copyright © 2015. Published by Elsevier B.V.

A conceptual model linking functional gene expression and reductive dechlorination rates of chlorinated ethenes in clay rich groundwater sediment

DEFF Research Database (Denmark)

Bælum, Jacob; Chambon, Julie Claire Claudia; Scheutz, Charlotte

2013-01-01

We used current knowledge of cellular processes involved in reductive dechlorination to develop a conceptual model to describe the regulatory system of dechlorination at the cell level; the model links bacterial growth and substrate consumption to the abundance of messenger RNA of functional gene...

Solidification of metal chloride waste from pyrochemical process via dechlorination-chlorination reaction system

Energy Technology Data Exchange (ETDEWEB)

Park, H.S.; Cho, I.H.; Lee, K.R.; Choi, J.H.; Eun, H.C.; Kim, I.T.; Park, G.I. [Korea Atomic Energy Research Inst., Deajeon (Korea, Republic of)

2014-07-01

The metal chloride wastes generated from the pyro-chemical process to recover uranium and TRUs has been considered as a problematic waste due to the high volatility and low compatibility with conventional silicate glass. Our research group has suggested the dechlorination approach for the solidification of this kind of waste by using a synthetic composite, SAP (SiO{sub 2}-Al{sub 2}O{sub 3}-P{sub 2}O{sub 5}). During the dechlorination, metal elements are chemically interacted with the inorganic composite, SAP, while chlorine is vaporized as gaseous chlorine. Metal elements in the salt were immobilized into phosphate and silicate glass which are uniformly distributed in tens of nm scale. During the dechlorination, gaseous chlorine is captured by Li{sub 2}O-Li{sub 2}O{sub 2} composite that can be converted into metal chloride (LiCl). About 98wt% of oxide composite was converted into LiCl that can be used as an electrolyte in the electrochemical process. The method suggested in this study can provide a chance to minimize the waste volume for the final disposal of salt wastes from a pyro-chemical process. (author)

Enhanced reductive dechlorination of DDT in an anaerobic system of dissimilatory iron-reducing bacteria and iron oxide

International Nuclear Information System (INIS)

Li, F.B.; Li, X.M.; Zhou, S.G.; Zhuang, L.; Cao, F.; Huang, D.Y.; Xu, W.; Liu, T.X.; Feng, C.H.

2010-01-01

The transformation of DDT was studied in an anaerobic system of dissimilatory iron-reducing bacteria (Shewanella decolorationis S12) and iron oxide (α-FeOOH). The results showed that S. decolorationis could reduce DDT into DDD, and DDT transformation rate was accelerated by the presence of α-FeOOH. DDD was observed as the primary transformation product, which was demonstrated to be transformed in the abiotic system of Fe 2+ + α-FeOOH and the system of DIRB + α-FeOOH. The intermediates of DDMS and DBP were detected after 9 months, likely suggesting that reductive dechlorination was the main dechlorination pathway of DDT in the iron-reducing system. The enhanced reductive dechlorination of DDT was mainly due to biogenic Fe(II) sorbed on the surface of α-FeOOH, which can serve as a mediator for the transformation of DDT. This study demonstrated the important role of DIRB and iron oxide on DDT and DDD transformation under anaerobic iron-reducing environments. - This is the first case reporting the reductive dechlorination of DDT in an anaerobic system of dissimilatory iron-reducing bacteria and iron oxide.

Enhanced reductive dechlorination of DDT in an anaerobic system of dissimilatory iron-reducing bacteria and iron oxide

Energy Technology Data Exchange (ETDEWEB)

Li, F.B., E-mail: cefbli@soil.gd.c [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Li, X.M. [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Zhou, S.G.; Zhuang, L. [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Cao, F. [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Huang, D.Y.; Xu, W.; Liu, T.X. [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Feng, C.H. [School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641 (China)

2010-05-15

The transformation of DDT was studied in an anaerobic system of dissimilatory iron-reducing bacteria (Shewanella decolorationis S12) and iron oxide (alpha-FeOOH). The results showed that S. decolorationis could reduce DDT into DDD, and DDT transformation rate was accelerated by the presence of alpha-FeOOH. DDD was observed as the primary transformation product, which was demonstrated to be transformed in the abiotic system of Fe{sup 2+} + alpha-FeOOH and the system of DIRB + alpha-FeOOH. The intermediates of DDMS and DBP were detected after 9 months, likely suggesting that reductive dechlorination was the main dechlorination pathway of DDT in the iron-reducing system. The enhanced reductive dechlorination of DDT was mainly due to biogenic Fe(II) sorbed on the surface of alpha-FeOOH, which can serve as a mediator for the transformation of DDT. This study demonstrated the important role of DIRB and iron oxide on DDT and DDD transformation under anaerobic iron-reducing environments. - This is the first case reporting the reductive dechlorination of DDT in an anaerobic system of dissimilatory iron-reducing bacteria and iron oxide.

Efficient dechlorination of carbon tetrachloride by hydrophobic green rust intercalated with dodecanoate anions

DEFF Research Database (Denmark)

Ayala Luis, Karina Barbara; Ginette Anneliese Cooper, Nicola; Bender Koch, Christian

2012-01-01

similar to those found in heavily contaminated groundwater close to polluted industrial sites (14 988 mu M) was reduced mainly to the fully dechlorinated products carbon monoxide (CO, yields >54 and formic acid (HCOOH, yields >6. Minor formation of chloroform (CF), the only chlorinated degradation product......The reductive dechlorination of carbon tetrachloride (CT) by Fe-II-Fe-III hydroxide (green rust) intercalated with dodecanoate, (Fe4Fe2III)-Fe-II (OH)(12)(C12H23O2)(2)center dot gamma H2O (designated GR(C12)), at pH similar to 8 and at room temperature was investigated. CT at concentration levels...

Reductive dechlorination of {gamma}-hexachlorocyclohexane using Fe-Pd bimetallic nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Nagpal, Varima; Bokare, Alok D. [Center for Nanobioscience, Agharkar Research Institute, G.G. Agarkar Road, Pune 411004, Maharashtra (India); Chikate, Rajeev C. [Department of Chemistry, MES Abasaheb Garware College, Karve Road, Pune 411004 (India); Rode, Chandrashekhar V. [Chemical Engineering and Process Development Division, National Chemical Laboratory, Pune 411008 (India); Paknikar, Kishore M., E-mail: paknikar@vsnl.com [Center for Nanobioscience, Agharkar Research Institute, G.G. Agarkar Road, Pune 411004, Maharashtra (India)

2010-03-15

Nanoscale Fe-Pd bimetallic particles were synthesized and used for degradation of lindane ({gamma}-hexachlorocyclohexane) in aqueous solution. Batch studies showed that 5 mg/L of lindane was completely dechlorinated within 5 min at a catalyst loading of 0.5 g/L and the degradation process followed first-order kinetics. GC-MS analysis in corroboration with GC-ECD results showed the presence of cyclohexane as the final degradation product. The proposed mechanism for the reductive dechlorination of lindane involves Fe corrosion-induced hydrogen atom transfer from the Pd surface. The enhanced degradation efficiency of Fe-Pd nanoparticles is attributed to: (1) high specific surface area of the nanoscale metal particles (60 m{sup 2}/g), manyfold greater that of commercial grade micro- or milli-scale iron particles ({approx}1.6 m{sup 2}/g); and, (2) increased catalytic reactivity due to the presence of Pd on the surface. Recycling and column studies showed that these nanoparticles exhibit efficient and sustained catalytic activity.

Borohydride, micellar, and exciplex-enhanced dechlorination of chlorobiphenyls

Energy Technology Data Exchange (ETDEWEB)

Epling, G.A.; Florio, E.M.; Bourque, A.J.; Qian, H.H.; Stuart, J.D.

1988-08-01

The photodechlorination of polychlorinated biphenyls (PCB's) has been studied in the presence of sodium borohydride, detergents, and exciplex-forming additives. In a family of 13 representative PCB's these variations generally led to a dramatically increased rate of photodegradation. Further, the products of photoreaction in the presence of sodium borohydride are more cleanly the simple dechlorinated aromatics, with fewer side reactions than observed with ordinary photolysis.

Dechlorination kinetics of TCE at toxic TCE concentrations: Assessment of different models.

Science.gov (United States)

Haest, P J; Springael, D; Smolders, E

2010-01-01

The reductive dechlorination of trichloroethene (TCE) in a TCE source zone can be self-inhibited by TCE toxicity. A study was set up to examine the toxicity of TCE in terms of species specific degradation kinetics and microbial growth and to evaluate models that describe this self-inhibition. A batch experiment was performed using the TCE dechlorinating KB-1 culture at initial TCE concentrations ranging from 0.04mM to saturation (8.4mM). Biodegradation activity was highest at 0.3mM TCE and no activity was found at concentrations from 4 to 8mM. Species specific TCE and cis-DCE (cis-dichloroethene) degradation rates and Dehalococcoides numbers were modeled with Monod kinetics combined with either Haldane inhibition or a log-logistic dose-response inhibition on these rates. The log-logistic toxicity model appeared the most appropriate model and predicts that the species specific degradation activities are reduced by a factor 2 at about 1mM TCE, respectively cis-DCE. However, the model showed that the inhibitive effects on the time for TCE to ethene degradation are a complex function of degradation kinetics and the initial cell densities of the dechlorinating species. Our analysis suggests that the self-inhibition on biodegradation cannot be predicted by a single concentration threshold without information on the cell densities.

Reductive dechlorination of chlorinated solvents in landfills

International Nuclear Information System (INIS)

Wang, J.Y.; Wu, C.

2002-01-01

The use of landfills as an in situ biological treatment system represents an alternative for source area remediation with a significant cost saving. The specific objective of this research is to investigate the intrinsic bioattenuation capacity of the landfill ecosystem for chlorinated aliphatic hydrocarbons (CAHs). The research was conducted in two complementary systems: simulated landfill bioreactors and batch degradation experiment in serum bottles. Refuse samples excavated from a landfill were tested in laboratory bioreactors designed and operated to facilitate refuse decomposition under landfilling conditions. Each bioreactor was operated with leachate recirculation and gas collection. Target CAHs, tetrachloroethene (PCE) and trichloroethene (TCE), were added to selected reactors and maintained at 20 μM each in leachate to simulate the effect of long-term exposure of refuse microorganisms to CAHs on the degradation potential of these chemicals in landfills. At two different stages of refuse decomposition, active refuse decomposition representing young landfills and maturation phase representing aged landfills, anaerobic microbial cultures were derived from selected bioreactors and tested in serum bottles for their abilities to biodegrade target CAHs. Results of this study suggest that landfills have an intrinsic reductive dechlorination capacity for PCE and TCE. The decomposition of refuse, a source of complex organics, enhances reductive dechlorination by the refuse cultures tested in this study. In addition, the test results suggest that it may be possible to develop engineering strategies to promote both CAHs degradation and refuse decomposition in landfills. (author)

Microbial dechlorination activity during and after chemical oxidant treatment

Energy Technology Data Exchange (ETDEWEB)

Doğan-Subaşı, Eylem [Flemish Institute for Technological Research (VITO), Separation and Conversion Technology, Boeretang 200, 2400 Mol (Belgium); Laboratory of Microbial Ecology and Technology (LabMET), Ghent University, Coupure Links 653, 9000 Gent (Belgium); Bastiaens, Leen, E-mail: leen.bastiaens@vito.be [Flemish Institute for Technological Research (VITO), Separation and Conversion Technology, Boeretang 200, 2400 Mol (Belgium); Boon, Nico [Laboratory of Microbial Ecology and Technology (LabMET), Ghent University, Coupure Links 653, 9000 Gent (Belgium); Dejonghe, Winnie [Flemish Institute for Technological Research (VITO), Separation and Conversion Technology, Boeretang 200, 2400 Mol (Belgium)

2013-11-15

Highlights: • Combined treatment was possible below 0.5 g/L of KMnO{sub 4} and 1 g/L of Na{sub 2}S{sub 2}O{sub 8}. • By-products SO{sub 4}{sup 2−} and MnO{sub 2(s)} had inhibitory effects on dehalogenating bacteria. • Oxidation reduction potential (ORP) was identified as a crucial parameter for recovery of oxidant exposed cells. • Bioaugmentation is a necessity at 0.5 g/L of KMnO{sub 4} and 1 g/L of Na{sub 2}S{sub 2}O{sub 8} and above. -- Abstract: Potassium permanganate (PM) and sodium persulfate (PS) are used in soil remediation, however, their compatibility with a coinciding or subsequent biotreatment is poorly understood. In this study, different concentrations of PM (0.005–2 g/L) and PS (0.01–4.52 g/L) were applied and their effects on the abundance, activity, and reactivation potential of a dechlorinating enrichment culture were investigated. Expression of the tceA, vcrA and 16S rRNA genes of Dehalococcoides spp. were detected at 0.005–0.01 g/L PM and 0.01–0.02 g/L PS. However, with 0.5–2 g/L PM and 1.13–4.52 g/L PS no gene expression was recorded, neither were indicator molecules for total cell activity (Adenosine triphosphate, ATP) detected. Dilution did not promote the reactivation of the microbial cells when the redox potential was above −100 mV. Similarly, inoculated cells did not dechlorinate trichloroethene (TCE) above −100 mV. When the redox potential was decreased to −300 mV and the reactors were bioaugmented for a second time, dechlorination activity recovered, but only in the reactors with 1.13 and 2.26 g/L PS. In conclusion, our results show that chemical oxidants can be combined with a biotreatment at concentrations below 0.5 g/L PM and 1 g/L PS.

Threshold amounts of organic carbon needed to initiate reductive dechlorination in groundwater systems

Science.gov (United States)

Chapelle, Francis H.; Thomas, Lashun K.; Bradley, Paul M.; Rectanus, Heather V.; Widdowson, Mark A.

2012-01-01

Aquifer sediment and groundwater chemistry data from 15 Department of Defense facilities located throughout the United States were collected and analyzed with the goal of estimating the amount of natural organic carbon needed to initiate reductive dechlorination in groundwater systems. Aquifer sediments were analyzed for hydroxylamine and NaOH-extractable organic carbon, yielding a probable underestimate of potentially bioavailable organic carbon (PBOC). Aquifer sediments were also analyzed for total organic carbon (TOC) using an elemental combustion analyzer, yielding a probable overestimate of bioavailable carbon. Concentrations of PBOC correlated linearly with TOC with a slope near one. However, concentrations of PBOC were consistently five to ten times lower than TOC. When mean concentrations of dissolved oxygen observed at each site were plotted versus PBOC, it showed that anoxic conditions were initiated at approximately 200 mg/kg of PBOC. Similarly, the accumulation of reductive dechlorination daughter products relative to parent compounds increased at a PBOC concentration of approximately 200 mg/kg. Concentrations of total hydrolysable amino acids (THAA) in sediments also increased at approximately 200 mg/kg, and bioassays showed that sediment CO2 production correlated positively with THAA. The results of this study provide an estimate for threshold amounts of bioavailable carbon present in aquifer sediments (approximately 200 mg/kg of PBOC; approximately 1,000 to 2,000 mg/kg of TOC) needed to support reductive dechlorination in groundwater systems.

Chemical dechlorination of pesticides at a superfund site in Region II

International Nuclear Information System (INIS)

Pendergrass, S.; Prince, J.

1991-01-01

Selecting technologies for cleaning up hazardous waste sites is a complex task, due in part to the rapidly changing nature of the state-of-the-art in technology. There is strong support for use of innovative technologies as specified in Section 121(b) of CERCLA. However, use of an innovative technology requires overcoming a variety of challenges. These challenges include: Screening potentially appropriate technologies, including innovative technologies, and selecting one or more potential innovative technologies for which preliminary results are promising; however, site-specific data are needed prior to technology evaluation. Evaluating the effectiveness of the proposed technology for the site through the use of treatability studies. Gaining acceptance for the innovative technology, which may employ new or unfamiliar concepts. Determining optimal design and operating parameters for full-scale remediation. This paper discusses the technology evaluation process and how that process supported the selection of an innovative technology for the Myers Property site, a Superfund site in Region II. A case study is presented showing how technology screening and laboratory treatability studies were used to evaluate an innovative technology (chemical dechlorination), which was selected as the technology for remediation of soils and sediments contaminated with pesticides at this environmentally sensitive site in New Jersey. The remedy selected by the U.S. EPA for this site designates chemical dechlorination as the selected technology, but does not specify any particular vendor or process. Rather, the remedy sets forth technology performance standards and recommends certain design tasks which may be used to select a particular chemical process. This paper discusses he of these design tasks as they might apply to innovative technologies, using chemical dechlorination as a model

Dechlorination of Environmental Contaminants Using a Hybrid Nanocatalyst: Palladium Nanoparticles Supported on Hierarchical Carbon Nanostructures

Directory of Open Access Journals (Sweden)

Hema Vijwani

2012-01-01

Full Text Available This paper demonstrates the effectiveness of a new type of hybrid nanocatalyst material that combines the high surface area of nanoparticles and nanotubes with the structural robustness and ease of handling larger supports. The hybrid material is made by fabricating palladium nanoparticles on two types of carbon supports: as-received microcellular foam (Foam and foam with carbon nanotubes anchored on the pore walls (CNT/Foam. Catalytic reductive dechlorination of carbon tetrachloride with these materials has been investigated using gas chromatography. It is seen that while both palladium-functionalized carbon supports are highly effective in the degradation of carbon tetrachloride, the rate of degradation is significantly increased with palladium on CNT/Foam. However, there is scope to increase this rate further if the wettability of these structures can be enhanced in the future. Microstructural and spectroscopic analyses of the fresh and used catalysts have been compared which indicates that there is no change in density or surface chemical states of the catalyst after prolonged use in dechlorination test. This implies that these materials can be used repeatedly and hence provide a simple, powerful, and cost-effective approach for dechlorination of water.

Kinetic analysis of dechlorination and oxidation of PrOCl by using a non-isothermal TG method

International Nuclear Information System (INIS)

Yang, H.C.; Eun, H.C.; Cho, Y.Z.; Lee, H.S.; Kim, I.T.

2009-01-01

Thermal dechlorination and oxidation process of praseodymium oxychloride, PrOCl, was studied from the view point of reaction kinetics. On the basis of data of thermogravimetry under different oxygen partial pressures at various heating rates, a kinetic analysis was performed using an isoconversional method and a master plot method. The results of the isoconversional method of TG data suggested that the dechlorination and oxidation of PrOCl followed a single step with activation energy of 112.6 ± 3.4 kJ mol -1 , and from master plot methods, the reaction was described by a linear-contracting phase boundary reaction

Development and sensitivity analysis of a fullykinetic model of sequential reductive dechlorination in subsurface

DEFF Research Database (Denmark)

Malaguerra, Flavio; Chambon, Julie Claire Claudia; Albrechtsen, Hans-Jørgen

2010-01-01

and natural degradation of chlorinated solvents frequently occurs in the subsurface through sequential reductive dechlorination. However, the occurrence and the performance of natural sequential reductive dechlorination strongly depends on environmental factor such as redox conditions, presence of fermenting...... organic matter / electron donors, presence of specific biomass, etc. Here we develop a new fully-kinetic biogeochemical reactive model able to simulate chlorinated solvents degradation as well as production and consumption of molecular hydrogen. The model is validated using batch experiment data......Chlorinated hydrocarbons originating from point sources are amongst the most prevalent contaminants of ground water and often represent a serious threat to groundwater-based drinking water resources. Natural attenuation of contaminant plumes can play a major role in contaminated site management...

Phreatophyte influence on reductive dechlorination in a shallow aquifer contaminated with trichloroethene (TCE)

Science.gov (United States)

Lee, R.W.; Jones, S.A.; Kuniansky, E.L.; Harvey, G.; Lollar, B.S.; Slater, G.F.

2000-01-01

Phytoremediation uses the natural ability of plants to degrade contaminants in groundwater. A field demonstration designed to remediate aerobic shallow groundwater contaminated with trichloroethene began in April 1996 with the planting of cottonwood trees, a short-rotation woody crop, over an approximately 0.2-ha area at the Naval Air Station, Fort Worth, Texas. The project was developed to demonstrate capture of contaminated groundwater and degradation of contaminants by phreatophytes. Analyses from samples of groundwater collected from July 1997 to June 1998 indicate that tree roots have the potential to create anaerobic conditions in the groundwater that will facilitate degradation of trichloroethene by microbially mediated reductive dechlorination. Organic matter from root exudates and decay of tree roots probably stimulate microbial activity, consuming dissolved oxygen. Dissolved oxygen concentrations, which varied across the site, were smallest near a mature cottonwood tree (about 20 years of age and 60 meters southwest of the cottonwood plantings) where degradation products of trichloroethene were measured. Oxidation of organic matter is the primary microbially mediated reaction occurring in the groundwater beneath the planted trees whereas near the mature cottonwood tree, data indicate that methanogenesis is the most probable reaction occurring. Reductive dechlorination in groundwater either is not occurring or is not a primary process away from the mature tree. Carbon-13 isotope values for trichloroethene are nearly identical at locations away from the mature tree, further confirming that dechlorination is not occurring at the site.

Thermal dechlorination of PCB-209 over Ca species-doped Fe₂O₃.

Science.gov (United States)

Su, Guijin; Huang, Linyan; Shi, Ruifang; Liu, Yexuan; Lu, Huijie; Zhao, Yuyang; Yang, Fan; Gao, Lirong; Zheng, Minghui

2016-02-01

Degradation reaction of decachlorobiphenyl (PCB-209) was investigated over the synthesized Ca species-doped Fe2O3 at 300 °C. The 1%Ca-Fe2O3 exhibited the highest activity among the four catalysts prepared with the pseudo-first order reaction at k(obs) = 0.103 min(-1). PCB-207, PCB-197, PCB-176, PCB-184, PCB-150, PCB-136, PCB-148, PCB-104, PCB-96, PCB-54, PCB-19, PCB-4 and PCB-1 were identified as the dominant isomers in their respective nonachlorobiphenyl (NonaCB) to monochlorobiphenyl (MonoCB) homologue groups. Analysis of the hydrodechlorination products indicated that dechlorination was much more favored on meta- and para-than on ortho-positions. The formation of significantly predominant NonaCB and octachlorobiphenyl (OctaCB) isomers was attributed to lower energy principles and to the 90° dihedral angles of two aromatic rings which prevented the hydrodechlorination at ortho-positions. When the number of chlorine atoms is not more than 7, the steric effect supports the formation of predominant PCB isomers having chlorines at four ortho-positions. During the dechlorination of tetrachlorobiphenyl (TetraCB) formed to generate monochlorobiphenyl (MonoCB) isomers, the chlorine atoms fully substituted at the ortho-positions have to be successively removed, with the first two dechlorinations preferentially occurring at the two different benzene rings. This is dissimilar to that of octachloronaphthalene (PCN-75) in which the hydrodechlorination reaction happened preferentially at ortho-position due to the existence of steric effects. The opposite roles of the steric effect in ortho-position between PCB-209 and PCN-75 might be due to the difference of the π-conjugated plane caused by the dihedral angle of 90° and 0° of the two aromatic rings. Copyright © 2015 Elsevier Ltd. All rights reserved.

The oxidative p-dichlorobenzene dechlorinating in the presence of copper (ΙΙ complexes and nitrogen (ΙΙ, ΙV oxides

Directory of Open Access Journals (Sweden)

Valentina Yemelyanova

2012-12-01

Full Text Available The results of dechlorination in the solution CuCl2–TBP–NaNO2–О2–Н2О kinetics research are presented in the article. All system components influence to the dechlorination process is studied and quantitatively described. The composition of copper intermediate complexes participating in reaction is studied by the instrumentality of UV-spectroscopy. Established part of binuclear copper complexes in the catalytic intermediate complex constants of formation were estimated and compared with the kinetic and spectrophotometric methods. The composition of the intermediate complexes responsible for process is defined, the mechanism scheme is offered, the p-dichlorobenzene dechlorination limiting stage including redox-disintegration of the intermediate complex consisting of dimeric complex of copper (II, I chloride, nitrogen oxide and p-dichlorobenzene is defined.

Biological reductive dechlorination of tetrachloroethylene and trichloroethylene to ethylene under methanogenic conditions

International Nuclear Information System (INIS)

Freedman, D.L.; Gossett, J.M.

1989-01-01

A biological process for remediation of groundwater contaminated with tetrachloroethylene (PCE) and trichloroethylene (TCE) can only be applied if the transformation products are environmentally acceptable. Studies with enrichment cultures of PCE- and TCE-degrading microorganisms provide evidence that, under methanogenic conditions, mixed cultures are able to completely dechlorinate PCE and TCE to ethylene, a product which is environmentally acceptable. Radiotracer studies with [ 14 C]PCE indicated that [ 14 C]ethylene was the terminal product; significant conversion to 14 CO 2 or 14 CH 4 was not observed. The rate-limiting step in the pathway appeared to be conversion of vinyl chloride to ethylene. To sustain reductive dechlorination of PCE and TCE, it was necessary to supply an electron donor; methanol was the most effective, although hydrogen, formate, acetate, and glucose also served. Studies with the inhibitor 2-bromoethanesulfonate suggested that methanogens played a key role in the observed biotransformations of PCE and TCE

Evidence of rock matrix back-diffusion and abiotic dechlorination using a field testing approach

Science.gov (United States)

Schaefer, Charles E.; Lippincott, David R.; Klammler, Harald; Hatfield, Kirk

2018-02-01

An in situ field demonstration was performed in fractured rock impacted with trichloroethene (TCE) and cis-1,2-dichloroethene (DCE) to assess the impacts of contaminant rebound after removing dissolved contaminants within hydraulically conductive fractures. Using a bedrock well pair spaced 2.4 m apart, TCE and DCE were first flushed with water to create a decrease in dissolved contaminant concentrations. While hydraulically isolating the well pair from upgradient contaminant impacts, contaminant rebound then was observed between the well pair over 151 days. The magnitude, but not trend, of TCE rebound was reasonably described by a matrix back-diffusion screening model that employed an effective diffusion coefficient and first-order abiotic TCE dechlorination rate constant that was based on bench-scale testing. Furthermore, a shift in the TCE:DCE ratio and carbon isotopic enrichment was observed during the rebound, suggesting that both biotic and abiotic dechlorination were occurring within the rock matrix. The isotopic data and back-diffusion model together served as a convincing argument that matrix back-diffusion was the mechanism responsible for the observed contaminant rebound. Results of this field demonstration highlight the importance and applicability of rock matrix parameters determined at the bench-scale, and suggest that carbon isotopic enrichment can be used as a line of evidence for abiotic dechlorination within rock matrices.

Photocatalytic dechlorination of PCB 138 using leuco-methylene blue and visible light; reaction conditions and mechanisms

International Nuclear Information System (INIS)

Izadifard, Maryam; Langford, Cooper H.; Achari, Gopal

2010-01-01

A study of dechlorination of PCB 138, under visible light employing methylene blue (MB) and triethylamine (TEA) in acetonitrile/water has been conducted to investigate the details of the mechanism of dechlorination and to determine the efficiency of the process for this representative congener. Two other amines, N-methyldiethanolamine (MEDA) and (triethanolamine) TEOA also replaced TEA and two other solvents, methanol and ethanol replacing acetonitrile were examined for effects on reaction rates. The results show that PCB 138 can be dechlorinated efficiently in this photocatalytic reaction. Clarifying ambiguities in several previous reports, the reduced form of MB, leuco-methylene blue (LMB) was identified as responsible for the photoreaction with its excited state transferring an electron to PCBs; oxidized LMB (i.e. MB) is reduced back to LMB by the excess amine present. The reaction depends on a cycle driven by the amine as a sacrificial electron donor. MEDA proved to be the most efficient electron donor; apparently in consequence of the most favourable steady state concentration of LMB. Methanol and ethanol may be used to replace acetonitrile with little change in the efficiency of the reaction.

Investigations in the microbial degradation of polychlorinated dibenzo-p-dioxins and means of reductive dechlorination and aerobic mineralization

International Nuclear Information System (INIS)

Rosenbrock, P.

1997-12-01

The work had the objective to develop a biological method for cleaning up PCDD/PCDF contaminated upper soil layers (PCDDs/PCDFs: polychlorinated dibenzo-p-dioxins and dibenzofurans). Since highly chlorinated aromatic compounds persist in soil under aerobic conditions, reductive dechlorination of the compounds under anaerobic conditions was aimed at in a first phase of the project. A second, topped phase was destined for aerobic mineralization of the dechlorinated matrices. The tests were carried out on three farmland soils following long-term contamination with PCDDs/PCDFs. (orig./MG)

Mineralization of 2-chlorophenol by sequential electrochemical reductive dechlorination and biological processes

Energy Technology Data Exchange (ETDEWEB)

Arellano-González, Miguel Ángel; González, Ignacio [Universidad Autónoma Metropolitana-Iztapalapa, Departamento de Química, Av. San Rafael Atlixco No. 186, Col. Vicentina, 09340 Mexico D.F. (Mexico); Texier, Anne-Claire, E-mail: actx@xanum.uam.mx [Universidad Autónoma Metropolitana-Iztapalapa, Departamento de Biotecnología, Av. San Rafael Atlixco No. 186, Col. Vicentina, 09340 Mexico, D.F. (Mexico)

2016-08-15

Highlights: • Dechlorination of 2-chlorophenol to phenol was 100% efficient on Pd-Ni/Ti electrode. • An ECCOCEL reactor was efficient and selective to obtain phenol from 2-chlorophenol. • Phenol was totally mineralized in a coupled denitrifying biorreactor. • Global time of 2-chlorophenol mineralization in the combined system was 7.5 h. - Abstract: In this work, a novel approach was applied to obtain the mineralization of 2-chlorophenol (2-CP) in an electrochemical-biological combined system where an electrocatalytic dehydrogenation process (reductive dechlorination) was coupled to a biological denitrification process. Reductive dechlorination of 2-CP was conducted in an ECCOCEL-type reactor on a Pd-Ni/Ti electrode at a potential of −0.40 V vs Ag/AgCl{sub (s)}/KCl{sub (sat)}, achieving 100 percent transformation of 2-CP into phenol. The electrochemically pretreated effluent was fed to a rotating cylinder denitrifying bioreactor where the totality of phenol was mineralized by denitrification, obtaining CO{sub 2} and N{sub 2} as the end products. The total time required for 2-CP mineralization in the combined electrochemical-biological process was 7.5 h. This value is close to those previously reported for electrochemical and advanced oxidation processes but in this case, an efficient process was obtained without accumulation of by-products or generation of excessive energy costs due to the selective electrochemical pretreatment. This study showed that the use of electrochemical reductive pretreatment combined with biological processes could be a promising technology for the removal of recalcitrant molecules, such as chlorophenols, from wastewaters by more efficient, rapid, and environmentally friendly processes.

Reductive dechlorination of chlorinated hydrocarbons as non-aqueous phase liquid (NAPL): Preliminary investigation on effects of cement doses

Energy Technology Data Exchange (ETDEWEB)

Do, Si-Hyun, E-mail: sihyun2@hanyang.ac.kr [Department of Chemical Engineering, Hanyang University, Seoul 133-791 (Korea, Republic of); Batchelor, Bill [Zachry Department of Civil Engineering, Texas A and M University, College Station, TX 77843 (United States)

2012-07-15

The reactivities of various types of iron mixtures to degrade chlorinated hydrocarbons (PCE, TCE and 1,1,1-TCA) in the form of non-aqueous phase liquids were investigated. The iron mixtures included a mixture of Fe(II) and Portland cement (Fe(II)-C), a mixture of Fe(II), Fe(III) and Ca(OH){sub 2} (Fe(II/III)-L), and a mixture of Fe(II), Fe(III), Ca(OH){sub 2}, and Portland cement (Fe(II/III)-C). When the same amount of Fe(II) was used, Fe(II)-C was more reactive with chlorinated ethylenes (i.e. PCE and TCE) than Fe(II/III)-L. The reductive pathway for high concentrations of total PCE (i.e. above solubility) with Fe(II)-C was determined to be a combination of two-electron transfer, {beta}-elimination and hydrogenolysis. Increasing the cement dose from 5% to 10% in Fe(II)-C did not affect PCE dechlorination rates, but it did favor the {beta}-elimination pathway. In addition, when Fe(II/III)-C with 5%C was used, PCE dechlorination was similar to that by Fe(II)-C, but this mixture did not effectively degrade TCE. A modified second-order kinetic model was developed and shown to appropriately describe degradation of TCE at high concentrations. Fe(II/III)-L effectively degraded high concentrations of 1,1,1-TCA at rates that were similar to those obtained with Fe(II)-C using 10% C. Moreover, both increasing cement doses and the presence of Fe(III) increased dechlorination rates of 1,1,1-TCA, which was mainly through the hydrogenolysis pathway. The reactivity of Fe(II/III)-L was strongly dependent on the target compound (i.e. less reactivity with TCE, more with 1,1,1-TCA). Therefore, Fe(II/III)-L could be a potential mixture for degrading 1,1,1-TCA, but it should be modified to degrade TCE more effectively. - Highlights: Black-Right-Pointing-Pointer TCE yield indicated that PCE dechlorination was through hydrogenolysis and {beta}-elimination. Black-Right-Pointing-Pointer {beta}-elimination, especially PCE to dichloroacetylene, was favored with the higher cement doses. Black

Influence of iron-bearing phyllosilicates on the dechlorination kinetics of 1,1,1-trichloroethane in Fe(II)/cement slurries.

Science.gov (United States)

Jung, Bahngmi; Batchelor, Bill

2007-07-01

This study examines the effect of iron-bearing phyllosilicates on dechlorination rates of chlorinated aliphatic hydrocarbons (CAHs) in iron-based degradative solidification/stabilization (DS/S-Fe(II)). Laboratory batch experiments were conducted to evaluate dechlorination rates of 1,1,1-trichloroethane (1,1,1-TCA) in a mixture solution of Fe(II), cement and three different iron-bearing phyllosilicates (biotite, vermiculite, and montmorillonite). A first-order rate model was generally used to describe the dechlorination kinetics and the rate constants were dependent on soil mineral type (biotite, vermiculite, and montmorillonite), Fe(II) dose, and the mass ratio of cement to soil mineral. The pseudo-first-order rate constant for montmorillonite was lower than that for biotite and vermiculite by factors of 11-27 when the mass ratio of cement to phyllosilicates was fixed at one. The presence of biotite and vermiculite increase and the presence of montmorillonite decrease the degradation rate that would be observed in their absence. The effect of cement/mineral ratio on rate constants with three different soil minerals indicates that biotite was more reactive than the other two phyllosilicates. This may be due to high accessible natural Fe(II) content in biotite. Montmorillonite appears to inhibit dechlorination by either inactivating Fe(II) by ion exchange or by physically blocking active sites on cement hydration products.

Efficient photocatalytic reductive dechlorination of 4-chlorophenol to phenol on {0 0 1}/{1 0 1} facets co-exposed TiO_2 nanocrystals

International Nuclear Information System (INIS)

Jiang, Guodong; Wei, Meng; Yuan, Songdong; Chang, Qing

2016-01-01

Graphical abstract: - Highlights: • 4-Chlorophenol is dechlorinated over {0 0 1}/{1 0 1} co-exposed TiO_2 nanocrystals. • Photo-electrons are accumulated on {1 0 1} facets due to surface heterojunction. • Fluorine will trap photoelectrons to depress the dechlorination performance. • Sufficient isopropanol promotes the dechlorination activity and selectivity. - Abstract: 4-chlorophenol could be efficiently photoreductively dechlorinated over anatase TiO_2 nanocrystals with co-exposed {0 0 1} and {1 0 1} facets, which were synthesized and further characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Although fluorine could adsorb on {0 0 1} facets to decrease their surface energy, enabling TiO_2 to expose high energy {0 0 1} facets, the surface bonded fluorine might depress the photoreductive dechlorination efficiency of 4-chlorophenol, attributed to the electron trapping role of surface ≡Ti−F groups. Due to the formation of a surface heterojunction between {1 0 1} and {0 0 1} facets in a single TiO_2 nanocrystal, electrons and holes were spontaneously self-separated and selectively migrate to {1 0 1} and {0 0 1} facets, respectively. Electron trapping experiments demonstrated that photogenerated electrons are the responsible for the reductive dechlorinaton of 4-chlorophenol to phenol. To avoid the oxidative degradation of 4-chlorophenol by holes and ensure sufficient electrons to reductively dechlorinate the substrate, moderate scavengers were required in the reaction system and dissolved oxygen, which might deplete electron on TiO_2, also should be removed. With the optimal scavengers, the conversion efficiency of 4-chlorophenol (4-CP) achieved 97.5% and the selectivity for phenol was 92.5%, which were much higher than that of commercial TiO_2 P25.

Anaerobic reductive dechlorination of tetrachloroethene: how can dual Carbon-Chlorine isotopic measurements help elucidating the underlying reaction mechanism?

Science.gov (United States)

Badin, Alice; Buttet, Géraldine; Maillard, Julien; Holliger, Christof; Hunkeler, Daniel

2014-05-01

Chlorinated ethenes (CEs) such as tetrachloroethene (PCE) are common persistent groundwater contaminants. Among clean-up strategies applied to sites affected by such pollution, bioremediation has been considered with a growing interest as it represents a cost-effective, environmental friendly approach. This technique however sometimes leads to an incomplete and slow biodegradation of CEs resulting in an accumulation of toxic metabolites. Understanding the reaction mechanisms underlying anaerobic reductive dechlorination would thus help assessing PCE biodegradation in polluted sites. Stable isotope analysis can provide insight into reaction mechanisms. For chlorinated hydrocarbons, carbon (C) and chlorine (Cl) isotope data (δ13C and δ37Cl) tend to show a linear correlation with a slope (m ≡ ɛC/ɛCl) characteristic of the reaction mechanism [1]. This study hence aims at exploring the potential of a dual C-Cl isotope approach in the determination of the reaction mechanisms involved in PCE reductive dechlorination. C and Cl isotope fractionation were investigated during anaerobic PCE dechlorination by two bacterial consortia containing members of the Sulfurospirillum genus. The specificity in these consortia resides in the fact that they each conduct PCE reductive dechlorination catalysed by one different reductive dehalogenase, i.e. PceADCE which yields trichloroethene (TCE) and cis-dichloroethene (cDCE), and PceATCE which yields TCE only. The bulk C isotope enrichment factors were -3.6±0.3 o for PceATCE and -0.7±0.1o for PceADCE. The bulk Cl isotope enrichment factors were -1.3±0.2 o for PceATCE and -0.9±0.1 o for PceADCE. When applying the dual isotope approach, two m values of 2.7±0.1 and 0.7±0.2 were obtained for the reductive dehalogenases PceATCE and PceADCE, respectively. These results suggest that PCE can be degraded according to two different mechanisms. Furthermore, despite their highly similar protein sequences, each reductive dehalogenase seems

Microbially enhanced dissolution and reductive dechlorination of PCE by a mixed culture: Model validation and sensitivity analysis

Science.gov (United States)

Chen, Mingjie; Abriola, Linda M.; Amos, Benjamin K.; Suchomel, Eric J.; Pennell, Kurt D.; Löffler, Frank E.; Christ, John A.

2013-08-01

Reductive dechlorination catalyzed by organohalide-respiring bacteria is often considered for remediation of non-aqueous phase liquid (NAPL) source zones due to cost savings, ease of implementation, regulatory acceptance, and sustainability. Despite knowledge of the key dechlorinators, an understanding of the processes and factors that control NAPL dissolution rates and detoxification (i.e., ethene formation) is lacking. A recent column study demonstrated a 5-fold cumulative enhancement in tetrachloroethene (PCE) dissolution and ethene formation (Amos et al., 2009). Spatial and temporal monitoring of key geochemical and microbial (i.e., Geobacter lovleyi and Dehalococcoides mccartyi strains) parameters in the column generated a data set used herein as the basis for refinement and testing of a multiphase, compositional transport model. The refined model is capable of simulating the reactive transport of multiple chemical constituents produced and consumed by organohalide-respiring bacteria and accounts for substrate limitations and competitive inhibition. Parameter estimation techniques were used to optimize the values of sensitive microbial kinetic parameters, including maximum utilization rates, biomass yield coefficients, and endogenous decay rates. Comparison and calibration of model simulations with the experimental data demonstrate that the model is able to accurately reproduce measured effluent concentrations, while delineating trends in dechlorinator growth and reductive dechlorination kinetics along the column. Sensitivity analyses performed on the optimized model parameters indicate that the rates of PCE and cis-1,2-dichloroethene (cis-DCE) transformation and Dehalococcoides growth govern bioenhanced dissolution, as long as electron donor (i.e., hydrogen flux) is not limiting. Dissolution enhancements were shown to be independent of cis-DCE accumulation; however, accumulation of cis-DCE, as well as column length and flow rate (i.e., column residence time

Organometallic copper I, II or III species in an intramolecular dechlorination reaction

KAUST Repository

Poater, Albert

2013-03-15

The present paper gives insight into an intramolecular dechlorination reaction involving Copper (I) and an ArCH2Cl moiety. The discussion of the presence of a CuIII organometallic intermediate becomes a challenge, and because of the lack of clear experimental detection of this proposed intermediate, and due to the computational evidence that it is less stable than other isomeric species, it can be ruled out for the complex studied here. Our calculations are completely consistent with the key hypothesis of Karlin et al. that TMPA-CuI is the substrate of intramolecular dechlorination reactions as well as the source to generate organometallic species. However the organometallic character of some intermediates has been refused because computationally these species are less stable than other isomers. Thus this study constitutes an additional piece towards the full understanding of a class of reaction of biological relevance. Further, the lack of high energy barriers and deep energy wells along the reaction pathway explains the experimental difficulties to trap other intermediates. © Springer-Verlag Berlin Heidelberg 2013.

Geochemical and microbial community determinants of reductive dechlorination at a site biostimulated with glycerol

NARCIS (Netherlands)

Atashgahi, Siavash; Lu, Yue; Zheng, Ying; Saccenti, Edoardo; Suarez-Diez, Maria; Ramiro-Garcia, Javier; Eisenmann, Heinrich; Elsner, Martin; J.M. Stams, Alfons; Springael, Dirk; Dejonghe, Winnie; Smidt, Hauke

2017-01-01

Biostimulation is widely used to enhance reductive dechlorination of chlorinated ethenes in contaminated aquifers. However, the knowledge on corresponding biogeochemical responses is limited. In this study, glycerol was injected in an aquifer contaminated with cis-dichloroethene (cDCE), and

Chasing halorespirers: High throughput multiplex detection of dechlorinating bacteria using Pri-Lock probes

Energy Technology Data Exchange (ETDEWEB)

Maphosa, F.; Doorn, R. van; Vos, W. de; Cor Schoen, C.; Smidt, H.

2009-07-01

Bioremediation management strategies for sites contaminated with chlorinated compounds require monitoring technologies that enable simultaneous detection and quantification of a wide range of microorganisms involved in reductive dechlorination. Many multiplex, quantitative detection methods available suffer from compromises between the level of multiplexing, throughput and accuracy of quantification. (Author)

Efficient photocatalytic reductive dechlorination of 4-chlorophenol to phenol on {0 0 1}/{1 0 1} facets co-exposed TiO{sub 2} nanocrystals

Energy Technology Data Exchange (ETDEWEB)

Jiang, Guodong; Wei, Meng; Yuan, Songdong [College of Chemistry and chemical engineering, Hubei Collaborative Innovation Center for High Efficient Utilization of Solar Energy, Hubei University of Technology, Wuhan 430068 (China); Chang, Qing, E-mail: changqinghust@163.com [Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission and Ministry of Education, College of Resources and Environmental Science, South-Central University for Nationalities, Wuhan 430074 (China)

2016-01-30

Graphical abstract: - Highlights: • 4-Chlorophenol is dechlorinated over {0 0 1}/{1 0 1} co-exposed TiO{sub 2} nanocrystals. • Photo-electrons are accumulated on {1 0 1} facets due to surface heterojunction. • Fluorine will trap photoelectrons to depress the dechlorination performance. • Sufficient isopropanol promotes the dechlorination activity and selectivity. - Abstract: 4-chlorophenol could be efficiently photoreductively dechlorinated over anatase TiO{sub 2} nanocrystals with co-exposed {0 0 1} and {1 0 1} facets, which were synthesized and further characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Although fluorine could adsorb on {0 0 1} facets to decrease their surface energy, enabling TiO{sub 2} to expose high energy {0 0 1} facets, the surface bonded fluorine might depress the photoreductive dechlorination efficiency of 4-chlorophenol, attributed to the electron trapping role of surface ≡Ti−F groups. Due to the formation of a surface heterojunction between {1 0 1} and {0 0 1} facets in a single TiO{sub 2} nanocrystal, electrons and holes were spontaneously self-separated and selectively migrate to {1 0 1} and {0 0 1} facets, respectively. Electron trapping experiments demonstrated that photogenerated electrons are the responsible for the reductive dechlorinaton of 4-chlorophenol to phenol. To avoid the oxidative degradation of 4-chlorophenol by holes and ensure sufficient electrons to reductively dechlorinate the substrate, moderate scavengers were required in the reaction system and dissolved oxygen, which might deplete electron on TiO{sub 2}, also should be removed. With the optimal scavengers, the conversion efficiency of 4-chlorophenol (4-CP) achieved 97.5% and the selectivity for phenol was 92.5%, which were much higher than that of commercial TiO{sub 2} P25.

Time-dependent bacterial community and electrochemical characterizations of cathodic biofilms in the surfactant-amended sediment-based bioelectrochemical reactor with enhanced 2,3,4,5-tetrachlorobiphenyl dechlorination.

Science.gov (United States)

Wan, Hui; Yi, Xiaoyun; Liu, Xiaoping; Feng, Chunhua; Dang, Zhi; Wei, Chaohai

2018-05-01

Applying an electric field to stimulate the microbial reductive dechlorination of polychlorinated biphenyls (PCBs) represents a promising approach for bioremediation of PCB-contaminated sites. This study aimed to demonstrate the biocathodic film-facilitated reduction of PCB 61 in a sediment-based bioelectrochemical reactor (BER) and, more importantly, the characterizations of electrode-microbe interaction from microbial and electrochemical perspectives particularly in a time-dependent manner. The application of a cathodic potential (-0.45 V vs. SHE) significantly improved the rate and extent of PCB 61 dechlorination compared to the open-circuit scenario (without electrical stimulation), and the addition of an external surfactant further increased the dechlorination, with Tween 80 exerting more pronounced effects than rhamnolipid. The bacterial composition of the biofilms and the bioelectrochemical kinetics of the BERs were found to be time-dependent and to vary considerably with the incubation time and slightly with the coexistence of an external surfactant. Excellent correlations were observed between the dechlorination rate and the relative abundance of Dehalogenimonas, Dechloromonas, and Geobacter, the dechlorination rate and the cathodic current density recorded from the chronoamperometry tests, and the dechlorination rate and the charge transfer resistance derived from the electrochemical impedance tests, with respect to the 120 day-operation. After day 120, PCB 61 was resistant to further appreciable reduction, but substantial hydrogen production was detected, and the bacterial community and electrochemical parameters observed on day 180 were not distinctly different from those on day 120. Copyright © 2018 Elsevier Ltd. All rights reserved.

Improved Dechlorinating Performance of Upflow Anaerobic Sludge Blanket Reactors by Incorporation of Dehalospirillum multivorans into Granular Sludge

Science.gov (United States)

Hörber, Christine; Christiansen, Nina; Arvin, Erik; Ahring, Birgitte K.

1998-01-01

Dechlorination of tetrachloroethene, also known as perchloroethylene (PCE), was investigated in an upflow anaerobic sludge blanket (UASB) reactor after incorporation of the strictly anaerobic, reductively dechlorinating bacterium Dehalospirillum multivorans into granular sludge. This reactor was compared to the reference 1 (R1) reactor, where the granules were autoclaved to remove all dechlorinating abilities before inoculation, and to the reference 2 (R2) reactor, containing only living granular sludge. All three reactors were fed mineral medium containing 3 to 57 μM PCE, 2 mM formate, and 0.5 mM acetate and were operated under sterile conditions. In the test reactor, an average of 93% (mole/mole) of the effluent chloroethenes was dichloroethene (DCE), compared to 99% (mole/mole) in the R1 reactor. The R2 reactor, with no inoculation, produced only trichloroethene (TCE), averaging 43% (mole/mole) of the effluent chloroethenes. No dechlorination of PCE was observed in an abiotic control consisting of sterile granules without inoculum. During continuous operation with stepwise-reduced hydraulic retention times (HRTs), both the test reactor and the R1 reactor showed conversion of PCE to DCE, even at HRTs much lower than the reciprocal maximum specific growth rate of D. multivorans, indicating that this bacterium was immobilized in the living and autoclaved granular sludge. In contrast, the R2 reactor, with no inoculation of D. multivorans, only converted PCE to TCE under the same conditions. Immobilization could be confirmed by using fluorescein-labeled antibody probes raised against D. multivorans. In granules obtained from the R1 reactor, D. multivorans grew mainly in microcolonies located in the centers of the granules, while in the test reactor, the bacterium mainly covered the surfaces of granules. PMID:9572963

The role of humic substances in the anaerobic reductive dechlorination of 2,4-dichlorophenoxyacetic acid by Comamonas koreensis strain CY01

Energy Technology Data Exchange (ETDEWEB)

Wang Yibo [College of Life Sciences, South China Normal University, Guangdong Key Lab of Biotechnology for Plant Development, Guangzhou, 510631 (China)] [Guangdong Institute of Eco-environment and Soil Sciences, Guangzhou, 510650 (China)] [College of Life Science and Chemistry, Tianshui Normal University, Tianshui, 741000 (China); Wu Chunyuan [Guangdong Institute of Eco-environment and Soil Sciences, Guangzhou, 510650 (China); Wang Xiaojing, E-mail: wangyb02@163.com [College of Life Sciences, South China Normal University, Guangdong Key Lab of Biotechnology for Plant Development, Guangzhou, 510631 (China); Zhou Shungui, E-mail: sgzhou@soil.gd.cn [Guangdong Institute of Eco-environment and Soil Sciences, Guangzhou, 510650 (China)

2009-05-30

The role of the humic model compound, anthraquinone-2,6-disulfonate (AQDS), in the anaerobic reductive dechlorination of 2,4-dichlorophenoxyacetic acid (2,4-D) by the Fe(III)- and humic substances (HS)-reducing bacterium, Comamonas koreensis strain CY01 was investigated. The results taken as a whole indicated that (i) strain CY01 could couple glucose oxidation to 2,4-D reductive dechlorination; (ii) reductive dechlorination of 2,4-D by strain CY01 was greatly stimulated by the addition of AQDS; (iii) the transfer of electrons from biogenic AH{sub 2}QDS to 2,4-D was an abiotic process which can take place in the absence of microorganisms; and (iv) AH{sub 2}QDS was reoxidized during the chemical reaction, AQDS can serve again as electron acceptor for microorganisms, thus acting as electron shuttles. All the results suggested that 2,4-D reductive dechlorination by CY01 strain was a biochemical process that oxidizes the electron donors and transfers the electron to the acceptors through redox mediator, AQDS. We proposed the possible mechanism for the HS dependent reduction of 2,4-D. Our results suggested that microbial reduction of HS and subsequent chemical reduction of organic pollutants represent an important path of electron flow in anoxic natural environments. This work is a necessary preliminary step for better understanding the biodegradation of 2,4-D in subsurface soil.

Dechlorination of Hexachlorobenzene in Contaminated Soils Using a Nanometallic Al/CaO Dispersion Mixture: Optimization through Response Surface Methodology

Science.gov (United States)

Jiang, Yuhui; Shang, Yixuan; Yu, Shuyao; Liu, Jianguo

2018-01-01

Hexachlorobenzene (HCB) contamination of soils remains a significant environmental challenge all over the world. Reductive stabilization is a developing technology that can decompose the HCB with a dechlorination process. A nanometallic Al/CaO (n-Al/CaO) dispersion mixture was developed utilizing ball-milling technology in this study. The dechlorination efficiency of HCB in contaminated soils by the n-Al/CaO grinding treatment was evaluated. Response surface methodology (RSM) was employed to investigate the effects of three variables (soil moisture content, n-Al/CaO dosage and grinding time) and the interactions between these variables under the Box-Behnken Design (BBD). A high regression coefficient value (R2 = 0.9807) and low p value (soil moisture content, n-Al/CaO dosage, and grinding time were found to be 7% (m/m), 17.7% (m/m), and 24 h, respectively, in the experimental ranges and levels. Under optimal conditions, the dechlorination efficiency was 80%. The intermediate product analysis indicated that dechlorination was the process by stepwise loss of chloride atoms. The main pathway observed within 24 h was HCB → pentachlorobenzene (PeCB) → 1,2,3,4-tetrachlorobenzene (TeCB) and 1,2,4,5-TeCB. The results indicated that the moderate soil moisture content was crucial for the hydrodechlorination of HCB. A probable mechanism was proposed wherein water acted like a hydrogen donor and promoted the hydrodechlorination process. The potential application of n-Al/CaO is an environmentally-friendly and cost-effective option for decontamination of HCB-contaminated soils. PMID:29702570

Comparison of Bimetallic and Trimetallic Catalyst in Reductive Dechlorination; Influence of Copper Addition

Czech Academy of Sciences Publication Activity Database

Kaštánek, František; Kaštánek, Petr; Maléterová, Ywetta; Kallistová, A.; Šolcová, Olga

2015-01-01

Roč. 2, č. 7 (2015), s. 1954-1958 E-ISSN 3159-0040 R&D Projects: GA TA ČR TA04020700 Institutional support: RVO:67985858 ; RVO:67985831 Keywords : PCB * reductive dechlorination * bimetallic and trimetallic catalysts Subject RIV: CI - Industrial Chemistry, Chemical Engineering http://www.jmest.org/wp-content/uploads/JMESTN42350950.pdf

Characterization of an H2-utilizing enrichment culture that reductively dechlorinates tetrachloroethene to vinyl chloride and ethene in the absence of methanogenesis and acetogenesis.

OpenAIRE

Maymó-Gatell, X; Tandoi, V; Gossett, J M; Zinder, S H

1995-01-01

We have been studying an anaerobic enrichment culture which, by using methanol as an electron donor, dechlorinates tetrachloroethene (PCE) to vinyl chloride and ethene. Our previous results indicated that H2 was the direct electron donor for rductive dechlorination of PCE by the methanol-PCE culture. Most-probable-number counts performed on this culture indicated low numbers ( or equal to 10(6)/ml...

Role of bicarbonate as a pH buffer and electron sink in microbial dechlorination of chloroethenes

Directory of Open Access Journals (Sweden)

Delgado Anca G

2012-09-01

Full Text Available Abstract Background Buffering to achieve pH control is crucial for successful trichloroethene (TCE anaerobic bioremediation. Bicarbonate (HCO3− is the natural buffer in groundwater and the buffer of choice in the laboratory and at contaminated sites undergoing biological treatment with organohalide respiring microorganisms. However, HCO3− also serves as the electron acceptor for hydrogenotrophic methanogens and hydrogenotrophic homoacetogens, two microbial groups competing with organohalide respirers for hydrogen (H2. We studied the effect of HCO3− as a buffering agent and the effect of HCO3−-consuming reactions in a range of concentrations (2.5-30 mM with an initial pH of 7.5 in H2-fed TCE reductively dechlorinating communities containing Dehalococcoides, hydrogenotrophic methanogens, and hydrogenotrophic homoacetogens. Results Rate differences in TCE dechlorination were observed as a result of added varying HCO3− concentrations due to H2-fed electrons channeled towards methanogenesis and homoacetogenesis and pH increases (up to 8.7 from biological HCO3− consumption. Significantly faster dechlorination rates were noted at all HCO3− concentrations tested when the pH buffering was improved by providing 4-(2-hydroxyethyl-1-piperazineethanesulfonic acid (HEPES as an additional buffer. Electron balances and quantitative PCR revealed that methanogenesis was the main electron sink when the initial HCO3− concentrations were 2.5 and 5 mM, while homoacetogenesis was the dominant process and sink when 10 and 30 mM HCO3− were provided initially. Conclusions Our study reveals that HCO3− is an important variable for bioremediation of chloroethenes as it has a prominent role as an electron acceptor for methanogenesis and homoacetogenesis. It also illustrates the changes in rates and extent of reductive dechlorination resulting from the combined effect of electron donor competition stimulated by HCO3− and the changes in pH exerted by

Green remediation: enhanced reductive dechlorination using recycled rinse water as bioremediation substrate

International Nuclear Information System (INIS)

Dawson, Gaynor; McKeon, Tom

2007-01-01

Enhanced reductive dechlorination (ERD) has rapidly become a remedy of choice for use on chlorinated solvent contamination when site conditions allow. With this approach, solutions of an organic substrate are injected into the affected aquifer to stimulate biological growth and the resultant production of reducing conditions in the target zone. Under the reducing conditions, hydrogen is produced and ultimately replaces chlorine atoms on the contaminant molecule causing sequential dechlorination. Under suitable conditions the process continues until the parent hydrocarbon precursor is produced, such as the complete dechlorination of trichloroethylene (TCE) to ethene. The process is optimized by use of a substrate that maximizes hydrogen production per unit cost. When natural biota are not present to promote the desired degradation, inoculates can be added with the substrate. The in-situ method both reduces cost and accelerates cleanup. Successful applications have been extended from the most common chlorinated compounds perchloroethylene (PCE) and TCE and related products of degradation, to perchlorate, and even explosives such as RDX and trinitrotoluene on which nitrates are attacked in lieu of chloride. In recent work, the process has been further improved through use of beverage industry wastewaters that are available at little or no cost. With material cost removed from the equation, applications can maximize the substrate loading without significantly increasing total cost. The extra substrate loading both accelerates reaction rates and extends the period of time over which reducing conditions are maintained. In some cases, the presence of other organic matter in addition to simple sugars provides for longer performance times of individual injections, thereby working in a fashion similar to emulsified vegetable oil. The paper discusses results of applications at three different sites contaminated with chlorinated ethylenes. The applications have included

Dechlorination of Hexachlorobenzene in Contaminated Soils Using a Nanometallic Al/CaO Dispersion Mixture: Optimization through Response Surface Methodology

Directory of Open Access Journals (Sweden)

Yuhui Jiang

2018-04-01

Full Text Available Hexachlorobenzene (HCB contamination of soils remains a significant environmental challenge all over the world. Reductive stabilization is a developing technology that can decompose the HCB with a dechlorination process. A nanometallic Al/CaO (n-Al/CaO dispersion mixture was developed utilizing ball-milling technology in this study. The dechlorination efficiency of HCB in contaminated soils by the n-Al/CaO grinding treatment was evaluated. Response surface methodology (RSM was employed to investigate the effects of three variables (soil moisture content, n-Al/CaO dosage and grinding time and the interactions between these variables under the Box-Behnken Design (BBD. A high regression coefficient value (R2 = 0.9807 and low p value (<0.0001 of the quadratic model indicated that the model was accurate in predicting the experimental results. The optimal soil moisture content, n-Al/CaO dosage, and grinding time were found to be 7% (m/m, 17.7% (m/m, and 24 h, respectively, in the experimental ranges and levels. Under optimal conditions, the dechlorination efficiency was 80%. The intermediate product analysis indicated that dechlorination was the process by stepwise loss of chloride atoms. The main pathway observed within 24 h was HCB → pentachlorobenzene (PeCB → 1,2,3,4-tetrachlorobenzene (TeCB and 1,2,4,5-TeCB. The results indicated that the moderate soil moisture content was crucial for the hydrodechlorination of HCB. A probable mechanism was proposed wherein water acted like a hydrogen donor and promoted the hydrodechlorination process. The potential application of n-Al/CaO is an environmentally-friendly and cost-effective option for decontamination of HCB-contaminated soils.

Dechlorination/Solidification of LiCl waste by using a synthetic inorganic composite with different compositions

Energy Technology Data Exchange (ETDEWEB)

Kim, Na Young; Cho, In Hak; Park, Hwan Seo; Ahn, Do Hee [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2016-09-15

Waste salt generated from a pyro-processing for the recovery of uranium and transuranic elements has high volatility at vitrification temperature and low compatibility in conventional waste glasses. For this reason, KAERI (Korea Atomic Energy Research Institute) suggested a new method to de-chlorinate waste salt by using an inorganic composite named SAP (SiO{sub 2}-Al{sub 2}O{sub 3}-P{sub 2}O{sub 5}). In this study, the de-chlorination behavior of waste salt and the microstructure of consolidated form were examined by adding B{sub 2}O{sub 3} and Fe{sub 2}O{sub 3} to the original SAP composition. De-chlorination behavior of metal chloride waste was slightly changed with given compositions, compared with that of original SAP. In the consolidated forms, the phase separation between Si-rich phase and P-rich phase decreases with the amount of Al{sub 2}O{sub 3} or B{sub 2}O{sub 3} as a connecting agent between Si and P-rich phase. The results of PCT (Product Consistency Test) indicated that the leach-resistance of consolidated forms out of reference composition was lowered, even though the leach-resistance was higher than that of EA (Environmental Assessment) glass. From these results, it could be inferred that the change in the content of Al or B in U-SAP affected the microstructure and leach-resistance of consolidated form. Further studies related with correlation between composition and characteristics of wasteform are required for a better understanding.

Radiation induced dechlorination of some chlorinated hydrocarbons in aqueous suspensions of various solid particles

Czech Academy of Sciences Publication Activity Database

Múčka, V.; Buňata, M.; Čuba, V.; Silber, R.; Juha, Libor

2015-01-01

Roč. 112, Jul (2015), s. 108-116 ISSN 0969-806X R&D Projects: GA ČR GA13-28721S Institutional support: RVO:68378271 Keywords : chlorinated hydrocarbons * TCE * PCE * PCBs * dechlorination * gamma irradiation * modifiers * cell membrane permeability Subject RIV: CH - Nuclear ; Quantum Chemistry Impact factor: 1.207, year: 2015

Session 6: Synergistic effects in selective hydro dechlorination on bimetallic catalysts

Energy Technology Data Exchange (ETDEWEB)

Srebowata, A.; Legawiec-Jarzyna, M.; Juszczyk, W.; Karpinski, Z. [Institute of Physical Chemistry of PAS, Warszawa (Poland)

2004-07-01

Catalytic removal of chlorine from organic compounds has recently attracted increasing interest. A special case of this important environmental issue is the hydro-dechlorination (HDC). HDC of three compounds was investigated: dichloro-difluoro-methane, carbon tetrachloride and 1,2-dichloroethane. Since the most desired products of the mentioned reactions are: CH{sub 2}F{sub 2}, chloroform and ethene (highlighted below), our attention was focused at the rates of formation of these products: CCl{sub 2}F{sub 2} {yields} CH{sub 2}F{sub 2} {yields} CH{sub 4}; CCl{sub 4} {yields} CHCl{sub 3} {yields} CH{sub 4}; ClCH{sub 2}-CH{sub 2}Cl {yields} CH{sub 2}=CH{sub 2} {yields} CH{sub 3}CH{sub 3}. In fact, Selection of the most suitable HDC catalyst depends on the C-Cl bond strength in a molecule subjected to reaction. A relatively weak C-Cl bond in CCl{sub 4} (306 kJ/mol) does not require a high dechlorination potential, which can be directly correlated with the strength of a metal-chlorine bond. Thus Pt is a better catalyst than Pd in CCl{sub 4} reaction. In addition, an improvement of Pt-based catalysts can be achieved by alloying with metals which bind chlorine even less strongly than Pt (i.e. with Au). In contrast, Pd is a better catalyst than Pt for hydro-dechlorination of a stronger C-Cl bond (about 350 kJ/mol), present in CCl{sub 2}F{sub 2} and ClCH{sub 2}-CH{sub 2}Cl. However, a good performance of Pd can still be improved by alloying it with much less active Pt (or Au), as a result of weakening of the metal-chlorine bond. This effect leads to a higher selectivity toward partial dehalogenation, i.e. to formation of a desired CH{sub 2}F{sub 2} (at the expense of CH{sub 4}). In a similar way, combination of Pd with Co and Cu is rationalized. For HDC of ClCH{sub 2}-CH{sub 2}Cl, addition of a metal characterized by a poor hydrogenation strength (like Cu or Ag) to Pd (or Pt) reduces undesired formation of ethane, giving higher yields of ethene. (authors)

Sustainable remediation: electrochemically assisted microbial dechlorination of tetrachloroethene-contaminated groundwater.

Science.gov (United States)

Patil, Sayali S; Adetutu, Eric M; Rochow, Jacqueline; Mitchell, James G; Ball, Andrew S

2014-01-01

Microbial electric systems (MESs) hold significant promise for the sustainable remediation of chlorinated solvents such as tetrachlorethene (perchloroethylene, PCE). Although the bio-electrochemical potential of some specific bacterial species such as Dehalcoccoides and Geobacteraceae have been exploited, this ability in other undefined microorganisms has not been extensively assessed. Hence, the focus of this study was to investigate indigenous and potentially bio-electrochemically active microorganisms in PCE-contaminated groundwater. Lab-scale MESs were fed with acetate and carbon electrode/PCE as electron donors and acceptors, respectively, under biostimulation (BS) and BS-bioaugmentation (BS-BA) regimes. Molecular analysis of the indigenous groundwater community identified mainly Spirochaetes, Firmicutes, Bacteroidetes, and γ and δ-Proteobacteria. Environmental scanning electron photomicrographs of the anode surfaces showed extensive indigenous microbial colonization under both regimes. This colonization and BS resulted in 100% dechlorination in both treatments with complete dechlorination occurring 4 weeks earlier in BS-BA samples and up to 11.5 μA of current being generated. The indigenous non-Dehalococcoides community was found to contribute significantly to electron transfer with ∼61% of the current generated due to their activities. This study therefore shows the potential of the indigenous non-Dehalococcoides bacterial community in bio-electrochemically reducing PCE that could prove to be a cost-effective and sustainable bioremediation practice. © 2013 The Authors. Microbial Biotechnology published by John Wiley & Sons Ltd and Society for Applied Microbiology.

Enhancement of Degradation and Dechlorination of Trichloroethylene via Supporting Palladium/Iron Bimetallic Nanoparticles onto Mesoporous Silica

Directory of Open Access Journals (Sweden)

Jianjun Wei

2016-07-01

Full Text Available This study is aimed to prevent the agglomeration of Pd/Fe bimetallic nanoparticles and thus improve the efficiency toward degradation and dechlorination of chlorinated organic contaminants. A mesoporous silica with a primary pore diameter of 8.3 nm and a specific surface area of 688 m2/g was prepared and used as the host of Pd/Fe nanoparticles. The Pd/Fe nanoparticles were deposited onto or into the mesoporous silica by reduction of ferrous ion and hexachloropalladate ion in aqueous phase. Batch degradation and dechlorination reactions of trichloroethylene were conducted with initial trichloroethylene concentration of 23.7 mg/L, iron loading of 203 or 1.91 × 103 mg/L and silica loading of 8.10 g/L at 25 °C. Concentration of trichloroethylene occurs on the supported Pd/Fe nanoparticles, with trichloroethylene degrading to 56% and 59% in 30 min on the supported Pd/Fe nanoparticles with weight percentage of palladium to iron at 0.075% and 0.10% respectively. The supported Pd/Fe nanoparticles exhibit better dechlorination activity. When the supported Pd/Fe nanoparticles with a weight percentage of palladium to iron of 0.10% were loaded much less than the bare counterpart, the yield of ethylene plus ethane in 10 h on them was comparable, i.e., 19% vs. 21%. This study offers a future approach to efficiently combine the reactivity of supported Pd/Fe nanoparticles and the adsorption ability of mesoporous silica.

A remediation performance model for enhanced metabolic reductive dechlorination of chloroethenes in fractured clay till

DEFF Research Database (Denmark)

Manoli, Gabriele; Chambon, Julie C.; Bjerg, Poul L.

2012-01-01

A numerical model of metabolic reductive dechlorination is used to describe the performance of enhanced bioremediation in fractured clay till. The model is developed to simulate field observations of a full scale bioremediation scheme in a fractured clay till and thereby to assess remediation...

Dechlorination Reaction of Metal Chloride Wastes with Inorganic Composite (SiO{sub 2}-Al{sub 2}O{sub 3}- P{sub 2}O{sub 5}) at 650 .deg. C

Energy Technology Data Exchange (ETDEWEB)

Ahn, Soo Na; Park, Hwan Seo; Cho, In Hak; Kim, In Tae; Cho, Yong Zun [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2011-05-15

Pyrochemical process to recover uranium and transuranic elements from the spent nuclear fuel indispensably generates radioactive metal chlorides waste containing fission products. These wastes are difficult to solidify and stabilize by conventional method due to their volatility and low comparability with silicate glass. Our research group is under development of dechlorination method to remove Clinduced problems. For dechlorination of metal chloride waste, an inorganic composite, SiO{sub 2}-Al{sub 2}O{sub 3}-P{sub 2}O{sub 5} (SAP), has been investigated as dechlorination agent. The composite reacts with metal chloride to produce aluminosilicates, alumino phosphate and orthophosphate. The products are thermally stable up to 1200 .deg. C and compatible with silicate glass. In this study, modified SAP containing Fe{sub 2}O{sub 3} as another component was investigated to enhance the dechlorination reaction and characterize the reaction behavior of LiCl

Parameter Sensitivity and Laboratory Benchmarking of a Biogeochemical Process Model for Enhanced Anaerobic Dechlorination

Science.gov (United States)

Kouznetsova, I.; Gerhard, J. I.; Mao, X.; Barry, D. A.; Robinson, C.; Brovelli, A.; Harkness, M.; Fisher, A.; Mack, E. E.; Payne, J. A.; Dworatzek, S.; Roberts, J.

2008-12-01

A detailed model to simulate trichloroethene (TCE) dechlorination in anaerobic groundwater systems has been developed and implemented through PHAST, a robust and flexible geochemical modeling platform. The approach is comprehensive but retains flexibility such that models of varying complexity can be used to simulate TCE biodegradation in the vicinity of nonaqueous phase liquid (NAPL) source zones. The complete model considers a full suite of biological (e.g., dechlorination, fermentation, sulfate and iron reduction, electron donor competition, toxic inhibition, pH inhibition), physical (e.g., flow and mass transfer) and geochemical processes (e.g., pH modulation, gas formation, mineral interactions). Example simulations with the model demonstrated that the feedback between biological, physical, and geochemical processes is critical. Successful simulation of a thirty-two-month column experiment with site soil, complex groundwater chemistry, and exhibiting both anaerobic dechlorination and endogenous respiration, provided confidence in the modeling approach. A comprehensive suite of batch simulations was then conducted to estimate the sensitivity of predicted TCE degradation to the 36 model input parameters. A local sensitivity analysis was first employed to rank the importance of parameters, revealing that 5 parameters consistently dominated model predictions across a range of performance metrics. A global sensitivity analysis was then performed to evaluate the influence of a variety of full parameter data sets available in the literature. The modeling study was performed as part of the SABRE (Source Area BioREmediation) project, a public/private consortium whose charter is to determine if enhanced anaerobic bioremediation can result in effective and quantifiable treatment of chlorinated solvent DNAPL source areas. The modelling conducted has provided valuable insight into the complex interactions between processes in the evolving biogeochemical systems

Validation of an Integrative Methodology to Assess and Monitor Reductive Dechlorination of Chlorinated Ethenes in Contaminated Aquifers

Czech Academy of Sciences Publication Activity Database

Tarnawski, S.E.; Rossi, P.; Brennerová, Mária; Stavělová, M.; Holliger, Ch.

2016-01-01

Roč. 4, February (2016), s. 7 E-ISSN 2296-665X R&D Projects: GA TA ČR TA02020534 Institutional support: RVO:61388971 Keywords : dechlorination * integrative methodology * chlorinated ethenes Subject RIV: EE - Microbiology, Virology

Preliminary Results of Reductive Dechlorination Conducted at the X-749/X-120 Area of the DOE Portsmouth Gaseous Diffusion Plant, Piketon, Ohio

International Nuclear Information System (INIS)

Rieske, D. E.; Baird, D. R.; Lawson, N. E.

2006-01-01

Reductive dechlorination is being implemented at the X-749/X-120 trichloroethene (TCE) plume South Barrier Wall containment site at the Department of Energy (DOE) Portsmouth Gaseous Diffusion Plant (PORTS). The purpose of this paper is to present the effectiveness of the reductive dechlorination at PORTS. Reductive dechlorination is an in situ remediation technology that utilizes existing subsurface microbes to biologically degrade volatile organic compounds in groundwater. Monitoring in the barrier wall area reveals the presence of Hydrogen Release Compound (HRC) injected in the spring of 2004 in two groundwater monitoring wells closest to the injection points. Oxidation/reduction potential in these two wells has decreased steadily since injection, but has not yet reached optimal reducing levels for TCE degradation. Monitoring the effectiveness of the injection is hampered by near-stagnant groundwater flow due in part to the South Barrier Wall. The X-749/X-120 TCE groundwater plume lies beneath approximately 91 acres in the southern portion of PORTS, and extends southward threatening to cross the DOE property boundary. A 1,077-foot long subsurface bentonite barrier wall was installed in 1993 at the southern DOE property boundary to restrict movement of contaminated groundwater from traveling off-site until other remedial technologies could be implemented. In 2003, TCE was detected on the south side of the barrier wall (but still within DOE property) above drinking water standards of 5 micrograms per liter. Monitoring has also detected TCE in groundwater beyond the western edge of the barrier wall. In the spring of 2004, DOE initiated the injection of a reductive dechlorination compound known as Hydrogen Release Compound-extended release formula (HRC-X) into the subsurface using direct push technology (DPT). The HRC-X was injected within the saturated zone from the top of bedrock to 10 feet above bedrock as the probe was withdrawn from the push. A total of 180 DPT

Effects of activated carbon on reductive dechlorination of PCBs by organohalide respiring bacteria indigenous to sediments.

Science.gov (United States)

Kjellerup, B V; Naff, C; Edwards, S J; Ghosh, U; Baker, J E; Sowers, K R

2014-04-01

Polychlorinated biphenyls (PCBs) have accumulated in aquatic sediments due to their inherent chemical stability and their presence poses a risk due to their potential toxicity in humans and animals. Granular activated carbon (GAC) has been applied to PCB contaminated sediment sites to reduce the aqueous concentration by sequestration thus reducing the PCB exposure and toxicity to both benthic and aquatic organisms. However, it is not known how the reduction of PCB bioavailability by adsorption to GAC affects bacterial transformation of PCBs by indigenous organohalide respiring bacteria. In this study, the impact of GAC on anaerobic dechlorination by putative organohalide respiring bacteria indigenous to sediment from Baltimore Harbor was examined. It was shown that the average Cl/biphenyl after dehalogenation of Aroclor 1260 was similar between treatments with and without GAC amendment. However, GAC caused a substantial shift in the congener distribution whereby a smaller fraction of highly chlorinated congeners was more extensively dechlorinated to mono- through tri-chlorinated congeners compared to the formation of tri- through penta-chlorinated congeners in unamended sediment. The results combined with comparative sequence analysis of 16S rRNA gene sequences suggest that GAC caused a community shift to putative organohalide respiring phylotypes that coincided with more extensive dechlorination of ortho and unflanked chlorines. This shift in activity by GAC shown here for the first time has the potential to promote greater degradation in situ by promoting accumulation of less chlorinated congeners that are generally more susceptible to complete mineralization by aerobic PCB degrading bacteria. Copyright © 2013 Elsevier Ltd. All rights reserved.

ENVIROMETAL TECHNOLOGIES, INC., METAL-ENHANCED DECHLORINATION OF VOLATILE ORGANIC COMPOUNDS USING AN IN-SITU REACTIVE IRON WALL

Science.gov (United States)

This report summarizes the results of a field demonstration conducted under the SITE program. The technology that was demonstrated was a metal-enhanced dechlorination process developed by EnviroMetal Technologies, Inc. to treat groundwater contaminated with chlorinated volatile ...

Use Of Statistical Tools To Evaluate The Reductive Dechlorination Of High Levels Of TCE In Microcosm Studies

Science.gov (United States)

A large, multi-laboratory microcosm study was performed to select amendments for supporting reductive dechlorination of high levels of trichloroethylene (TCE) found at an industrial site in the United Kingdom (UK) containing dense non-aqueous phase liquid (DNAPL) TCE. The study ...

Hydroxyl-radical induced dechlorination of pentachlorophenol in water

International Nuclear Information System (INIS)

He Yongke; Wu Jilan; Fang Xingwang; Sonntag, C. von

1998-01-01

The hydroxyl-radical induced dechlorination of pentachlorophenol (PCP) in water has been investigated pulse radiolytically. Hydroxyl radicals react with PCP by both electron transfer and addition. The former process results in pentachlorophenoxyl radicals (PCP-O), the latter process followed by rapid HCl elimination gives birth to deprotonated hydroxytetrachlorophenoxyl radicals ( - O-TCP-O). These phenoxyl radicals exhibit maximum absorption around 452 nm, which hinders the proper estimation of the ratio of the two processes. However, these two processes cause different changes in conductivity. In basic solution, the electron transfer causes a conductivity increase due to the formation of OH - whereas an addition followed by HCl elimination results in a conductivity decrease. The concurrence of these two processes reduces the relative variation in conductivity, from which about 53% electron transfer is deduced

Estimation of rate constants of PCB dechlorination reactions using an anaerobic dehalogenation model.

Science.gov (United States)

Karakas, Filiz; Imamoglu, Ipek

2017-02-15

This study aims to estimate anaerobic dechlorination rate constants (k m ) of reactions of individual PCB congeners using data from four laboratory microcosms set up using sediment from Baltimore Harbor. Pathway k m values are estimated by modifying a previously developed model as Anaerobic Dehalogenation Model (ADM) which can be applied to any halogenated hydrophobic organic (HOC). Improvements such as handling multiple dechlorination activities (DAs) and co-elution of congeners, incorporating constraints, using new goodness of fit evaluation led to an increase in accuracy, speed and flexibility of ADM. DAs published in the literature in terms of chlorine substitutions as well as specific microorganisms and their combinations are used for identification of pathways. The best fit explaining the congener pattern changes was found for pathways of Phylotype DEH10, which has the ability to remove doubly flanked chlorines in meta and para positions, para flanked chlorines in meta position. The range of estimated k m values is between 0.0001-0.133d -1 , the median of which is found to be comparable to the few available published biologically confirmed rate constants. Compound specific modelling studies such as that performed by ADM can enable monitoring and prediction of concentration changes as well as toxicity during bioremediation. Copyright © 2016 Elsevier B.V. All rights reserved.

Effects of ferrous ions on the reductive dechlorination of trichloroethylene by zero-valent iron

International Nuclear Information System (INIS)

Liu, C.-C.; Tseng, D.-H.; Wang, C.-Y.

2006-01-01

The surface characteristics of zero-valent iron (ZVI) and the efficiency of reductive dechlorination of trichloroethylene (TCE) in the presence of ferrous ions were studied. The experimental results indicated that the acid-washing of a metallic iron sample enhanced the efficiency of TCE degradation by ZVI. This occurred because acid-washing changed the conformation of oxides on the surface of iron from maghemite (γ-Fe 2 O 3 ) to the more hydrated goethite (α-FeOOH), as was confirmed by XPS analysis. However, when ferrous ions were simultaneous with TCE in water, the TCE degradation rate decreased as the concentration of ferrous ion increased. This was due to the formation of passive precipitates of ferrous hydroxide, including maghemite and magnetite (Fe 3 O 4 ), that coated on the surface of acid-washed ZVI, which as a result inhibited the electron transfer and catalytic hydrogenation mechanisms. On the other hand, in an Fe 0 -TCE system without the acid-washing pretreatment of ZVI, ferrous ions were adsorbed into the maghemite lattice which was then converted to semiconductive magnetite. Thus, the electrons were transferred from the iron surface and passed through the precipitates, allowing for the reductive dechlorination of TCE

Effect of emplaced nZVI mass and groundwater velocity on PCE dechlorination and hydrogen evolution in water-saturated sand

International Nuclear Information System (INIS)

Kim, Hye-Jin; Leitch, Megan; Naknakorn, Bhanuphong; Tilton, Robert D.; Lowry, Gregory V.

2017-01-01

Highlights: • Reactivity of nZVI increased linearly with nZVI concentration above 10 g/L, but was non-linear below 10 g/L. • nZVI reactivity with PCE is more sensitive to solution redox potential than solution pH. • Mass transfer limits the reactivity of emplaced nZVI under typical groundwater flow velocity. • Lowering pH increases H_2 evolution from nZVI more than reactivity with PCE. • Design of nZVI remediation strategies should consider mass loading and flow velocity on performance and lifetime. - Abstract: The effect of nZVI mass loading and groundwater velocity on the tetrachloroethylene (PCE) dechlorination rate and the hydrogen evolution rate for poly(maleic acid-co-olefin) (MW = 12 K) coated nZVI was examined. In batch reactors, the PCE reaction rate constant (3.7 × 10"−"4 L hr"−"1 m"−"2) and hydrogen evolution rate constant (1.4 nanomol L hr"−"1 m"−"2) were independent of nZVI concentration above 10 g/L, but the PCE dechlorination rate decreased and the hydrogen evolution rate increased for nZVI concentration below 10 g/L. The nonlinearity between nZVI mass loading and PCE dechlorination and H_2 evolution was explained by differences in pH and E_h at each nZVI mass loading; PCE reactivity increased when solution E_h decreased, and the H_2 evolution rate increased with decreasing pH. Thus, nZVI mass loading of <5 g/L yields lower reactivity with PCE and lower efficiency of Fe° utilization than for higher nZVI mass loading. The PCE dechlorination rate increased with increasing pore-water velocity, suggesting that mass transfer limits the reaction at low porewater velocity. Overall, this work suggests that design of nZVI-based reactive barriers for groundwater treatment should consider the non-linear effects of both mass loading and flow velocity on performance and expected reactive lifetime.

Effect of emplaced nZVI mass and groundwater velocity on PCE dechlorination and hydrogen evolution in water-saturated sand

Energy Technology Data Exchange (ETDEWEB)

Kim, Hye-Jin [Civil & Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States); Chemical Research Division, Environmental Health Research Department, National Institute of Environmental Research, Incheon 404-708 (Korea, Republic of); Leitch, Megan [Civil & Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States); Center for Environmental Implications of Nanotechnology, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States); Naknakorn, Bhanuphong [Civil & Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States); Tilton, Robert D. [Chemical Engineering, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States); Biomedical Engineering, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States); Center for Environmental Implications of Nanotechnology, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States); Lowry, Gregory V., E-mail: glowry@cmu.edu [Civil & Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States); Chemical Engineering, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States); Center for Environmental Implications of Nanotechnology, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States)

2017-01-15

Highlights: • Reactivity of nZVI increased linearly with nZVI concentration above 10 g/L, but was non-linear below 10 g/L. • nZVI reactivity with PCE is more sensitive to solution redox potential than solution pH. • Mass transfer limits the reactivity of emplaced nZVI under typical groundwater flow velocity. • Lowering pH increases H{sub 2} evolution from nZVI more than reactivity with PCE. • Design of nZVI remediation strategies should consider mass loading and flow velocity on performance and lifetime. - Abstract: The effect of nZVI mass loading and groundwater velocity on the tetrachloroethylene (PCE) dechlorination rate and the hydrogen evolution rate for poly(maleic acid-co-olefin) (MW = 12 K) coated nZVI was examined. In batch reactors, the PCE reaction rate constant (3.7 × 10{sup −4} L hr{sup −1} m{sup −2}) and hydrogen evolution rate constant (1.4 nanomol L hr{sup −1} m{sup −2}) were independent of nZVI concentration above 10 g/L, but the PCE dechlorination rate decreased and the hydrogen evolution rate increased for nZVI concentration below 10 g/L. The nonlinearity between nZVI mass loading and PCE dechlorination and H{sub 2} evolution was explained by differences in pH and E{sub h} at each nZVI mass loading; PCE reactivity increased when solution E{sub h} decreased, and the H{sub 2} evolution rate increased with decreasing pH. Thus, nZVI mass loading of <5 g/L yields lower reactivity with PCE and lower efficiency of Fe° utilization than for higher nZVI mass loading. The PCE dechlorination rate increased with increasing pore-water velocity, suggesting that mass transfer limits the reaction at low porewater velocity. Overall, this work suggests that design of nZVI-based reactive barriers for groundwater treatment should consider the non-linear effects of both mass loading and flow velocity on performance and expected reactive lifetime.

Dechlorination of 2,4-dichlorophenoxyacetic acid by sodium carboxymethyl cellulose-stabilized Pd/Fe nanoparticles

International Nuclear Information System (INIS)

Zhou, Hongyi; Han, Jian; Baig, Shams Ali; Xu, Xinhua

2011-01-01

Highlights: ► CMC-stabilized Pd/Fe nanoparticles were synthesized and used for 2,4-D removal. ► Particle stability, ζ-potential and IEP of non- and stabilized Pd/Fe were compared. ► Dechlorination of 2,4-D by different Pd/Fe systems was investigated. ► The reaction mechanism has been discussed and presented in the article. ► Effects of CMC/Fe mass ratio and pH were also investigated. - Abstract: This paper describes the synthesis of sodium carboxymethyl cellulose (CMC)-stabilized Pd/Fe nanoparticles and their applications to the dechlorination of 2,4-dichlorophenoxyacetic acid (2,4-D) under controlled laboratorial conditions. For this purpose batch mode experiments were conducted to understand the effects of CMC on the surface characteristics of Pd/Fe nanoparticles, optimum removal of 2,4-D and other surface interactions mechanism. Our experimental results demonstrated considerable enhancements in particle stability and chemical reactivity with the addition of CMC to Pd/Fe nanoparticles. Transmission electron microscopy (TEM) analysis indicated that CMC-stabilized Pd/Fe nanoparticles were well dispersed, and nanoparticles remained in suspension for days compared to non-stabilized Pd/Fe nanoparticles precipitated within minutes. The isoelectric point (IEP) of the nanoparticles shifted from pH 6.5 to 2.5, suggesting that CMC-stabilized Pd/Fe nanoparticles were negatively charged over a wider pH range. Our batch experiments demonstrated that CMC-stabilized Pd/Fe nanoparticles (0.6 g Fe L −1 ) were able to remove much higher levels of 2,4-D with only one intermediate 2-chlorophenoxyacetic acid (2-CPA) and the final organic product phenoxyacetic acid (PA), than non-stabilized Pd/Fe nanoparticles or microsized Pd/Fe particles. The removal percentage of 2,4-D increased from 10% to nearly 100% as the reaction pH decreased from 11.5 to 2.5. The optimal CMC/Fe mass ratio for the dechlorination of 2,4-D was determined to be 5/1, and the removal of 2,4-D was

Stabilization/Solidification of Radioactive LiCl-KCl Waste Salt by Using SiO2-Al2O3-P2O5(SAP) Inorganic Composite: Part 1. Dechlorination Behavior of LiCl-KCl and Characteristics of Consolidation

International Nuclear Information System (INIS)

Cho, In Hak; Park, Hwan Seo; Ahn, Soo Na; Kim, In Tae; Cho, Yong Zun

2012-01-01

The metal chloride wastes from a pyrochemical process to recover uranium and transuranic elements has been considered as a problematic waste difficult to apply to a conventional solidification method due to the high volatility and low compatibility with silicate glass. In this study, a dechlorination approach to treat LiCl-KCl waste for final disposal was adapted. In this study, a SiO 2 -Al 2 O 3 -P 2 O 5 (SAP) inorganic composite as a dechlorination agent was prepared by a conventional sol-gel process. By using a series of SAPs, the dechlorination behavior and consolidation of reaction products were investigated. Different from LiCl waste, the dechlorination reaction occurred mainly at two temperature ranges. The thermogravimetric test indicated that the first reaction range was about 400 degree C for LiCl and the second was about 700 degree C for KCl. The SAP 1071 (Si/Al/P=1/0.75/1 in molar) was found to be the most favorable SAP as a dechlorination agent under given conditions. The consolidation test revealed that the bulk shape and the densification of consolidated forms depended on the SAP/Salt ratios. The leaching test by PCT-A method was performed to evaluate the durability of consolidated forms. This study provided the basic information on the dechlorination approach. Based on the experimental results, the dechlorination method using a SiO 2 -Al 2 O 3 -P 2 O 5 (SAP) could be considered as one of alternatives for the immobilization of waste salt.

A stereospecific pathway for the introduction of deuterium on the brassinosteroid skeleton by reductive dechlorination of chlorocarbonates

Czech Academy of Sciences Publication Activity Database

Marek, Aleš; Patil, Mahadeo Rajshekhar; Klepetářová, Blanka; Kohout, Ladislav; Elbert, Tomáš

2012-01-01

Roč. 53, č. 16 (2012), s. 2048-2050 ISSN 0040-4039 R&D Projects: GA AV ČR IAA400550801 Institutional research plan: CEZ:AV0Z40550506 Keywords : brassinosteroids * reductive dechlorination * stereospecific reactions Subject RIV: CC - Organic Chemistry Impact factor: 2.397, year: 2012

Effects of ferrous ions on the reductive dechlorination of trichloroethylene by zero-valent iron

Energy Technology Data Exchange (ETDEWEB)

Liu, C.-C. [Graduate Institute of Environmental Engineering, National Central University, Chungli, Taiwan 32001 (China); Tseng, D.-H. [Graduate Institute of Environmental Engineering, National Central University, Chungli, Taiwan 32001 (China)]. E-mail: dhtseng@ncuen.ncu.edu.tw; Wang, C.-Y. [Graduate Institute of Environmental Engineering, National Central University, Chungli, Taiwan 32001 (China)

2006-08-25

The surface characteristics of zero-valent iron (ZVI) and the efficiency of reductive dechlorination of trichloroethylene (TCE) in the presence of ferrous ions were studied. The experimental results indicated that the acid-washing of a metallic iron sample enhanced the efficiency of TCE degradation by ZVI. This occurred because acid-washing changed the conformation of oxides on the surface of iron from maghemite ({gamma}-Fe{sub 2}O{sub 3}) to the more hydrated goethite ({alpha}-FeOOH), as was confirmed by XPS analysis. However, when ferrous ions were simultaneous with TCE in water, the TCE degradation rate decreased as the concentration of ferrous ion increased. This was due to the formation of passive precipitates of ferrous hydroxide, including maghemite and magnetite (Fe{sub 3}O{sub 4}), that coated on the surface of acid-washed ZVI, which as a result inhibited the electron transfer and catalytic hydrogenation mechanisms. On the other hand, in an Fe{sup 0}-TCE system without the acid-washing pretreatment of ZVI, ferrous ions were adsorbed into the maghemite lattice which was then converted to semiconductive magnetite. Thus, the electrons were transferred from the iron surface and passed through the precipitates, allowing for the reductive dechlorination of TCE.

Dechlorination of 2,4-dichlorophenoxyacetic acid by sodium carboxymethyl cellulose-stabilized Pd/Fe nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Zhou, Hongyi, E-mail: zhouhy@zjut.edu.cn [College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032 (China); Han, Jian [College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032 (China); Baig, Shams Ali; Xu, Xinhua [Department of Environmental Engineering, Zhejiang University, Hangzhou 310027 (China)

2011-12-30

Highlights: Black-Right-Pointing-Pointer CMC-stabilized Pd/Fe nanoparticles were synthesized and used for 2,4-D removal. Black-Right-Pointing-Pointer Particle stability, {zeta}-potential and IEP of non- and stabilized Pd/Fe were compared. Black-Right-Pointing-Pointer Dechlorination of 2,4-D by different Pd/Fe systems was investigated. Black-Right-Pointing-Pointer The reaction mechanism has been discussed and presented in the article. Black-Right-Pointing-Pointer Effects of CMC/Fe mass ratio and pH were also investigated. - Abstract: This paper describes the synthesis of sodium carboxymethyl cellulose (CMC)-stabilized Pd/Fe nanoparticles and their applications to the dechlorination of 2,4-dichlorophenoxyacetic acid (2,4-D) under controlled laboratorial conditions. For this purpose batch mode experiments were conducted to understand the effects of CMC on the surface characteristics of Pd/Fe nanoparticles, optimum removal of 2,4-D and other surface interactions mechanism. Our experimental results demonstrated considerable enhancements in particle stability and chemical reactivity with the addition of CMC to Pd/Fe nanoparticles. Transmission electron microscopy (TEM) analysis indicated that CMC-stabilized Pd/Fe nanoparticles were well dispersed, and nanoparticles remained in suspension for days compared to non-stabilized Pd/Fe nanoparticles precipitated within minutes. The isoelectric point (IEP) of the nanoparticles shifted from pH 6.5 to 2.5, suggesting that CMC-stabilized Pd/Fe nanoparticles were negatively charged over a wider pH range. Our batch experiments demonstrated that CMC-stabilized Pd/Fe nanoparticles (0.6 g Fe L{sup -1}) were able to remove much higher levels of 2,4-D with only one intermediate 2-chlorophenoxyacetic acid (2-CPA) and the final organic product phenoxyacetic acid (PA), than non-stabilized Pd/Fe nanoparticles or microsized Pd/Fe particles. The removal percentage of 2,4-D increased from 10% to nearly 100% as the reaction pH decreased from 11

Stabilization/Solidification of Radioactive LiCl-KCl Waste Salt by Using SiO{sub 2}-Al{sub 2}O{sub 3}-P{sub 2}O{sub 5}(SAP) Inorganic Composite: Part 1. Dechlorination Behavior of LiCl-KCl and Characteristics of Consolidation

Energy Technology Data Exchange (ETDEWEB)

Cho, In Hak; Park, Hwan Seo; Ahn, Soo Na; Kim, In Tae; Cho, Yong Zun [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2012-03-15

The metal chloride wastes from a pyrochemical process to recover uranium and transuranic elements has been considered as a problematic waste difficult to apply to a conventional solidification method due to the high volatility and low compatibility with silicate glass. In this study, a dechlorination approach to treat LiCl-KCl waste for final disposal was adapted. In this study, a SiO{sub 2}-Al{sub 2}O{sub 3}-P{sub 2}O{sub 5} (SAP) inorganic composite as a dechlorination agent was prepared by a conventional sol-gel process. By using a series of SAPs, the dechlorination behavior and consolidation of reaction products were investigated. Different from LiCl waste, the dechlorination reaction occurred mainly at two temperature ranges. The thermogravimetric test indicated that the first reaction range was about 400 degree C for LiCl and the second was about 700 degree C for KCl. The SAP 1071 (Si/Al/P=1/0.75/1 in molar) was found to be the most favorable SAP as a dechlorination agent under given conditions. The consolidation test revealed that the bulk shape and the densification of consolidated forms depended on the SAP/Salt ratios. The leaching test by PCT-A method was performed to evaluate the durability of consolidated forms. This study provided the basic information on the dechlorination approach. Based on the experimental results, the dechlorination method using a SiO{sub 2}-Al{sub 2}O{sub 3}-P{sub 2}O{sub 5}(SAP) could be considered as one of alternatives for the immobilization of waste salt.

Introduction of a De Novo Bioremediation Ability, Aryl Reductive Dechlorination, into Anaerobic Granular Sludge by Inoculation of Sludge with Desulfomonile tiedjei

DEFF Research Database (Denmark)

Ahring, Birgitte Kiær; Christiansen, Nina; Mathrani, Indra Madan

1992-01-01

Methanogenic upflow anaerobic granular-sludge blanket (UASB) reactors treat wastewaters at a high rate while simultaneously producing a useful product, methane; however, recalcitrant environmental pollutants may not be degraded. To impart 3-chlorobenzoate (3-CB)-dechlorinating ability to UASB rea...

Metagenomic and Metatranscriptomic Analyses Reveal the Structure and Dynamics of a Dechlorinating Community Containing Dehalococcoides mccartyi and Corrinoid-Providing Microorganisms under Cobalamin-Limited Conditions

Energy Technology Data Exchange (ETDEWEB)

Men, Yujie; Yu, Ke; Bælum, Jacob; Gao, Ying; Tremblay, Julien; Prestat, Emmanuel; Stenuit, Ben; Tringe, Susannah G.; Jansson, Janet; Zhang, Tong; Alvarez-Cohen, Lisa; Liu, Shuang-Jiang

2017-02-10

The aim of this study is to obtain a systems-level understanding of the interactions betweenDehalococcoidesand corrinoid-supplying microorganisms by analyzing community structures and functional compositions, activities, and dynamics in trichloroethene (TCE)-dechlorinating enrichments. Metagenomes and metatranscriptomes of the dechlorinating enrichments with and without exogenous cobalamin were compared. Seven putative draft genomes were binned from the metagenomes. At an early stage (2 days), more transcripts of genes in theVeillonellaceaebin-genome were detected in the metatranscriptome of the enrichment without exogenous cobalamin than in the one with the addition of cobalamin. Among these genes, sporulation-related genes exhibited the highest differential expression when cobalamin was not added, suggesting a possible release route of corrinoids from corrinoid producers. Other differentially expressed genes include those involved in energy conservation and nutrient transport (including cobalt transport). The most highly expressed corrinoidde novobiosynthesis pathway was also assigned to theVeillonellaceaebin-genome. Targeted quantitative PCR (qPCR) analyses confirmed higher transcript abundances of those corrinoid biosynthesis genes in the enrichment without exogenous cobalamin than in the enrichment with cobalamin. Furthermore, the corrinoid salvaging and modification pathway ofDehalococcoideswas upregulated in response to the cobalamin stress. This study provides important insights into the microbial interactions and roles played by members of dechlorinating communities under cobalamin-limited conditions.

IMPORTANCEThe key

On the mechanism of dechlorination of polychlorinated biphenyls (PCBs) induced by electron beam irradiation in aqueous and aqueous micellar solutions, transformer oil, and sediment

International Nuclear Information System (INIS)

Chaychian, M.; Silverman, J.; Al-Sheirkhly, M.

2011-01-01

Complete text of publication follows. The widespread release of PCBs into the environment presents a serious problem due to their persistence and toxicity. Ionizing radiation, such as gamma rays and high-energy electron beam, is remarkably effective in dechlorinating PCBs into biphenyls. The kinetics of the reductive dechlorination of PCBs in aqueous and aqueous micellar solutions and in transformer oil is being studied by pulse radiolysis and steady-state radiolysis. In aqueous micellar solutions, dichlori-, tetrachloro-, and decachlorobiphenyl congeners were solubilized in water using a commercially available non-ionic surfactant, Triton X-100, and subsequently pulse irradiated by electron accelerator using optical detection method. The reaction rate constant between decachlorobiphenyl and aqueous electrons e aq ·- , and Triton with e aq ·- in the 2% Triton solution, were measured as 2.6 x 10 9 Lmol -1 s -1 and 1.2 x 10 7 Lmol -1 s -1 , respectively. We have also measured in aqueous solutions, the reaction rate constant of e aq ·- with dichlorobiphenyl as 3.8 x 10 9 Lmol -1 s -1 . In aqueous-propanol, the reaction rate constants of e aq ·- with dichlorobiphenyl, tetrachlorobiphenyl, and dechachlorobiphenyl are 2 x 10 9 Lmol -1 s -1 , 3 x 10 9 Lmol -1 s -1 , and 7 x 10 9 Lmol -1 s -1 , respectively. In addition to the presence of PCBs as high-dielectric component, transformer oil contains many aromatic hydrocarbons; the most abundant being biphenyl, fluorine, and phenanthrene. Solvated electrons formed by irradiation of the oil react either with PCB to lead to dechlorination or with the aromatic hydrocarbons present in the oil to form radical anions. These species are shown to transfer an electron to chlorinated biphenyls relative rapidly, leading to dechlorination. The rate constants for several such reactions, determined in 2-propanol solutions, are in the range of 10 7 - 10 8 Lmol -1 s -1 . These rapid reactions explain why PCB can be dechlorinated in oil

Deposition of Fe-Ni nanoparticles on Al2O3 for dechlorination of chloroform and trichloroethylene

International Nuclear Information System (INIS)

Hsieh, S.-H.; Horng, J.-J.

2006-01-01

This research proposes an efficient method for depositing Fe-Ni nanoparticles on Al 2 O 3 microparticles to decompose containments in ground water, such as chloroform and trichloroethylene. The Fe-Ni nanoparticles can be deposited onto the surface of Al 2 O 3 microparticles by electroless plating technique. The reasons why the Fe-Ni nanoparticles would be deposited on the surface of Al 2 O 3 microparticles is to avoid the agglomeration of Fe-Ni nanoparticles due to their surface effect and magnetic property. The results show that the sizes of Fe-Ni particles on Al 2 O 3 particles are between several and several hundreds of nanometers, the contents of Fe and Ni in Fe-Ni nanoparticles can be adjusted from 8 to 60 at.% for Fe and 40 to 92 at.% for Ni, the specific surface area of Fe-Ni nanoparticles can reach to 117 m 2 /g, and the reaction mechanism of dechlorination of chloroform of 2 mg/L by Fe-Ni/Al 2 O 3 particles of 5 g/L appears to be pseudo first order with a half life of 0.7 h and the half life is 0.25 h for the dechlorination of trichloroethylene of 2 mg/L

Exploring the Genome and Proteome of Desulfitobacterium hafniense DCB2 for its Protein Complexes Involved in Metal Reduction and Dechlorination

Energy Technology Data Exchange (ETDEWEB)

Sang-Hoon, Kim; Hardzman, Christina; Davis, John k.; Hutcheson, Rachel; Broderick, Joan B.; Marsh, Terence L.; Tiedje, James M.

2012-09-27

Desulfitobacteria are of interest to DOE mission because of their ability to reduce many electron acceptors including Fe(III), U(VI), Cr(VI), As(V), Mn(IV), Se(VI), NO₃- and well as CO₂, sulfite, fumarate and humates, their ability to colonize more stressful environments because they form spores, fix nitrogen and they have the more protective Gram positive cell walls. Furthermore at least some of them reductively dechlorinate aromatic and aliphatic pollutants. Importantly, most of the metals and the organochlorine reductions are coupled to ATP production and support growth providing for the organism's natural selection at DOE's contaminant sites. This work was undertaken to gain insight into the genetic and metabolic pathways involved in dissimilatory metal reduction and reductive dechlorination, (ii) to discern the commonalities among these electron-accepting processes, (iii) to identify multi-protein complexes catalyzing these functions and (iv) to elucidate the coordination in expression of these pathways and processes.

Reductive dechlorination of trichloroethene DNAPL source zones: source zone architecture versus electron donor availability

Science.gov (United States)

Krol, M.; Kokkinaki, A.; Sleep, B.

2014-12-01

The persistence of dense-non-aqueous-phase liquids (DNAPLs) in the subsurface has led practitioners and regulatory agencies to turn towards low-maintenance, low-cost remediation methods. Biological degradation has been suggested as a possible solution, based on the well-proven ability of certain microbial species to break down dissolved chlorinated ethenes under favorable conditions. However, the biodegradation of pure phase chlorinated ethenes is subject to additional constraints: the continuous release of electron acceptor at a rate governed by mass transfer kinetics, and the temporal and spatial heterogeneity of DNAPL source zones which leads to spatially and temporally variable availability of the reactants for reductive dechlorination. In this work, we investigate the relationship between various DNAPL source zone characteristics and reaction kinetics using COMPSIM, a multiphase groundwater model that considers non-equilibrium mass transfer and Monod-type kinetics for reductive dechlorination. Numerical simulations are performed for simple, homogeneous trichloroethene DNAPL source zones to demonstrate the effect of single source zone characteristics, as well as for larger, more realistic heterogeneous source zones. It is shown that source zone size, and mass transfer kinetics may have a decisive effect on the predicted bio-enhancement. Finally, we evaluate the performance of DNAPL bioremediation for realistic, thermodynamically constrained, concentrations of electron donor. Our results indicate that the latter may be the most important limitation for the success of DNAPL bioremediation, leading to reduced bio-enhancement and, in many cases, comparable performance with water flooding.

INFLUENCE OF HYDRAULIC RETENTION TIME ON EXTENT OF PCE DECHLORINATION AND PRELIMINARY CHARACTERIZATION OF THE ENRICHMENT CULTURE. (R826694C703)

Science.gov (United States)

The extent of tetrachloroethene (PCE) dechlorination in two chemostats was evaluated as a function of hydraulic retention time (HRT). The inoculum of these chemostats was from an upflow anaerobic sludge blanket (UASB) reactor that rapidly converts PCE to vinyl chloride (VC) an...

Innovative leaching of cobalt and lithium from spent lithium-ion batteries and simultaneous dechlorination of polyvinyl chloride in subcritical water

Energy Technology Data Exchange (ETDEWEB)

Liu, Kang; Zhang, Fu-Shen, E-mail: fszhang@rcees.ac.cn

2016-10-05

Highlights: • A co-treatment process for recovery of Co and Li and simultaneous detoxification of PVC in subcritical water was proposed. • PVC was used as a hydrochloric acid source. • More than 95% Co and nearly 98% Li were leached under the optimum conditions. • Neither corrosive acid nor reducing agent was used. • The co-treatment process has technical, economic and environmental benefits over the traditional recovery processes. - Abstract: In this work, an effective and environmentally friendly process for the recovery of cobalt (Co) and lithium (Li) from spent lithium-ion batteries (LIBs) and simultaneously detoxification of polyvinyl chloride (PVC) in subcritical water was developed. Lithium cobalt oxide (LiCoO{sub 2}) power from spent LIBs and PVC were co-treated by subcritical water oxidation, in which PVC served as a hydrochloric acid source to promote metal leaching. The dechlorination of PVC and metal leaching was achieved simultaneously under subcritical water oxidation. More than 95% Co and nearly 98% Li were recovered under the optimum conditions: temperature 350 °C, PVC/LiCoO{sub 2} ratio 3:1, time 30 min, and a solid/liquid ratio 16:1 (g/L), respectively. Moreover, PVC was completely dechlorinated at temperatures above 350 °C without any release of toxic chlorinated organic compounds. Assessment on economical and environmental impacts revealed that the PVC and LiCoO{sub 2} subcritical co-treatment process had significant technical, economic and environmental benefits over the traditional hydrometallurgy and pyrometallurgy processes. This innovative co-treatment process is efficient, environmentally friendly and adequate for Co and Li recovery from spent LIBs and simultaneous dechlorination of PVC in subcritical water.

Understanding Hydrothermal Dechlorination of PVC by Focusing on the Operating Conditions and Hydrochar Characteristics

Directory of Open Access Journals (Sweden)

Tian Li

2017-03-01

Full Text Available To remove chlorine from chlorinated wastes efficiently, the hydrothermal treatment (HT of PVC was investigated with a lower alkaline dosage in this work. Some typical operating conditions were investigated to find out the most important factor affecting the dechlorination efficiency (DE. The FTIR technique was employed to detect the functional groups in PVC and hydrochars generated to reveal the possible pathways for chlorine removal. The results show that the HT temperature was a key parameter to control the dechlorination reaction rate. At a HT temperature of 240 °C, about 94.3% of chlorine could be removed from the PVC with 1% NaOH. The usage of NaOH was helpful for chlorine removal, while a higher dosage might also hinder this process because of the surface poisoning and coverage of free sites. To some extent, the DE was increased with the residence time. At a residence time of 30 min, the DE reached a maximum of 76.74%. A longer residence time could promote the generation of pores in hydrochar which is responsible for the reduction in DE because of the re-absorption of water-soluble chlorine. According to the FTIR results, the peak intensities of both C=CH and C=C stretching vibrations in hydrochar were increased, while the peak at around 3300 cm−1 representing the –OH group was not obvious, indicating that the dehydrochlorination (elimination reaction was a main route for chlorine removal under these conditions studied in this work.

Isolation of novel bacteria within the Chloroflexi capable of reductive dechlorination of 1,2,3-trichloropropane.

Science.gov (United States)

Yan, J; Rash, B A; Rainey, F A; Moe, W M

2009-04-01

Two strictly anaerobic bacterial strains were isolated from contaminated groundwater at a Superfund site located near Baton Rouge, LA, USA. These strains represent the first isolates reported to reductively dehalogenate 1,2,3-trichloropropane. Allyl chloride (3-chloro-1-propene), which is chemically unstable, was produced from 1,2,3-trichloropropane, and it was hydrolysed abiotically to allyl alcohol and also reacted with the sulfide- and cysteine-reducing agents in the medium to form various allyl sulfides. Both isolates also dehalogenated a variety of other vicinally chlorinated alkanes (1,2-dichloropropane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,2,2- tetrachloroethane) via dichloroelimination reactions. A quantitative real-time PCR (qPCR) approach targeting 16S rRNA genes indicated that both strains couple reductive dechlorination to cell growth. Growth was not observed in the absence of hydrogen (H2) as an electron donor and a polychlorinated alkane as an electron acceptor. Alkanes containing only a single chlorine substituent (1-chloropropane, 2-chloropropane), chlorinated alkenes (tetrachlorothene, trichlorothene, cisdichloroethene, trans-dichloroethene, vinyl chloride) and chlorinated benzenes (1-chlorobenzene and 1,2- dichlorobenzene) were not dechlorinated. Phylogenetic analysis based on 16S rRNA gene sequence data showed these isolates to represent a new lineage within the Chloroflexi. Their closest previously cultured relatives are 'Dehalococcoides' strains, with 16S rRNA gene sequence similarities of only 90%.

Fabrication and evaluation of Au-Pd core-shell nanocomposites for dechlorination of diclofenac in water.

Science.gov (United States)

Wang, Xu; Li, Jian-Rong; Fu, Ming-Lai; Yuan, Baoling; Cui, Hao-Jie; Wang, Ya-Fen

2015-01-01

Nanocomposites with core-shell structure usually exhibit excellent catalytic properties due to unique interfaces and synergistic effect among composites. In this study, Au-Pd bimetallic nanoparticles (NPs) with core-shell structure (Au-Pd cs) by using Au NPs as core and Pd as shell were successfully fabricated and, for the first time, were used to investigate the dechlorination of diclofenac (DCF) at H2 atmosphere in water at room temperature. The degradation products were studied as well by using HPLC/Q-ToF MS/MS. The operational factors such as pH and composition of the Au-Pd cs were also studied. The results showed that nearly 100% of DCF (30 mg L(-1), 50 mL, pH=7) was dechlorinated in 4.5 h by 10 mL of 56 mg L(-1) of Au-Pd cs. Ninety per cent of DCF was degraded in 6.5 h by the mixture of Au and Pd NPs. However, the individual Au NPs had no obvious effect in degrading DCF and the monometallic Pd NPs with comparable concentration only degraded less than 20% of DCF. Furthermore, the reaction mechanism of this catalytic process was studied in detail. It was found that the degradation was a second-order exponential reaction. The two main degradation products were obtained by cleaving the carbon-halogen bond of DCF and this made the degradation products more environmentally friendly.

Enhanced CAH dechlorination in a low permeability, variably-saturated medium

Science.gov (United States)

Martin, J.P.; Sorenson, K.S.; Peterson, L.N.; Brennan, R.A.; Werth, C.J.; Sanford, R.A.; Bures, G.H.; Taylor, C.J.; ,

2002-01-01

An innovative pilot-scale field test was performed to enhance the anaerobic reductive dechlorination (ARD) of chlorinated aliphatic hydrocarbons (CAHs) in a low permeability, variably-saturated formation. The selected technology combines the use of a hydraulic fracturing (fracking) technique with enhanced bioremediation through the creation of highly-permeable sand- and electron donor-filled fractures in the low permeability matrix. Chitin was selected as the electron donor because of its unique properties as a polymeric organic material and based on the results of lab studies that indicated its ability to support ARD. The distribution and impact of chitin- and sand-filled fractures to the system was evaluated using hydrologic, geophysical, and geochemical parameters. The results indicate that, where distributed, chitin favorably impacted redox conditions and supported enhanced ARD of CAHs. These results indicate that this technology may be a viable and cost-effective approach for remediation of low-permeability, variably saturated systems.

Reductive dechlorination of trichloroethylene (TCE) in competition with Fe and Mn oxides – observed dynamics in H2-dependent terminal electron accepting processes

DEFF Research Database (Denmark)

Paul, Laiby; Jakobsen, Rasmus; Smolders, Erik

2016-01-01

The determination of hydrogen (H2) concentration together with the products of microbial reduction reactions in a trichloroethylene dechlorinating system is conducted to delineate the ongoing predominant terminal electron accepting processes (TEAP). Formate was used as electron donor and synthetic...

Synergistic effect of nano-sized mackinawite with cyano-cobalamin in cement slurries for reductive dechlorination of tetrachloroethylene

International Nuclear Information System (INIS)

Kyung, Daeseung; Sihn, Youngho; Kim, Sangwoo; Bae, Sungjun; Amin, Muhammad Tahir; Alazba, Abdulrahman Ali; Lee, Woojin

2016-01-01

Highlights: • Complete degradation of PCE was observed in nFeS-Cbl(III)-cement at pH 12. • PCE was completely degraded to non-chlorinated organic compounds by this system. • Co redox couple and Ca species in cement played a pivotal role for PCE reduction. • Increases in Cbl(III) concentration, cement ratio, and pH enhanced PCE degradation. • Efficiency of the system for PCE reduction was good even at high concentration of PCE. - Abstract: Experiments were conducted to investigate the reductive dechlorination of tetrachloroethylene (PCE) by nano-Mackinawite (nFeS) with cyano-cobalamin (Cbl(III)) in cement slurries. Almost complete degradation of PCE by nFeS-Cbl(III) was observed in cement slurries in 5 h and its degradation kinetics (k_o_b_s_-_P_C_E = 0.57 h"−"1) was 6-times faster than that of nFeS-Cbl(III) without the cement slurries. PCE was finally transformed to non-chlorinated organic compounds such as ethylene, acetylene, and C3-C4 hydrocarbons by nFeS-Cbl(III) in cement slurries. X-ray photoelectron spectroscopy and PCE degradation by cement components (SiO_2, Al_2O_3, and CaO) revealed that both the reduced Co species in Cbl(III) and the presence of Ca in cement played an important role for the enhanced reductive dechlorination of PCE. The increase in the concentration of Cbl(III) (0.005–0.1 mM), cement ratio (0.05–0.2), and suspension pH (11.5–13.5) accelerated the PCE degradation kinetics by providing more favorable environments for the production of reactive Ca species and reduction of Co species. We also observed that the degradation efficiency of PCE by nFeS-Cbl(III)-cement lasted even at high concentration of PCE. The experimental results obtained from this study could provide fundamental knowledge of redox interactions among nFeS, Cbl(III), and cement, which could significantly enhance reductive dechlorination of chlorinated organics in contaminated natural and engineered environments.

Synergistic effect of nano-sized mackinawite with cyano-cobalamin in cement slurries for reductive dechlorination of tetrachloroethylene

Energy Technology Data Exchange (ETDEWEB)

Kyung, Daeseung [Department of Civil and Environmental Engineering, Korea Advanced Institute of Science and Technology (KAIST), 291 Daehak-ro, Yuseong-gu, Daejeon 34141 (Korea, Republic of); Sihn, Youngho [Department of Nuclear and Quantum Engineering, Korea Advanced Institute of Science and Technology (KAIST), 291 Daehak-ro, Yuseong-gu, Daejeon 34141 (Korea, Republic of); Kim, Sangwoo [Department of Civil and Environmental Engineering, Korea Advanced Institute of Science and Technology (KAIST), 291 Daehak-ro, Yuseong-gu, Daejeon 34141 (Korea, Republic of); Bae, Sungjun [Department of Environmental Engineering, Konkuk University, 120 Neungdong-ro, Gwangjin-gu, Seoul 05029 (Korea, Republic of); Amin, Muhammad Tahir; Alazba, Abdulrahman Ali [Alamoudi Water Chair, King Saud University, Riyadh 11451 (Saudi Arabia); Lee, Woojin, E-mail: woojin_lee@kaist.ac.kr [Department of Civil and Environmental Engineering, Korea Advanced Institute of Science and Technology (KAIST), 291 Daehak-ro, Yuseong-gu, Daejeon 34141 (Korea, Republic of)

2016-07-05

Highlights: • Complete degradation of PCE was observed in nFeS-Cbl(III)-cement at pH 12. • PCE was completely degraded to non-chlorinated organic compounds by this system. • Co redox couple and Ca species in cement played a pivotal role for PCE reduction. • Increases in Cbl(III) concentration, cement ratio, and pH enhanced PCE degradation. • Efficiency of the system for PCE reduction was good even at high concentration of PCE. - Abstract: Experiments were conducted to investigate the reductive dechlorination of tetrachloroethylene (PCE) by nano-Mackinawite (nFeS) with cyano-cobalamin (Cbl(III)) in cement slurries. Almost complete degradation of PCE by nFeS-Cbl(III) was observed in cement slurries in 5 h and its degradation kinetics (k{sub obs-PCE} = 0.57 h{sup −1}) was 6-times faster than that of nFeS-Cbl(III) without the cement slurries. PCE was finally transformed to non-chlorinated organic compounds such as ethylene, acetylene, and C3-C4 hydrocarbons by nFeS-Cbl(III) in cement slurries. X-ray photoelectron spectroscopy and PCE degradation by cement components (SiO{sub 2}, Al{sub 2}O{sub 3}, and CaO) revealed that both the reduced Co species in Cbl(III) and the presence of Ca in cement played an important role for the enhanced reductive dechlorination of PCE. The increase in the concentration of Cbl(III) (0.005–0.1 mM), cement ratio (0.05–0.2), and suspension pH (11.5–13.5) accelerated the PCE degradation kinetics by providing more favorable environments for the production of reactive Ca species and reduction of Co species. We also observed that the degradation efficiency of PCE by nFeS-Cbl(III)-cement lasted even at high concentration of PCE. The experimental results obtained from this study could provide fundamental knowledge of redox interactions among nFeS, Cbl(III), and cement, which could significantly enhance reductive dechlorination of chlorinated organics in contaminated natural and engineered environments.

Reductive dechlorination of 3,3',4,4'-tetrachlorobiphenyl (PCB77) using palladium or palladium/iron nanoparticles and assessment of the reduction in toxic potency in vascular endothelial cells

International Nuclear Information System (INIS)

Venkatachalam, Karthik; Arzuaga, Xabier; Chopra, Nitin; Gavalas, Vasilis G.; Xu, Jian; Bhattacharyya, Dibakar; Hennig, Bernhard; Bachas, Leonidas G.

2008-01-01

Palladium-based nanoparticles immobilized in polymeric matrices were applied to the reductive dechlorination of 3,3',4,4'-tetrachlorobiphenyl (PCB77) at room temperature. Two different dechlorination platforms were evaluated using (1) Pd nanoparticles within conductive polypyrrole films; or (2) immobilized Fe/Pd nanoparticles within polyvinylidene fluoride microfiltration membranes. For the first approach, the polypyrrole film was electrochemically formed in the presence of perchlorate ions that were incorporated into the film to counter-balance the positive charges of the polypyrrole chain. The film was then incubated in a solution containing tetrachloropalladate ions, which were exchanged with the perchlorate ions within the film. During this exchange, reduction of tetrachloropalladate by polypyrrole occurred, which led to the formation of palladium nanoparticles within the film. For the second approach, the membrane-supported Fe/Pd nanoparticles were prepared in three steps: polymerization of acrylic acid in polyvinylidene fluoride microfiltration membrane pores was followed by ion exchange of Fe 2+ , and then chemical reduction of the ferrous ions bound to the carboxylate groups. The membrane-supported iron nanoparticles were then soaked in a solution of tetrachloropalladate resulting in the deposition of Pd on the Fe surface. The nanoparticles prepared by both approaches were employed in the dechlorination of PCB77. The presence of hydrogen was required when the monometallic Pd nanoparticles were employed. The results indicate the removal of chlorine atoms from PCB77, which led to the formation of lower chlorinated intermediates and ultimately biphenyl. Toxicity associated with vascular dysfunction by PCB77 and biphenyl was compared using cultured endothelial cells. The data strongly suggest that the dechlorination system used in this study markedly reduced the proinflammatory activity of PCB77, a persistent organic pollutant

De-chlorination and solidification of radioactive LiCl waste salt by using SiO_2-Al_2O_3-P_2O_5 (SAP) inorganic composite including B_2O_3 component

International Nuclear Information System (INIS)

Lee, Ki Rak; Park, Hwan-Seo; Cho, In-Hak; Choi, Jung-Hoon; Eun, Hee-Chul; Lee, Tae-Kyo; Han, Seung Youb; Ahn, Do-Hee

2017-01-01

SAP (SiO_2-Al_2O_3-P_2O_5) composite has been recently studied in KAERI to deal with the immobilization of radioactive salt waste, one of the most problematic wastes in the pyro-chemical process. Highly unstable salt waste was successfully converted into stable compounds by the dechlorination process with SAPs, and then a durable waste form with a high waste loading was produced when adding glassy materials to dechlorination product. In the present study, U-SAP composite which is SAP bearing glassy component (Boron) was synthesized to remove the adding and mixing steps of glassy materials for a monolithic wasteform. With U-SAPs prepared by a sol-gel process, a series of wasteforms were fabricated to identify a proper reaction condition. Physical and chemical properties of dechlorination products and U-SAP wasteforms were characterized by XRD, DSC, SEM, TGA and PCT-A. A U-SAP wasteform showed suitable properties as a radioactive wasteform such as dense surface morphology, high waste loading, and high durability at the optimized U-SAP/salt ratio 2.

Comment on 'evaluation of dechlorination mechanisms during anaerobic fermentation of blached kraft mill effluent by W.J. Parker, E.R. Hall and G.J. Farquhar'

Digital Repository Service at National Institute of Oceanography (India)

Sarkar, A.

Comment on "Evaluation of dechlorination mechanisms during anaerobic fermentation of bleached kraft mill effluent", is put forth. The data reproduced in Table 1 does not seem to be authentic as the method of preprationo of the chlorinated organic...

Effect of heterogeneity on enhanced reductive dechlorination: Analysis of remediation efficiency and groundwater acidification

Science.gov (United States)

Brovelli, A.; Lacroix, E.; Robinson, C. E.; Gerhard, J.; Holliger, C.; Barry, D. A.

2011-12-01

Enhanced reductive dehalogenation is an attractive in situ treatment technology for chlorinated contaminants. The process includes two acid-forming microbial reactions: fermentation of an organic substrate resulting in short-chain fatty acids, and dehalogenation resulting in hydrochloric acid. The accumulation of acids and the resulting drop of groundwater pH are controlled by the mass and distribution of chlorinated solvents in the source zone, type of electron donor, alternative terminal electron acceptors available and presence of soil mineral phases able to buffer the pH (such as carbonates). Groundwater acidification may reduce or halt microbial activity, and thus dehalogenation, significantly increasing the time and costs required to remediate the aquifer. In previous work a detailed geochemical and groundwater flow simulator able to model the fermentation-dechlorination reactions and associated pH change was developed. The model accounts for the main processes influencing microbial activity and groundwater pH, including the groundwater composition, the electron donor used and soil mineral phase interactions. In this study, the model was applied to investigate how spatial variability occurring at the field scale affects dechlorination rates, groundwater pH and ultimately the remediation efficiency. Numerical simulations were conducted to examine the influence of heterogeneous hydraulic conductivity on the distribution of the injected, fermentable substrate and on the accumulation/dilution of the acidic products of reductive dehalogenation. The influence of the geometry of the DNAPL source zone was studied, as well as the spatial distribution of soil minerals. The results of this study showed that the heterogeneous distribution of the soil properties have a potentially large effect on the remediation efficiency. For examples, zones of high hydraulic conductivity can prevent the accumulation of acids and alleviate the problem of groundwater acidification. The

Deposition of Fe-Ni nanoparticles on Al{sub 2}O{sub 3} for dechlorination of chloroform and trichloroethylene

Energy Technology Data Exchange (ETDEWEB)

Hsieh, S.-H. [Graduate School of Engineering Science and Technology, National Yunlin University of Science and Technology, Taiwan (China) and Department of Materials Science and Engineering, National Formosa University, Taiwan (China)]. E-mail: shhsieh@sunws.nfu.edu.tw; Horng, J.-J. [Department of Safety, Health, and Environmental Engineering, National Yunlin University of Science and Technology, Douliou, Yunlin 640, Taiwan (China)

2006-11-30

This research proposes an efficient method for depositing Fe-Ni nanoparticles on Al{sub 2}O{sub 3} microparticles to decompose containments in ground water, such as chloroform and trichloroethylene. The Fe-Ni nanoparticles can be deposited onto the surface of Al{sub 2}O{sub 3} microparticles by electroless plating technique. The reasons why the Fe-Ni nanoparticles would be deposited on the surface of Al{sub 2}O{sub 3} microparticles is to avoid the agglomeration of Fe-Ni nanoparticles due to their surface effect and magnetic property. The results show that the sizes of Fe-Ni particles on Al{sub 2}O{sub 3} particles are between several and several hundreds of nanometers, the contents of Fe and Ni in Fe-Ni nanoparticles can be adjusted from 8 to 60 at.% for Fe and 40 to 92 at.% for Ni, the specific surface area of Fe-Ni nanoparticles can reach to 117 m{sup 2}/g, and the reaction mechanism of dechlorination of chloroform of 2 mg/L by Fe-Ni/Al{sub 2}O{sub 3} particles of 5 g/L appears to be pseudo first order with a half life of 0.7 h and the half life is 0.25 h for the dechlorination of trichloroethylene of 2 mg/L.

Photocatalytic reductive dechlorination of 2-chlorodibenzo-p-dioxin by Pd modified g-C3N4 photocatalysts under UV-vis irradiation: Efficacy, kinetics and mechanism.

Science.gov (United States)

Ding, Jiafeng; Long, Gaoyuan; Luo, Yang; Sun, Runze; Chen, Mengxia; Li, Yajun; Zhou, Yanfang; Xu, Xinhua; Zhao, Weirong

2018-05-09

Polychlorinated dibenzo-p-dioxins (PCDDs), as a group of notorious anthropogenic environmental toxicants, are arguably ubiquitous in nature. In this study, we investigated the photocatalytic reductive dechlorination of 2-chlorodibenzo-p-dioxin (2-CDD) over Pd/g-C 3 N 4 catalysts under UV-vis irradiation. The g-C 3 N 4 and a series of Pd/g-C 3 N 4 catalysts were prepared by thermal polymerization and mechanical mixing-illumination method and characterized by XRD, TEM, BET, SEM and UV-vis DRS analyses. Among all the samples, the Pd/g-C 3 N 4 (5 wt%) yielded the optimal dechlorination activity with a total 2-CDD conversion of 54% within 4 h, and 76% of those converted 2-CDD were evolved to dibenzo-p-dioxin (DD). The kinetics of dechlorination could be described as pseudo-first-order decay model (R 2  > 0.84). Corresponding rate constants (k) increased from 0.052 to 0.17 h -1 with Pd contents up to 5 wt% and decreased to 0.13 h -1 with a 10 wt% of Pd. The enhanced activities originated from the surface plasmonic resonance (SPR) effect of Pd nanoparticles and the formation of Schottky barrier between Pd and g-C 3 N 4 , which extend the spectrum responsive range and suppress the charge recombination of g-C 3 N 4 . This is the first report on the photocatalytic reductive removal of PCDDs and may provide a new approach for PCDDs pollution control. Copyright © 2018 Elsevier B.V. All rights reserved.

Dechlorination of PCBs in Aqueous Extracts from Soils Contaminated by PCBs by Application of Zero-valent Nano-iron in Statu Nascendi. Influence of Microwaves on the Rate of Reaction

Czech Academy of Sciences Publication Activity Database

Kaštánek, František; Maléterová, Ywetta; Šolcová, Olga; Kaštánek, P.

2010-01-01

Roč. 1, č. 1 (2010), s. 50-56 R&D Projects: GA AV ČR KAN400720701; GA ČR GA104/09/0694 Keywords : nano-Fe * PCB * reductive dechlorination Subject RIV: CI - Industrial Chemistry, Chemical Engineering

Bioelectrocatalytic dechlorination of trichloroacetic acid at gel-immobilized hemoglobin on multiwalled carbon nanotubes modified graphite electrode: Kinetic modeling and reaction pathways

International Nuclear Information System (INIS)

Liu, Qi; Yu, Jianming; Xu, Yinghua; Wang, Jiade; Ying, Le; Song, Xinxin; Zhou, Gendi; Chen, Jianmeng

2013-01-01

Highlights: ► The electrons transfer from enzyme in the electrode to COCs was the key step. ► The average current efficiency was influenced by pH and temperature of the systems. ► The most favourable degradation conditions for TCA were found to be pH 3 and 310 K. ► The activation energy of 26.2 kJ mol −1 was also calculated by the Arrhenius equation. ► Bioelectrocatalytic mechanism of TCA was verified by kinetic expressions. -- Abstract: In bioelectrochemically reductive dechlorination of chlorinated organic compounds (COCs), the electrons transfer from enzyme in the electrode to COCs was the key step, which determined the average current efficiency (CE) and was influenced by the pH and temperature of the systems. In this work, the effect of temperature (288–318 K) and pH (2–11) of the electrolyte on decholrination of trichloroacetic acid (TCA) was investigated in the sodium alginate/hemoglobin-multiwalled carbon nanotubes-graphite composite electrode (Hb/SA–MWCNT–GE). The results showed that the most favourable degradation conditions for TCA by Hb/SA–MWCNT–GE were found to be pH 3 and 310 K. By varying the pH of the systems, it was found that a proton accompanied with an electron transfer between the electrode and heme Fe(III)/Fe(II) of Hb during the reaction. Additionally, the activation energy of 26.2 kJ mol −1 was also calculated by the Arrhenius equation for the reaction. The total mass balance of the reactant and the products was in the range of 97–105% during the bioelectrochemically reductive reaction. The CE only decreased from 87% to 83% when the Hb/SA–MWCNT–GE was used 5 times. Based on the intermediates detected, a pathway was proposed for TCA degradation in which it underwent dechlorination process. The main degradation mechanism described by a parallel reaction rather than by a sequential reaction for dechlorination of TCA in Hb/SA–MWCNT–GE system was proposed. These data provided relevant information about the

De-chlorination and solidification of radioactive LiCl waste salt by using SiO{sub 2}-Al{sub 2}O{sub 3}-P{sub 2}O{sub 5} (SAP) inorganic composite including B{sub 2}O{sub 3} component

Energy Technology Data Exchange (ETDEWEB)

Lee, Ki Rak; Park, Hwan-Seo; Cho, In-Hak; Choi, Jung-Hoon; Eun, Hee-Chul; Lee, Tae-Kyo; Han, Seung Youb; Ahn, Do-Hee [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2017-09-15

SAP (SiO{sub 2}-Al{sub 2}O{sub 3}-P{sub 2}O{sub 5}) composite has been recently studied in KAERI to deal with the immobilization of radioactive salt waste, one of the most problematic wastes in the pyro-chemical process. Highly unstable salt waste was successfully converted into stable compounds by the dechlorination process with SAPs, and then a durable waste form with a high waste loading was produced when adding glassy materials to dechlorination product. In the present study, U-SAP composite which is SAP bearing glassy component (Boron) was synthesized to remove the adding and mixing steps of glassy materials for a monolithic wasteform. With U-SAPs prepared by a sol-gel process, a series of wasteforms were fabricated to identify a proper reaction condition. Physical and chemical properties of dechlorination products and U-SAP wasteforms were characterized by XRD, DSC, SEM, TGA and PCT-A. A U-SAP wasteform showed suitable properties as a radioactive wasteform such as dense surface morphology, high waste loading, and high durability at the optimized U-SAP/salt ratio 2.

Biosupported Bimetallic Pd Au Nanocatalysts for Dechlorination of Environmental Contaminants

Energy Technology Data Exchange (ETDEWEB)

De Corte, S.; Fitts, J.; Hennebel, T.; Sabbe, T.; Bliznuk, V.; Verschuere, S.; van der Lelie, D.; Verstraete, W.; Boon, N.

2011-08-30

Biologically produced monometallic palladium nanoparticles (bio-Pd) have been shown to catalyze the dehalogenation of environmental contaminants, but fail to efficiently catalyze the degradation of other important recalcitrant halogenated compounds. This study represents the first report of biologically produced bimetallic Pd/Au nanoparticle catalysts. The obtained catalysts were tested for the dechlorination of diclofenac and trichloroethylene. When aqueous bivalent Pd(II) and trivalent Au(III) ions were both added to concentrations of 50 mg L{sup -1} and reduced simultaneously by Shewanella oneidensis in the presence of H{sub 2}, the resulting cell-associated bimetallic nanoparticles (bio-Pd/Au) were able to dehalogenate 78% of the initially added diclofenac after 24 h; in comparison, no dehalogenation was observed using monometallic bio-Pd or bio-Au. Other catalyst-synthesis strategies did not show improved dehalogenation of TCE and diclofenac compared with bio-Pd. Synchrotron-based X-ray diffraction, (scanning) transmission electron microscopy and energy dispersive X-ray spectroscopy indicated that the simultaneous reduction of Pd and Au supported on cells of S. oneidensis resulted in the formation of a unique bimetallic crystalline structure. This study demonstrates that the catalytic activity and functionality of possibly environmentally more benign biosupported Pd-catalysts can be improved by coprecipitation with Au.

Diverse Reductive Dehalogenases Are Associated with Clostridiales-Enriched Microcosms Dechlorinating 1,2-Dichloroethane

KAUST Repository

Merlino, Giuseppe; Balloi, Annalisa; Marzorati, Massimo; Mapelli, Francesca; Rizzi, Aurora; Lavazza, Davide; de Ferra, Francesca; Carpani, Giovanna; Daffonchio, Daniele

2015-01-01

The achievement of successful biostimulation of active microbiomes for the cleanup of a polluted site is strictly dependent on the knowledge of the key microorganisms equipped with the relevant catabolic genes responsible for the degradation process. In this work, we present the characterization of the bacterial community developed in anaerobic microcosms after biostimulation with the electron donor lactate of groundwater polluted with 1,2-dichloroethane (1,2-DCA). Through a multilevel analysis, we have assessed (i) the structural analysis of the bacterial community; (ii) the identification of putative dehalorespiring bacteria; (iii) the characterization of functional genes encoding for putative 1,2-DCA reductive dehalogenases (RDs). Following the biostimulation treatment, the structure of the bacterial community underwent a notable change of the main phylotypes, with the enrichment of representatives of the order Clostridiales . Through PCR targeting conserved regions within known RD genes, four novel variants of RDs previously associated with the reductive dechlorination of 1,2-DCA were identified in the metagenome of the Clostridiales-dominated bacterial community.

Diverse Reductive Dehalogenases Are Associated with Clostridiales-Enriched Microcosms Dechlorinating 1,2-Dichloroethane

KAUST Repository

Merlino, Giuseppe

2015-03-06

The achievement of successful biostimulation of active microbiomes for the cleanup of a polluted site is strictly dependent on the knowledge of the key microorganisms equipped with the relevant catabolic genes responsible for the degradation process. In this work, we present the characterization of the bacterial community developed in anaerobic microcosms after biostimulation with the electron donor lactate of groundwater polluted with 1,2-dichloroethane (1,2-DCA). Through a multilevel analysis, we have assessed (i) the structural analysis of the bacterial community; (ii) the identification of putative dehalorespiring bacteria; (iii) the characterization of functional genes encoding for putative 1,2-DCA reductive dehalogenases (RDs). Following the biostimulation treatment, the structure of the bacterial community underwent a notable change of the main phylotypes, with the enrichment of representatives of the order Clostridiales . Through PCR targeting conserved regions within known RD genes, four novel variants of RDs previously associated with the reductive dechlorination of 1,2-DCA were identified in the metagenome of the Clostridiales-dominated bacterial community.

Reductive dechlorination of trichloroacetic acid (TCAA) by electrochemical process over Pd-In/Al_2O_3 catalyst

International Nuclear Information System (INIS)

Liu, Yanzhen; Mao, Ran; Tong, Yating; Lan, Huachun; Zhang, Gong; Liu, Huijuan; Qu, Jiuhui

2017-01-01

Highlights: • TCAA was efficiently removed by Pd-In/Al_2O_3 based electro-reductive process. • The active species for TCAA electroreduction involved electron (e"−) and atomic H*. • The atomic H* played a major contribution to TCAA removal. - Abstract: Electrochemical reduction treatment was found to be a promising method for dechlorination of Trichloroacetic acid (TCAA), and acceleration of electron transfer or enhancement of the concentration of atomic H* significantly improve the electrochemical dechlorination process. Bimetallic Pd-based catalysts have the unique property of simultaneously catalyzing the production of atomic H* and reducing target pollutants. Herein, a bimetallic Pd–In electrocatalyst with atomic ratio of 1:1 was evenly deposited on an Al_2O_3 substrate, and the bimetallic Pd-In structure was confirmed via X-ray photoelectron spectroscopy (XPS). Electrochemical removal of trichloroacetic acid (TCAA) by the Pd-In/Al_2O_3 catalyst was performed in a three-dimensional reactor. 94% of TCAA with the initial concentration of 500 μg L"−"1 could be degraded within 30 min under a relatively low current density (0.9 mA cm"−"2). In contrast to the presence of refractory intermediates (dichloroacetic acid (DCAA)) found in the Pd/Al_2O_3 system, TCAA could be thoroughly reduced to monochloroacetic acid (MCAA) using Pd-In/Al_2O_3 catalysts. According to scavenger experiments, an electron transfer process and atomic H* formation function both existed in the TCAA reduction process, and the enhanced indirect atomic H* reduction process (confirmed by ESR signals) played a chief role in the TCAA removal. Moreover, the synergistic effects of Pd and In were proven to be able to enhance both direct electron transfer and indirect atomic H* formation, indicating a promising prospect for bimetallic electrochemical reduction treatment.

Characteristics of dechlorination for LiCl salt by the surface temperature-controlled reactor

Energy Technology Data Exchange (ETDEWEB)

Cho, In Hak [Chungnam National University, Daejeon (Korea, Republic of); Park, Hwan Seo; Ahn, Soo Na; Eun, Hee Chul; Kim, In Tae; Cho, Yong Jun [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2011-05-15

Molten salt waste is generated from a pyrochemical process to separate reusable U and TRU elements from a spent nuclear fuel. The spent lithium chloride waste is highly soluble in water and contains volatile radioactive elements such as Cs. However, these wastes are difficult to directly immobilize into durable matrix such as glass or ceramic wasteform for final disposal. ANL(Argonne National Laboratory) suggested the conversion of metal chloride into a sodalite for the immobilization of a chloride waste, glass-bonded sodalite, which was fabricated at about 915 .deg. C after mixing the salt-loaded zeolite and borosilicate glass powder. Although this wasteform shows high leach-resistance, the waste volume greatly increases. The previous study was to treat metal chloride wastes by using SAP(SiO{sub 2}-Al{sub 2}O{sub 3}-P{sub 2}O{sub 5}) materials. By using this method, the final waste volume reduced and leach-resistance was good. In this study, characteristics of dechlorination reaction of LiCl with an inorganic composite, SAP, was investigated by using a specific surface temperature-controlled reactor

Characterization of natural anaerobic dechlorination of TCE and 1,1,1-TCA in clay till including isotope fractionation and molecular biological tools

DEFF Research Database (Denmark)

Damgaard, Ida; Bælum, J.; Hunkeler, D.

2010-01-01

One of the major challenges when using enhanced reductive dechlorination (ERD) as a remediation technology at clay till sites is to obtain good contact between added agents such as donor, bacteria and the contamination. It is unclear whether degradation only takes place in fractures and/or sand l...... including the location of degradation in the fracture matrix geology. An extensive field collection of cores and discrete soil sampling has been conducted and samples have been analysed using state of the art microbial and chemical tools including isotope fractionation....

Dechlorination of PCBs, CAHs, herbicides and pesticides neat and in soils at 25 degrees C using Na/NH3.

Science.gov (United States)

Pittman, Charles U; He, Jinbao

2002-05-03

Na/NH3 reductions have been used to dehalogenate polychlorinated biphenyls (PCBs), chlorinated aliphatic hydrocarbons (CAHs) and pesticides at diffusion controlled rates at room temperature in model compound studies in both dry NH3 and when water was added. The rate ratio of dechlorination (aliphatic and aromatic compounds) versus reaction of the solvated electron with water is very large, allowing wet soils or sludges to be remediated without an unreasonable consumption of sodium. Several soils, purposely contaminated with 1,1,1-trichloroethane, 1-chlorooctane and tetrachloroethylene, were remediated by slurring the soils in NH3 followed by addition of sodium. The consumption of sodium per mole of chlorine removed was examined as a function of both the hazardous substrate's concentration in the soil and the amount of water present. The Na consumption per Cl removed increases as the amount of water increases and as the substrate concentration in soil decreases. However, remediation was still readily accomplished from 5000 to 3000ppm to sub ppm levels of RCl in the presence of substantial amounts of water. PCB- and dioxin-contaminated oils were remediated with Na/NH3 as were PCB-contaminated soils and sludges from contaminated sites. Ca/NH3 treatments also successfully remediated PCB-contaminated clay, sandy and organic soils but laboratory studies demonstrated that Ca was less efficient than Na when substantial amounts of water were present. The advantages of solvated electron reductions using Na/NH3 include: (1) very rapid dehalogenation rates at ambient temperature, (2) soils (even clay soils) break down into particles and slurry nicely in NH3, (3) liquid ammonia handling technology is well known and (4) removal from soils, recovery and recycle of ammonia is easy due to its low boiling point. Finally, dechlorination is extremely fast even for the 'corner' chlorines in the substrate Mirex (structure in Eq. (5)).

Simulation Of Enhanced Reductive Dechlorination For Remediation Of Tce In A Fractured Clay System: A New Model Approach And Application To Field Site

DEFF Research Database (Denmark)

Manoli, Gabriele; Chambon, Julie Claire Claudia; Christiansen, Camilla Maymann

2010-01-01

with interspersed sand lenses and stringers. The transport model couples diffusion dominated transport in the clay matrix, with advective‐dispersive transport in the fractures and higher permeability sand lenses. The reactive model calculates sequential reductive dechlorination of TCE (trichloroethylene) to its...... a contamination of trichloroethylene located in a fractured clay till. The site is simulated using the model developed. Fracture geometry, site parameters and degradation rates are based on observations from the site and lab studies. The risk for drinking water is assessed and cleanup times are simulated using...

Identification of abiotic and biotic reductive dechlorination in a chlorinated ethene plume after thermal source remediation by means of isotopic and molecular biology tools

DEFF Research Database (Denmark)

Badin, Alice; Broholm, Mette Martina; Jacobsen, Carsten S.

2016-01-01

-Cl isotope analysis together with the almost absent VC 13C depletion in comparison to cDCE 13C depletion suggested that cDCE was subject to abiotic degradation due to the presence of pyrite, possible surface-bound iron (II) or reduced iron sulphides in the downgradient part of the plume. This interpretation...... reduced redox conditions which favor active reductive dechlorination and/or may lead to a series of redox reactions which may consecutively trigger biotically induced abiotic degradation. Finally, this study illustrates the valuable complementary application of compound-specific isotopic analysis combined...

Potential of isotope analysis (C, Cl) to identify dechlorination mechanisms

Science.gov (United States)

Cretnik, Stefan; Thoreson, Kristen; Bernstein, Anat; Ebert, Karin; Buchner, Daniel; Laskov, Christine; Haderlein, Stefan; Shouakar-Stash, Orfan; Kliegman, Sarah; McNeill, Kristopher; Elsner, Martin

2013-04-01

Chloroethenes are commonly used in industrial applications, and detected as carcinogenic contaminants in the environment. Their dehalogenation is of environmental importance in remediation processes. However, a detailed understanding frequently accounted problem is the accumulation of toxic degradation products such as cis-dichloroethylene (cis-DCE) at contaminated sites. Several studies have addressed the reductive dehalogenation reactions using biotic and abiotic model systems, but a crucial question in this context has remained open: Do environmental transformations occur by the same mechanism as in their corresponding in vitro model systems? The presented study shows the potential to close this research gap using the latest developments in compound specific chlorine isotope analysis, which make it possible to routinely measure chlorine isotope fractionation of chloroethenes in environmental samples and complex reaction mixtures.1,2 In particular, such chlorine isotope analysis enables the measurement of isotope fractionation for two elements (i.e., C and Cl) in chloroethenes. When isotope values of both elements are plotted against each other, different slopes reflect different underlying mechanisms and are remarkably insensitive towards masking. Our results suggest that different microbial strains (G. lovleyi strain SZ, D. hafniense Y51) and the isolated cofactor cobalamin employ similar mechanisms of reductive dechlorination of TCE. In contrast, evidence for a different mechanism was obtained with cobaloxime cautioning its use as a model for biodegradation. The study shows the potential of the dual isotope approach as a tool to directly compare transformation mechanisms of environmental scenarios, biotic transformations, and their putative chemical lab scale systems. Furthermore, it serves as an essential reference when using the dual isotope approach to assess the fate of chlorinated compounds in the environment.

Two dechlorinated chlordecone derivatives formed by in situ chemical reduction are devoid of genotoxicity and mutagenicity and have lower proangiogenic properties compared to the parent compound.

Science.gov (United States)

Legeay, Samuel; Billat, Pierre-André; Clere, Nicolas; Nesslany, Fabrice; Bristeau, Sébastien; Faure, Sébastien; Mouvet, Christophe

2018-05-01

Chlordecone (CLD) is a chlorinated hydrocarbon insecticide, now classified as a persistent organic pollutant. Several studies have previously reported that chronic exposure to CLD leads to hepatotoxicity, neurotoxicity, raises early child development and pregnancy complications, and increases the risk of liver and prostate cancer. In situ chemical reduction (ISCR) has been identified as a possible way for the remediation of soils contaminated by CLD. In the present study, the objectives were (i) to evaluate the genotoxicity and the mutagenicity of two CLD metabolites formed by ISCR, CLD-5a-hydro, or CLD-5-hydro (5a- or 5- according to CAS nomenclature; CLD-1Cl) and tri-hydroCLD (CLD-3Cl), and (ii) to explore the angiogenic properties of these molecules. Mutagenicity and genotoxicity were investigated using the Ames's technique on Salmonella typhimurium and the in vitro micronucleus micromethod with TK6 human lymphoblastoid cells. The proangiogenic properties were evaluated on the in vitro capillary network formation of human primary endothelial cells. Like CLD, the dechlorinated derivatives of CLD studied were devoid of genotoxic and mutagenic activity. In the assay targeting angiogenic properties, significantly lower microvessel lengths formed by endothelial cells were observed for the CLD-3Cl-treated cells compared to the CLD-treated cells for two of the three tested concentrations. These results suggest that dechlorinated CLD derivatives are devoid of mutagenicity and genotoxicity and have lower proangiogenic properties than CLD.

Dechlorination of polychlorinated biphenyls by iron and its oxides.

Science.gov (United States)

Sun, Yifei; Liu, Xiaoyuan; Kainuma, Masashi; Wang, Wei; Takaoka, Masaki; Takeda, Nobuo

2015-10-01

The decomposition efficiency of polychlorinated biphenyls (PCBs) was determined using elemental iron (Fe) and three iron (hydr)oxides, i.e., α-Fe2O3, Fe3O4, and α-FeOOH, as catalysts. The experiments were performed using four distinct PCB congeners (PCB-209, PCB-153, and the coplanar PCB-167 and PCB-77) at temperatures ranging from 180 °C to 380 °C and under an inert, oxidizing or reducing atmosphere composed of N2, N2+O2, or N2+H2. From these three options N2 showed to provide the best reaction atmosphere. Among the iron compounds tested, Fe3O4 showed the highest activity for decomposing PCBs. The decomposition efficiencies of PCB-209, PCB-167, PCB-153, and PCB-77 by Fe3O4 in an N2 atmosphere at 230 °C were 88.5%, 82.5%, 69.9%, and 66.4%, respectively. Other inorganic chlorine (Cl) products which were measured by the amount of inorganic Cl ions represented 82.5% and 76.1% of the reaction products, showing that ring cleavage of PCBs was the main elimination process. Moreover, the dechlorination did not require a particular hydrogen donor. We used X-ray photoelectron spectroscopy to analyze the elemental distribution at the catalyst's surface. The O/Fe ratio influenced upon the decomposition efficiency of PCBs: the lower this ratio, the higher the decomposition efficiency. X-ray absorption near edge structure spectra showed that α-Fe2O3 effectively worked as a catalyst, while Fe3O4 and α-FeOOH were consumed as reactants, as their final state is different from their initial state. Finally, a decomposition pathway was postulated in which the Cl atoms in ortho-positions were more difficult to eliminate than those in the para- or meta-positions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Chlorinated Electron Acceptor Abundance Drives Selection of Dehalococcoides mccartyi (D. mccartyi Strains in Dechlorinating Enrichment Cultures and Groundwater Environments

Directory of Open Access Journals (Sweden)

Alfredo Pérez-de-Mora

2018-05-01

Full Text Available Dehalococcoides mccartyi (D. mccartyi strains differ primarily from one another by the number and identity of the reductive dehalogenase homologous catalytic subunit A (rdhA genes within their respective genomes. While multiple rdhA genes have been sequenced, the activity of the corresponding proteins has been identified in only a few cases. Examples include the enzymes whose substrates are groundwater contaminants such as trichloroethene (TCE, cis-dichloroethene (cDCE and vinyl chloride (VC. The associated rdhA genes, namely tceA, bvcA, and vcrA, along with the D. mccartyi 16S rRNA gene are often used as biomarkers of growth in field samples. In this study, we monitored an additional 12 uncharacterized rdhA sequences identified in the metagenome in the mixed D. mccartyi-containing culture KB-1 to monitor population shifts in more detail. Quantitative PCR (qPCR assays were developed for 15 D. mccartyi rdhA genes and used to measure population diversity in 11 different sub-cultures of KB-1, each enriched on different chlorinated ethenes and ethanes. The proportion of rdhA gene copies relative to D. mccartyi 16S rRNA gene copies revealed the presence of multiple distinct D. mccartyi strains in each culture, many more than the two strains inferred from 16S rRNA analysis. The specific electron acceptor amended to each culture had a major influence on the distribution of D. mccartyi strains and their associated rdhA genes. We also surveyed the abundance of rdhA genes in samples from two bioaugmented field sites (Canada and United Kingdom. Growth of the dominant D. mccartyi strain in KB-1 was detected at the United Kingdom site. At both field sites, the measurement of relative rdhA abundances revealed D. mccartyi population shifts over time as dechlorination progressed from TCE through cDCE to VC and ethene. These shifts indicate a selective pressure of the most abundant chlorinated electron acceptor, as was also observed in lab cultures. These

Enhanced dechlorination of trichloroethylene using electrospun polymer nanofibrous mats immobilized with iron/palladium bimetallic nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Ma, Hui [State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai 201620 (China); College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620 (China); Huang, Yunpeng; Shen, Mingwu; Guo, Rui; Cao, Xueyan [College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620 (China); Shi, Xiangyang, E-mail: xshi@dhu.edu.cn [State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai 201620 (China); College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620 (China); CQM - Centro de Quimica da Madeira, Universidade da Madeira, Campus da Penteada, 9000-390 Funchal (Portugal)

2012-04-15

Fe/Pd bimetallic nanoparticles (NPs) have held great promise for treating trichloroethylene (TCE)-contaminated groundwater, without the accumulation of chlorinated intermediates. However, the conventionally used colloidal Fe/Pd NPs usually aggregate rapidly, resulting in a reduced reactivity. To reduce the particle aggregation, we employed electrospun polyacrylic acid (PAA)/polyvinyl alcohol (PVA) polymer nanofibers as a nanoreactor to immobilize Fe/Pd bimetallic NPs. In the study, the water-stable PAA/PVA nanofibrous mats were complexed with Fe (III) ions via the binding with the free carboxyl groups of PAA for subsequent formation and immobilization of zero-valent iron (ZVI) NPs. Fe/Pd bimetallic NPs were then formed by the partial reduction of Pd(II) ions with ZVI NPs. The formed electrospun nanofibrous mats containing Fe/Pd bimetallic NPs with a diameter of 2.8 nm were characterized by scanning electron microscopy, energy-dispersive spectroscopy, transmission electron microscopy, thermogravimetric analysis, and inductively coupled plasma-atomic emission spectroscopy. The Fe/Pd NP-containing electrospun PAA/PVA nanofibrous mats exhibited higher reactivity than that of the ZVI NP-containing mats or colloidal Fe/Pd NPs in the dechlorination of trichloroethylene (TCE), which was used as a model contaminant. With the high surface area to volume ratio, high porosity, and great reusability of the fibrous mats immobilized with the bimetallic NPs, the composite nanofibrous mats should be amenable for applications in remediation of various environmental contaminants.

Enhanced dechlorination of trichloroethylene using electrospun polymer nanofibrous mats immobilized with iron/palladium bimetallic nanoparticles

International Nuclear Information System (INIS)

Ma, Hui; Huang, Yunpeng; Shen, Mingwu; Guo, Rui; Cao, Xueyan; Shi, Xiangyang

2012-01-01

Fe/Pd bimetallic nanoparticles (NPs) have held great promise for treating trichloroethylene (TCE)-contaminated groundwater, without the accumulation of chlorinated intermediates. However, the conventionally used colloidal Fe/Pd NPs usually aggregate rapidly, resulting in a reduced reactivity. To reduce the particle aggregation, we employed electrospun polyacrylic acid (PAA)/polyvinyl alcohol (PVA) polymer nanofibers as a nanoreactor to immobilize Fe/Pd bimetallic NPs. In the study, the water-stable PAA/PVA nanofibrous mats were complexed with Fe (III) ions via the binding with the free carboxyl groups of PAA for subsequent formation and immobilization of zero-valent iron (ZVI) NPs. Fe/Pd bimetallic NPs were then formed by the partial reduction of Pd(II) ions with ZVI NPs. The formed electrospun nanofibrous mats containing Fe/Pd bimetallic NPs with a diameter of 2.8 nm were characterized by scanning electron microscopy, energy-dispersive spectroscopy, transmission electron microscopy, thermogravimetric analysis, and inductively coupled plasma-atomic emission spectroscopy. The Fe/Pd NP-containing electrospun PAA/PVA nanofibrous mats exhibited higher reactivity than that of the ZVI NP-containing mats or colloidal Fe/Pd NPs in the dechlorination of trichloroethylene (TCE), which was used as a model contaminant. With the high surface area to volume ratio, high porosity, and great reusability of the fibrous mats immobilized with the bimetallic NPs, the composite nanofibrous mats should be amenable for applications in remediation of various environmental contaminants.

Investigation of mechanisms of dechlorination of archaeological ferrous objects corroded in marine environment. Case of processing in aerated and deaerated alkaline solutions

International Nuclear Information System (INIS)

Kergourlay, Florian

2012-01-01

After a bibliographic study on the present knowledge on dechlorination mechanisms within corrosion layers of archaeological objects of submarine origin, this research thesis presents an analytical methodology which comprises characterization experimental techniques (from optical microscopy to Raman spectroscopy) and in situ investigation of the evolution of the corrosion layer during a processing under synchrotron radiation. The obtained results are then presented and discussed: morphological, elemental and structural characteristics. The author also compares the corrosion system between an object recently taken out of water and an object which has been air dried. He also comments and discusses the in situ observation by X ray diffraction under micro-beam of the evolution of the corrosion system during the processing. The ex situ characterization of corrosion systems after the rinsing and drying steps (after processing) is reported. Results are discussed in terms of thermodynamics. A kinetic approach is proposed

Defining the sources of airborne polychlorinated biphenyls: evidence for the influence of microbially dechlorinated congeners from river sediment?

Energy Technology Data Exchange (ETDEWEB)

Chiarenzelli, J. [SUNYat Oswego, NY (United States); Bush, B.; Casey, A.; O' Keefe, P. [SUNY at Albany, School of Public Health, Rensselaer, NY (United States); Barnard, E.; Smith, B. [New York State Dept. of Health, Wadsworth Center for Laboratories and Research, Albany, NY (United States); Gilligan, E. [Syracuse Univ., Dept. of Civil an Environmental Engineering, NY (United States); Johnson, G. [Energy and Geoscience Institute, Dept, of Civil and Environmental Engineering, Salt Lake City, UT (United States)

2000-07-01

During sampling in 1993, elevated levels of polychlorinated biphenyls were discovered near three industrial facilities on the Akwesasne Mohawk Nation Reserve along the St. Lawrence River, straddling the Canadian-US. border. Volatilization of Aroclor 1248, which was used extensively at all three sites, was identified as the dominant source, augmented in a minor way by a dechlorinated source, presumably from river sediment and waters. These two sources were found to account for 80 per cent of the contamination. Further, it was established that at a small cove adjacent to an industrial landfill, summer concentrations of PCBs exceeded winter concentrations by a factor of 27. Observation showed the presence of similar congener-specific PCB patterns at all sample sites and an increase in the concentrations of chlorine to biphenyl ratios during the summer months. During the colder months PCB concentrations at all sites declined, nevertheless, PCB levels were still higher than those measured elsewhere in the Great Lakes region during the same time period. Results of this investigation suggest that atmospheric deposition from local contaminant sources can elevate concentrations in produce and vegetative matter, complicating exposure routes and bioaccumulation via modeling of food chain. 22 refs., 4 tabs. 1 fig.

Identification of abiotic and biotic reductive dechlorination in a chlorinated ethene plume after thermal source remediation by means of isotopic and molecular biology tools

DEFF Research Database (Denmark)

Badin, Alice; Broholm, Mette Martina; Jacobsen, Carsten S.

2016-01-01

Thermal tetrachloroethene (PCE) remediation by steam injection in a sandy aquifer led to the release of dissolved organic carbon (DOC) from aquifer sediments resulting in more reduced redox conditions, accelerated PCE biodegradation, and changes in microbial populations. These changes were...... documented by comparing data collected prior to the remediation event and eight years later. Based on the premise that dual C-Cl isotope slopes reflect ongoing degradation pathways, the slopes associated with PCE and TCE suggest the predominance of biotic reductive dechlorination near the source area. PCE...... is supported by the relative lack of Dhc in the downgradient part of the plume. The results of this study show that thermal remediation can enhance the biodegradation of chlorinated ethenes, and that this effect can be traced to the mobilisation of DOC due to steam injection. This, in turn, results in more...

Reactive Minerals and Dechlorinating Communities: Mechanisms Governing the Degradation of Chlorinated Ethenes during Back Diffusion from Low Permeability Zones in Aerobic and Anaerobic Environments

Science.gov (United States)

Berns, E. C.; Zeng, R.; Singh, H.; Valocchi, A. J.; Sanford, R. A.; Strathmann, T. J.; Schaefer, C. E.; Werth, C. J.

2017-12-01

Low permeability zones (LPZs) comprised of silts and clays, and contaminated with chlorinated ethenes, can act as a long term source of contaminated groundwater by diffusion into adjacent high permeability zones (HPZs). Following initial remediation efforts, chlorinated ethenes that have diffused into LPZs will back diffuse and recontaminate HPZs. Because chlorinated ethenes are known to cause cancer and damage the liver, kidneys, and central nervous system, it is important to understand how they degrade in natural systems and how to model their fate and transport. Previous work has shown that anaerobic hydrogenolysis reactions are facilitated by both dechlorinating microorganisms and reactive minerals. Abiotic dichloro-elimination reactions with reactive minerals can also degrade chlorinated ethenes to acetylene, albeit at slower rates than biotic processes. More recently, studies have explored aerobic abiotic degradation of chlorinated ethenes to formate, glycolate, and carbon dioxide. This study focuses on these biotic and abiotic reactions and their contributions to chlorinated ethene degradation under aerobic and anaerobic conditions at the LPZ/HPZ interface. A two-dimensional flow cell was constructed to model this interface using clay and sand from Pease Air Force Base. The clay was inoculated with a dechlorinating enrichment culture. Tenax adsorbent beads equilibrated with trichloroethylene (TCE) were used as a chlorinated ethene source zone at the base of the clay. TCE and its degradation products diffused from the clay into the sand, where they were removed from the flow cell by groundwater at a rate of 50 mL/day. Volatile compounds were trapped in a sample loop and removed every 48 hours for analysis by GC-FID. Organic and inorganic ions in the effluent were analyzed on the HPLC and IC. The experiment was terminated by freezing the flow cell, and chemical profiles through the flow cell material were created to show the spatial distribution of degradation

Consequence assessment for Airborne Releases of SO2 from the Y-12 Pilot Dechlorination Facility

International Nuclear Information System (INIS)

Pendergrass, W.R.

1992-06-01

The Atmospheric Turbulence and Diffusion Division was requested by the Department of Energy's Oak Ridge Operations Office to conduct a consequence assessment for potential atmospheric releases of SO 2 from the Y-12 Pilot Dechlorination Facility. The focus of the assessment was to identify ''worst'' case meteorology which posed the highest concentration exposure potential for both on-site as well as off-site populations. A series of plausible SO 2 release scenarios were provided by Y-12 for the consequence assessment. Each scenario was evaluated for predictions of downwind concentration, estimates of a five-minute time weighted average, and estimate of the dimension of the puff. The highest hazard potential was associated with Scenario 1, in which a total of eight SO 2 cylinders are released internally to the Pilot Facility and exhausted through the emergency venting system. A companion effort was also conducted to evaluate the potential for impact of releases of SO 2 from the Pilot Facility on the population of Oak Ridge. While specific transport trajectory data is not available for the Pilot Facility, extrapolations based on the Oak Ridge Site Survey and climatological records from the Y-12 meteorological program does not indicate the potential for impact on the city of Oak Ridge. Steering by the local topographical features severely limits the potential impact ares. Due to the lack of specific observational data, both tracer and meteorological, only inferences can be made concerning impact zones. It is recommended tat the Department of Energy Oak Ridge Operations examine the potential for off-site impact and develop the background data to prepare impact zones for releases of hazardous materials from the Y-12 facility

Modeling 3D-CSIA data: Carbon, chlorine, and hydrogen isotope fractionation during reductive dechlorination of TCE to ethene.

Science.gov (United States)

Van Breukelen, Boris M; Thouement, Héloïse A A; Stack, Philip E; Vanderford, Mindy; Philp, Paul; Kuder, Tomasz

2017-09-01

Reactive transport modeling of multi-element, compound-specific isotope analysis (CSIA) data has great potential to quantify sequential microbial reductive dechlorination (SRD) and alternative pathways such as oxidation, in support of remediation of chlorinated solvents in groundwater. As a key step towards this goal, a model was developed that simulates simultaneous carbon, chlorine, and hydrogen isotope fractionation during SRD of trichloroethene, via cis-1,2-dichloroethene (and trans-DCE as minor pathway), and vinyl chloride to ethene, following Monod kinetics. A simple correction term for individual isotope/isotopologue rates avoided multi-element isotopologue modeling. The model was successfully validated with data from a mixed culture Dehalococcoides microcosm. Simulation of Cl-CSIA required incorporation of secondary kinetic isotope effects (SKIEs). Assuming a limited degree of intramolecular heterogeneity of δ 37 Cl in TCE decreased the magnitudes of SKIEs required at the non-reacting Cl positions, without compromising the goodness of model fit, whereas a good fit of a model involving intramolecular CCl bond competition required an unlikely degree of intramolecular heterogeneity. Simulation of H-CSIA required SKIEs in H atoms originally present in the reacting compounds, especially for TCE, together with imprints of strongly depleted δ 2 H during protonation in the products. Scenario modeling illustrates the potential of H-CSIA for source apportionment. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Dechlorination of chloropicrin and 1,3-dichloropropene by hydrogen sulfide species: redox and nucleophilic substitution reactions.

Science.gov (United States)

Zheng, Wei; Yates, Scott R; Papiernik, Sharon K; Guo, Mingxin; Gan, Jianying

2006-03-22

The chlorinated fumigants chloropicrin (trichloronitromethane) and 1,3-dichloropropene (1,3-D) are extensively used in agricultural production for the control of soilborne pests. The reaction of these two fumigants with hydrogen sulfide species (H2S and HS-) was examined in well-defined anoxic aqueous solutions. Chloropicrin underwent an extremely rapid redox reaction in the hydrogen sulfide solution. Transformation products indicated reductive dechlorination of chloropicrin by hydrogen sulfide species to produce dichloro- and chloronitromethane. The transformation of chloropicrin in hydrogen sulfide solution significantly increased with increasing pH, indicating that H2S is less reactive toward chloropicrin than HS- is. For both 1,3-D isomers, kinetics and transformation products analysis revealed that the reaction between 1,3-D and hydrogen sulfide species is an S(N)2 nucleophilic substitution process, in which the chlorine at C3 of 1,3-D is substituted by the sulfur nucleophile to form corresponding mercaptans. The 50% disappearance time (DT50) of 1,3-D decreased with increasing hydrogen sulfide species concentration at a constant pH. Transformation of 1,3-D was more rapid at high pH, suggesting that the reactivity of hydrogen sulfide species in the experimental system stems primarily from HS-. Because of the relatively low smell threshold values and potential environmental persistence of organic sulfur products yielded by the reaction of 1,3-D and HS-, the effects of reduced sulfide species should be considered in the development of alternative fumigation practices, especially in the integrated application of sulfur-containing fertilizers.

Successful operation of continuous reactors at short retention times results in high-density, fast-rate Dehalococcoides dechlorinating cultures.

Science.gov (United States)

Delgado, Anca G; Fajardo-Williams, Devyn; Popat, Sudeep C; Torres, César I; Krajmalnik-Brown, Rosa

2014-03-01

The discovery of Dehalococcoides mccartyi reducing perchloroethene and trichloroethene (TCE) to ethene was a key landmark for bioremediation applications at contaminated sites. D. mccartyi-containing cultures are typically grown in batch-fed reactors. On the other hand, continuous cultivation of these microorganisms has been described only at long hydraulic retention times (HRTs). We report the cultivation of a representative D. mccartyi-containing culture in continuous stirred-tank reactors (CSTRs) at a short, 3-d HRT, using TCE as the electron acceptor. We successfully operated 3-d HRT CSTRs for up to 120 days and observed sustained dechlorination of TCE at influent concentrations of 1 and 2 mM TCE to ≥ 97 % ethene, coupled to the production of 10(12) D. mccartyi cells Lculture (-1). These outcomes were possible in part by using a medium with low bicarbonate concentrations (5 mM) to minimize the excessive proliferation of microorganisms that use bicarbonate as an electron acceptor and compete with D. mccartyi for H2. The maximum conversion rates for the CSTR-produced culture were 0.13 ± 0.016, 0.06 ± 0.018, and 0.02 ± 0.007 mmol Cl(-) Lculture (-1) h(-1), respectively, for TCE, cis-dichloroethene, and vinyl chloride. The CSTR operation described here provides the fastest laboratory cultivation rate of high-cell density Dehalococcoides cultures reported in the literature to date. This cultivation method provides a fundamental scientific platform for potential future operations of such a system at larger scales.

Influence of physical factors and geochemical conditions on groundwater acidification during enhanced reductive dechlorination

Science.gov (United States)

Brovelli, A.; Barry, D. A.; Robinson, C.; Gerhard, J.

2010-12-01

Enhanced reductive dehalogenation is an attractive in situ treatment technology for chlorinated contaminants. The process includes two acid-forming microbial reactions: fermentation of an organic substrate resulting in short-chain fatty acids, and dehalogenation resulting in hydrochloric acid. The accumulation of acids and the resulting drop of groundwater pH are controlled by the mass and distribution of chlorinated solvents in the source zone, type of electron donor, availability of alternative terminal electron acceptors and presence of soil mineral phases able to buffer the pH (such as carbonates). Groundwater acidification may reduce or halt microbial activity, and thus dehalogenation, significantly increasing the time and costs required to remediate the aquifer. For this reason, research in this area is gaining increasing attention. In previous work (Robinson et al., 2009 407:4560, Sci. Tot. Environ, Robinson and Barry, 2009 24:1332, Environ. Model. & Software, Brovelli et al., 2010, submitted), a detailed geochemical and groundwater flow model able to predict the pH change occurring during reductive dehalogenation was developed. The model accounts for the main processes influencing groundwater pH, including the groundwater composition, the electron donor used and soil mineral phase interactions. In this study, the model was applied to investigate how spatial variability occurring at the field scale affects groundwater pH and dechlorination rates. Numerical simulations were conducted to examine the influence of heterogeneous hydraulic conductivity on the distribution of the injected, fermentable substrate and on the accumulation/dilution of the acidic products of reductive dehalogenation. The influence of the geometry of the DNAPL source zone was studied, as well as the spatial distribution of soil minerals. The results of this study showed that the heterogeneous distribution of the soil properties have a potentially large effect on the remediation efficiency

Low and high acetate amendments are equally as effective at promoting complete dechlorination of trichloroethylene (TCE).

Science.gov (United States)

Wei, Na; Finneran, Kevin T

2013-06-01

Experiments with trichloroethylene-contaminated aquifer material demonstrated that TCE, cis-DCE, and VC were completely degraded with concurrent Fe(III) or Fe(III) and sulfate reduction when acetate was amended at stoichiometric concentration; competing TEAPs did not inhibit ethene production. Adding 10× more acetate did not increase the rate or extent of TCE reduction, but only increased methane production. Enrichment cultures demonstrated that ~90 μM TCE or ~22 μM VC was degraded primarily to ethene within 20 days with concurrent Fe(III) or Fe(III) + sulfate reduction. The dechlorination rates were comparable between the low and high acetate concentrations (0.36 vs 0.34 day(-1), respectively), with a slightly slower rate in the 10× acetate amended incubations. Methane accumulated to 13.5 (±0.5) μmol/tube in the TCE-degrading incubations with 10× acetate, and only 1.4 (±0.1) μmol/tube with low acetate concentration. Methane accumulated to 16 (±1.5) μmol/tube in VC-degrading enrichment with 10× acetate and 2 (±0.1) μmol/tube with stoichiometric acetate. The estimated fraction of electrons distributed to methanogenesis increased substantially when excessive acetate was added. Quantitative PCR analysis indicated that 10× acetate did not enhance Dehalococcoides biomass but rather increased the methanogen abundance by nearly one order of magnitude compared to that with stoichiometric acetate. The data suggest that adding low levels of substrate may be equally if not more effective as high concentrations, without producing excessive methane. This has implications for field remediation efforts, in that adding excess electron donor may not benefit the reactions of interest, which in turn will increase treatment costs without direct benefit to the stakeholders.

Dechlorination and chlorine rearrangement of 1,2,5,5,6,9,10-heptachlorodecane mediated by the whole pumpkin seedlings.

Science.gov (United States)

Li, Yanlin; Hou, Xingwang; Yu, Miao; Zhou, Qunfang; Liu, Jiyan; Schnoor, Jerald L; Jiang, Guibin

2017-05-01

Short chain chlorinated paraffins (SCCPs) are ubiquitously present as persistent organic pollutants in the environment. However, little information on the interaction of SCCPs with plants is currently available. In this work, young pumpkin plants (Cucurbita maxima × C. Moschata) were hydroponically exposed to the congener of chlorinated decane, 1,2,5,5,6,9,10-heptachlorodecane (1,2,5,5,6,9,10-HepCD), to investigate the uptake, translocation and transformation of chlorinated decanes in the intact plants. It was found that parent HepCD was taken up by the pumpkin roots, translocated from root to shoots, and phytovolatilized from pumpkin plants to air via the plant transpiration flux. Our data suggested that dechlorination of 1,2,5,5,6,9,10-HepCD to lower chlorinated decanes and rearrangement of chlorine atoms in the molecule were all mediated by the whole pumpkin seedlings. Chlorinated decanes were found in the shoots and roots of blank controls, indicating that chlorinated decanes in the air could be absorbed by leaves and translocated from shoots to roots. Lower chlorinated congeners (C 10 H 17 Cl 5 ) tended to detain in air compared to higher chlorinated congeners (C 10 H 16 Cl 6 and other C 10 H 15 Cl 7 ). Potential transformation pathway and behavior of 1,2,5,5,6,9,10-HepCD in pumpkin were proposed based on these experiments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Carbon, Chlorine, and Hydrogen Isotope Fractionation in Transformation of TCE to Ethene by a Dehalococcoides Culture

NARCIS (Netherlands)

Kuder, T.; van Breukelen, B.M.; Vanderford, M.; Philip, P.

2013-01-01

Carbon (C), chlorine (Cl), and hydrogen (H) isotope effects were determined during dechlorination of TCE to ethene by a mixed Dehalococcoides (Dhc) culture. The C isotope effects for the dechlorination steps were consistent with data published in the past for reductive dechlorination (RD) by Dhc.

Treatment of chlorofluorocarbons in alcohol solutions by γ-irradiation

International Nuclear Information System (INIS)

Shimokawa, Toshinari; Nakagawa, Seiko; Sawai, Teruko

1995-01-01

A study was done on dechlorination of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC113) in neutral and alkaline alcohol solutions by means of γ-irradiation. The dechlorination yield (G (Cl - )) was found to depend on the kind of alcohol used as solvents and the presence of hydroxide ion. The order of G (Cl - ) value in alkaline solution was isopropyl alcohol>> ethyl alcohol > methyl alcohol. It was suggested that the high yield obtained in alkaline isopropyl alcohol solution is explained by a chain process in dechlorination reaction. In case of alkaline isopropyl alcohol solution, CFC113 was dechlorinated to lower chlorinated ethane, and 1,1-dichloro-1,2,2-trifluoroetane was a main product. We have discussed on the chain dechlorination mechanism in alkaline isopropyl alcohol solution. (author)

Treatment of radioactive waste salt by using synthetic silica-based phosphate composite for de-chlorination and solidification

Science.gov (United States)

Cho, In-Hak; Park, Hwan-Seo; Lee, Ki-Rak; Choi, Jung-Hun; Kim, In-Tae; Hur, Jin Mok; Lee, Young-Seak

2017-09-01

In the radioactive waste management, waste salts as metal chloride generated from a pyrochemical process to recover uranium and transuranic elements are one of problematic wastes due to their intrinsic properties such as high volatility and low compatibility with conventional glasses. This study reports a method to stabilize and solidify LiCl waste via de-chlorination using a synthetic composite, U-SAP (SiO2-Al2O3-B2O3-Fe2O3-P2O5) prepared by a sol-gel process. The composite was reacted with alkali metal elements to produce some metal aluminosilicates, aluminophosphates or orthophosphate as a crystalline or amorphous compound. Different from the original SAP (SiO2-Al2O3-P2O5), the reaction product of U-SAP could be successfully fabricated as a monolithic wasteform without a glassy binder at a proper reaction/consolidation condition. From the results of the FE-SEM, FT-IR and MAS-NMR analysis, it could be inferred that the Si-rich phase and P-rich phase as a glassy grains would be distributed in tens of nm scale, where alkali metal elements would be chemically interacted with Si-rich or P-rich region in the virgin U-SAP composite and its products was vitrified into a silicate or phosphate glass after a heat-treatment at 1150 °C. The PCT-A (Product Consistency Test, ASTM-1208) revealed that the mass loss of Cs and Sr in the U-SAP wasteform had a range of 10-3∼10-1 g/m2 and the leach-resistance of the U-SAP wasteform was comparable to other conventional wasteforms. From the U-SAP method, LiCl waste salt was effectively stabilized and solidified with high waste loading and good leach-resistance.

Enhanced reductive de-chlorination of a solvent contaminated aquifer through addition and apparent fermentation of cyclodextrin

Science.gov (United States)

Blanford, William James; Pecoraro, Michael Philip; Heinrichs, Rebecca; Boving, Thomas Bernhard

2018-01-01

In a field study, aqueous cyclodextrin (CD) was investigated for its ability to extract chlorinated volatile organic compounds (cVOC), such as trichloroethylene (TCE), 1,1,1-trichloroethane (TCA), and dichloroethene (DCE) through in-situ flushing of a sandy aquifer. After cessation of aquifer flushing, a plume of CD was left. Changes in CD, cVOC, and inorganic terminal electron acceptors (TEAs) (DO, nitrate, sulfate, iron) were monitored in four rounds of wellwater sampling (20, 210, 342, and 425 days after cessation of active pumping). Post-CD flushing VOC levels rebounded (850% for TCE, 190% for TCA, and 53% for DCE) between the first two sampling rounds, apparently due to rate-limited desorption from aquifer media and dissolution from remaining NAPL. However, substantial reduction in the mass of TCE (6.3 to 0.11 mol: 98%) and TCA (2.8 to 0.73 mol: 74%) in groundwater was observed between 210 and 425 days. DCE should primarily be produced from the degradation of TCE and is expected to subsequently degrade to chloroethene. Since DCE levels decreased only slightly (0.23 to 0.17 mol: 26%), its degradation rate should be similar to that produced from the decaying TCE. Cyclodextrin was monitored starting from day 210. The mass of residual CD (as measured by Total Organic Carbon) decreased from 150 mol (day 210) to 66 (day 425) (56% decrease). The naturally anaerobic zone within the aquifer where residual CD mass decreased coincided with a loss of other major potential TEAs: nitrate (97% loss), sulfate (31%) and iron (31%). In other studies, TCE and 1,1,1-TCA have been found to be more energetically favorable TEAs than sulfate and iron and their degradation via reductive dechlorination has been found to be enhanced by the fermentation of carbohydrates. Such processes can explain these observations, but more investigation is needed to evaluate whether residual levels of CD can facilitate the anaerobic degradation of chlorinated VOCs.

Recycling of PVC Waste via Environmental Friendly Vapor Treatment

Science.gov (United States)

Cui, Xin; Jin, Fangming; Zhang, Guangyi; Duan, Xiaokun

2010-11-01

This paper focused on the dechlorination of polyvinyl chloride (PVC), a plastic which is widely used in the human life and thereby is leading to serious "white pollution", via vapor treatment process to recycle PVC wastes. In the process, HCl emitted was captured into water solution to avoid hazardous gas pollution and corruption, and remaining polymers free of chlorine could be thermally degraded for further energy recovery. Optimal conditions for the dechlorination of PVC using vapor treatment was investigated, and economic feasibility of this method was also analyzed based on the experimental data. The results showed that the efficiency of dechlorination increased as the temperature increased from 200° C to 250° C, and the rate of dechlorination up to 100% was obtained at the temperature near 250° C. Meanwhile, about 12% of total organic carbon was detected in water solution, which indicated that PVC was slightly degraded in this process. The main products in solution were identified to be acetone, benzene and toluene. In addition, the effects of alkali catalysis on dechlorination were also studied in this paper, and it showed that alkali could not improve the efficiency of the dechlorination of PVC.

Effects of 1,1,1-Trichloroethane and Triclocarban on Reductive Dechlorination of Trichloroethene in a TCE-Reducing Culture.

Science.gov (United States)

Wen, Li-Lian; Chen, Jia-Xian; Fang, Jia-Yi; Li, Ang; Zhao, He-Ping

2017-01-01

Chlorinated compounds were generally present in the environment due to widespread use in the industry. A short-term study was performed to evaluate the effects of 1,1,1- trichloroethane (TCA) and triclocarban (TCC) on trichloroethene (TCE) removal in a reactor fed with lactate as the sole electron donor. Both TCA and TCC inhibited TCE reduction, but the TCC had a more pronounced effect compared to TCA. The TCE-reducing culture, which had never been exposed to TCA before, reductively dechlorinated TCA to 1,1-dichloroethane (DCA). Below 15 μM, TCA had little effect on the transformation of TCE to cis -dichloroethene (DCE); however, the reduction of cis -DCE and vinyl chloride (VC) were more sensitive to TCA, and ethene production was completely inhibited when the concentration of TCA was above 15 μM. In cultures amended with TCC, the reduction of TCE was severely affected, even at concentrations as low as 0.3 μM; all the cultures stalled at VC, and no ethene was detected. The cultures that fully transformed TCE to ethene contained 5.2-8.1% Dehalococcoides . Geobacter and Desulfovibrio , the bacteria capable of partially reducing TCE to DCE, were detected in all cultures, but both represented a larger proportion of the community in TCC-amended cultures. All cultures were dominated by Clostridium _sensu_stricto_7, a genus that belongs to Firmicutes with proportions ranging from 40.9% (in a high TCC (15 μM) culture) to 88.2%. Methanobacteria was detected at levels of 1.1-12.7%, except in cultures added with 15 and 30 μM TCA, in which they only accounted for ∼0.4%. This study implies further environmental factors needed to be considered in the successful bioremediation of TCE in contaminated sites.

Effects of 1,1,1-Trichloroethane and Triclocarban on Reductive Dechlorination of Trichloroethene in a TCE-Reducing Culture

Directory of Open Access Journals (Sweden)

Li-Lian Wen

2017-08-01

Full Text Available Chlorinated compounds were generally present in the environment due to widespread use in the industry. A short-term study was performed to evaluate the effects of 1,1,1- trichloroethane (TCA and triclocarban (TCC on trichloroethene (TCE removal in a reactor fed with lactate as the sole electron donor. Both TCA and TCC inhibited TCE reduction, but the TCC had a more pronounced effect compared to TCA. The TCE-reducing culture, which had never been exposed to TCA before, reductively dechlorinated TCA to 1,1-dichloroethane (DCA. Below 15 μM, TCA had little effect on the transformation of TCE to cis-dichloroethene (DCE; however, the reduction of cis-DCE and vinyl chloride (VC were more sensitive to TCA, and ethene production was completely inhibited when the concentration of TCA was above 15 μM. In cultures amended with TCC, the reduction of TCE was severely affected, even at concentrations as low as 0.3 μM; all the cultures stalled at VC, and no ethene was detected. The cultures that fully transformed TCE to ethene contained 5.2–8.1% Dehalococcoides. Geobacter and Desulfovibrio, the bacteria capable of partially reducing TCE to DCE, were detected in all cultures, but both represented a larger proportion of the community in TCC-amended cultures. All cultures were dominated by Clostridium_sensu_stricto_7, a genus that belongs to Firmicutes with proportions ranging from 40.9% (in a high TCC (15 μM culture to 88.2%. Methanobacteria was detected at levels of 1.1–12.7%, except in cultures added with 15 and 30 μM TCA, in which they only accounted for ∼0.4%. This study implies further environmental factors needed to be considered in the successful bioremediation of TCE in contaminated sites.

Dechlorane Plus and its dechlorinated analogs from an e-waste recycling center in maternal serum and breast milk of women in Wenling, China

International Nuclear Information System (INIS)

Ben Yujie; Li Xinghong; Yang Youlin; Li Long; Di Junping; Wang Wenyue; Zhou, Ren-Fang; Xiao Ke; Zheng Meiyun; Tian Yuan; Xu Xiaobai

2013-01-01

We measured Dechlorane Plus (DP) and its dechlorinated analogs in the blood and milk from women living in e-waste recycling sites in Wenling of Taizhou region, China (n = 49). Both syn-DP and anti-DP were detected in all samples. Another compound, Cl 11 -DP, was detected in 45% and 84% of milk and serum samples, respectively. DP levels in blood and milk from residents living in the local environment >20 yrs (R 20 group) were significantly higher than those living in Taizhou 3 group) (p anti ) in serum suggested that stereoselective DP bio-accumulation did not occur during the DP transport from blood to milk. This result indicate that DP can bio-accumulate in blood and milk with the low milk/serum partition coefficient and similar blood and milk stereoselective bio-accumulation profiles. - Highlights: ► Our study observed that DP and Cl 11 -DP can bioaccumulate in maternal blood and milk. ► A stable partitioning of DP between milk and serum was observed. ► Stereoselective DP accumulation did not occur during DP transport from blood to milk. ► Exposure from e-waste recycling was a dominant factor affecting the DP level. - DP can bio-accumulate in human with the low milk/serum partition coefficient and similar blood and milk stereo-selective bio-accumulation profiles.

The hydrogen concentration as parameter to identify natural attenuation processes of volatile chlorinated hydrocarbons in ground water; Die Wasserstoffkonzentration als Parameter zur Identifizierung des natuerlichen Abbaus von leichtfluechtigen Chlorkohlenwasserstoffen (LCKW) im Grundwasser

Energy Technology Data Exchange (ETDEWEB)

Alter, M.D.

2006-06-15

In this study, the hydrogen concentration as parameter to identify natural attenuation processes of volatile chlorinated hydrocarbons was investigated. The currently accepted and recommended bubble strip method for hydrogen sampling was optimized, and a storage method for hydrogen samples was developed. Furthermore batch experiments with a dechlorinating mixed culture and pure cultures were carried out to study H{sub 2}-concentrations of competing redox processes. The extraction of hydrogen from ground water was optimized by a reduced inlet diameter of the usually applied gas sampling bulbs, allowing a maximal turbulent ow and gas transfer. With a gas volume of 10 ml and flow rates of 50 to 140 ml/min, the course of extraction almost followed the theoretical course of equilibration. At flow rates > 100 ml/min a equilibrium of 98% was achieved within 20 min. Until recently it was generally accepted that hydrogen samples can be stored only for 2 hours and therefore have to be analyzed immediately in the eld. Here, it was shown that eld samples can be stored for 1-3 days until analysis. For the dechlorination of tetrachloroethene (PCE), a hydrogen threshold concentration of 1-2 nM was found with the dechlorinating mixed culture as well as with a pure culture of Sulfurospirillum multivorans in combination with another pure culture Methanosarcina mazei. No dechlorination was detectable below this concentration. With the dechlorinating mixed culture, this finding is valid for all successive dechlorination steps until ethene. The hydrogen threshold concentration for denitrification were below the detection limit of 0,2 nM with the dechlorinating mixed culture. A threshold concentration of 3,1-3,5 nM was found for sulphate reduction and a threshold of 7-9 nM H{sub 2} for hydrogenotrophic methanogenesis. This implies that the natural dechlorination at contaminated sites is preferred to competing processes like sulphate reduction and methanogenesis. The threshold

Quantitative and functional dynamics of Dehalococcoides spp. and its tceA and vcrA genes under TCE exposure.

Science.gov (United States)

Doğan-Subaşi, Eylem; Bastiaens, Leen; Leys, Natalie; Boon, Nico; Dejonghe, Winnie

2014-07-01

This study aimed at monitoring the dynamics of phylogenetic and catabolic genes of a dechlorinating enrichment culture before, during, and after complete dechlorination of chlorinated compounds. More specifically, the effect of 40 μM trichloroethene (TCE) and 5.6 mM lactate on the gene abundance and activity of an enrichment culture was investigated for 40 days. Although tceA and vcrA gene copy numbers were relatively stable in DNA extracts over time, tceA and vcrA mRNA abundances were upregulated from undetectable levels to 2.96 × and 6.33 × 10⁴ transcripts/mL, respectively, only after exposure to TCE and lactate. While tceA gene transcripts decreased over time with TCE dechlorination, the vcrA gene was expressed steadily even when the concentration of vinyl chloride was at undetectable levels. In addition, ratios between catabolic and phylogenetic genes indicated that tceA and vcrA gene carrying organisms dechlorinated TCE and its produced daughter products, while vcrA gene was mainly responsible for the dechlorination of the lower VC concentrations in a later stage of degradation.

Microbial transformation and degradation of polychlorinated biphenyls

Energy Technology Data Exchange (ETDEWEB)

Field, Jim A. [Department of Chemical and Environmental Engineering, University of Arizona, PO Box 210011, Tucson, AZ 85721 (United States)], E-mail: jimfield@email.arizona.edu; Sierra-Alvarez, Reyes [Department of Chemical and Environmental Engineering, University of Arizona, PO Box 210011, Tucson, AZ 85721 (United States)

2008-09-15

This paper reviews the potential of microorganisms to transform polychlorinated biphenyls (PCBs). In anaerobic environments, higher chlorinated biphenyls can undergo reductive dehalogenation. Meta- and para-chlorines in PCB congeners are more susceptible to dechlorination than ortho-chlorines. Anaerobes catalyzing PCB dechlorination have not been isolated in pure culture but there is strong evidence from enrichment cultures that some Dehalococcoides spp. and other microorganisms within the Chloroflexi phylum can grow by linking the oxidation of H{sub 2} to the reductive dechlorination of PCBs. Lower chlorinated biphenyls can be co-metabolized aerobically. Some aerobes can also grow by utilizing PCB congeners containing only one or two chlorines as sole carbon/energy source. An example is the growth of Burkholderia cepacia by transformation of 4-chlorobiphenyl to chlorobenzoates. The latter compounds are susceptible to aerobic mineralization. Higher chlorinated biphenyls therefore are potentially fully biodegradable in a sequence of reductive dechlorination followed by aerobic mineralization of the lower chlorinated products. - Higher chlorinated biphenyls are potentially fully biodegradable in a sequence of anaerobic reductive dechlorination followed by aerobic mineralization of the lower chlorinated products.

Complete biological reductive transformation of tetrachloroethene to ethane.

Science.gov (United States)

de Bruin, W P; Kotterman, M J; Posthumus, M A; Schraa, G; Zehnder, A J

1992-01-01

Reductive dechlorination of tetrachloroethene (perchloroethylene; PCE) was observed at 20 degrees C in a fixed-bed column, filled with a mixture (3:1) of anaerobic sediment from the Rhine river and anaerobic granular sludge. In the presence of lactate (1 mM) as an electron donor, 9 microM PCE was dechlorinated to ethene. Ethene was further reduced to ethane. Mass balances demonstrated an almost complete conversion (95 to 98%), with no chlorinated compounds remaining (less than 0.5 micrograms/liter). When the temperature was lowered to 10 degrees C, an adaptation of 2 weeks was necessary to obtain the same performance as at 20 degrees C. Dechlorination by column material to ethene, followed by a slow ethane production, could also be achieved in batch cultures. Ethane was not formed in the presence of bromoethanesulfonic acid, an inhibitor of methanogenesis. The high dechlorination rate (3.7 mumol.l-1.h-1), even at low temperatures and considerable PCE concentrations, together with the absence of chlorinated end products, makes reductive dechlorination an attractive method for removal of PCE in bioremediation processes. PMID:1622277

Microbial transformation and degradation of polychlorinated biphenyls

International Nuclear Information System (INIS)

Field, Jim A.; Sierra-Alvarez, Reyes

2008-01-01

This paper reviews the potential of microorganisms to transform polychlorinated biphenyls (PCBs). In anaerobic environments, higher chlorinated biphenyls can undergo reductive dehalogenation. Meta- and para-chlorines in PCB congeners are more susceptible to dechlorination than ortho-chlorines. Anaerobes catalyzing PCB dechlorination have not been isolated in pure culture but there is strong evidence from enrichment cultures that some Dehalococcoides spp. and other microorganisms within the Chloroflexi phylum can grow by linking the oxidation of H 2 to the reductive dechlorination of PCBs. Lower chlorinated biphenyls can be co-metabolized aerobically. Some aerobes can also grow by utilizing PCB congeners containing only one or two chlorines as sole carbon/energy source. An example is the growth of Burkholderia cepacia by transformation of 4-chlorobiphenyl to chlorobenzoates. The latter compounds are susceptible to aerobic mineralization. Higher chlorinated biphenyls therefore are potentially fully biodegradable in a sequence of reductive dechlorination followed by aerobic mineralization of the lower chlorinated products. - Higher chlorinated biphenyls are potentially fully biodegradable in a sequence of anaerobic reductive dechlorination followed by aerobic mineralization of the lower chlorinated products

Experimental Evaluation and Mathematical Modeling of Microbially Enhanced Tetrachloroethene (PCE) Dissolution

National Research Council Canada - National Science Library

Amos, Benjamin K; Crhist, John A; Abriola, Linda M; Pennell, Kurt D; Loeffler, Frank E

2006-01-01

...) and Desulfitobacterium sp. strain Viet1, a PCE-to-trichloroethene (TCE) dechlorinating isolate. Despite recent evidence suggesting bacterial PCE-to- cis-DCE dechlorination occurs at or near PCE saturation (0.9-1.2 mM...

EFFECT OF CONTAMINANT AND ORGANIC MATTER BIOAVAILABILITY ON THE MICROBIAL DEHALOGENATION OF SEDIMENT-BOUND CHLOROBENZENES. (R825513C007)

Science.gov (United States)

The extent of reductive dechlorination occurring in contaminated, estuarine sediments was investigated. Contaminant and organic matter bioavailability and their effect on the reductive dechlorination of sediment-bound chlorobenzenes was the main focus of the work presented her...

Biological reduction of chlorinated solvents: Batch-scale geochemical modeling

Science.gov (United States)

Kouznetsova, Irina; Mao, Xiaomin; Robinson, Clare; Barry, D. A.; Gerhard, Jason I.; McCarty, Perry L.

2010-09-01

Simulation of biodegradation of chlorinated solvents in dense non-aqueous phase liquid (DNAPL) source zones requires a model that accounts for the complexity of processes involved and that is consistent with available laboratory studies. This paper describes such a comprehensive modeling framework that includes microbially mediated degradation processes, microbial population growth and decay, geochemical reactions, as well as interphase mass transfer processes such as DNAPL dissolution, gas formation and mineral precipitation/dissolution. All these processes can be in equilibrium or kinetically controlled. A batch modeling example was presented where the degradation of trichloroethene (TCE) and its byproducts and concomitant reactions (e.g., electron donor fermentation, sulfate reduction, pH buffering by calcite dissolution) were simulated. Local and global sensitivity analysis techniques were applied to delineate the dominant model parameters and processes. Sensitivity analysis indicated that accurate values for parameters related to dichloroethene (DCE) and vinyl chloride (VC) degradation (i.e., DCE and VC maximum utilization rates, yield due to DCE utilization, decay rate for DCE/VC dechlorinators) are important for prediction of the overall dechlorination time. These parameters influence the maximum growth rate of the DCE and VC dechlorinating microorganisms and, thus, the time required for a small initial population to reach a sufficient concentration to significantly affect the overall rate of dechlorination. Self-inhibition of chlorinated ethenes at high concentrations and natural buffering provided by the sediment were also shown to significantly influence the dechlorination time. Furthermore, the analysis indicated that the rates of the competing, nonchlorinated electron-accepting processes relative to the dechlorination kinetics also affect the overall dechlorination time. Results demonstrated that the model developed is a flexible research tool that is

Use of emulsified vegetable oil to support bioremediation of TCE DNAPL in soil columns.

Science.gov (United States)

Harkness, Mark; Fisher, Angela

2013-08-01

The interaction between emulsified vegetable oil (EVO) and trichloroethylene (TCE) dense non-aqueous phase liquid (DNAPL) was observed using two soil columns and subsequent reductive dechlorination of TCE was monitored over a three year period. Dyed TCE DNAPL (~75 g) was emplaced in one column (DNAPL column), while the second was DNAPL-free (plume column). EVO was added to both columns and partitioning of the EVO into the TCE DNAPL was measured and quantified. TCE (1.9 mM) was added to the influent of the plume column to simulate conditions down gradient of a DNAPL source area and the columns were operated independently for more than one year, after which they were connected in series. Initially limited dechlorination of TCE to cDCE was observed in the DNAPL column, while the plume column supported complete reductive dechlorination of TCE to ethene. Upon connection and reamendment of the plume column with EVO, near saturation levels of TCE from the effluent of the DNAPL column were rapidly dechlorinated to c-DCE and VC in the plume column; however, this high rate dechlorination produced hydrochloric acid which overwhelmed the buffering capacity of the system and caused the pH to drop below 6.0. Dechlorination efficiency in the columns subsequently deteriorated, as measured by the chloride production and Dehalococcoides counts, but was restored by adding sodium bicarbonate buffer to the influent groundwater. Robust dechlorination was eventually observed in the DNAPL column, such that the TCE DNAPL was largely removed by the end of the study. Partitioning of the EVO into the DNAPL provided significant operational benefits to the remediation system both in terms of electron donor placement and longevity. Copyright © 2013 Elsevier B.V. All rights reserved.

Benzoate-driven dehalogenation of chlorinated ethenes in microbial cultures from a contaminated aquifer

Energy Technology Data Exchange (ETDEWEB)

Bunge, M.; Kleikemper, J.; Miniaci, C.; Duc, L.; Muusse, M.G.; Zeyer, J. [Swiss Federal Institute of Technology (ETH), Zurich (Switzerland). Inst. of Biogeochemistry and Pollutant Dynamics, Soil Biology; Hause, G. [Halle-Wittenberg Univ., Halle (Germany). Biocenter

2007-10-15

Microbial dehalogenation of tetrachloroethene (PCE) and cis-dichloroethene (cis-DCE) was studied in cultures from a continuous stirred tank reactor initially inoculated with aquifer material from a PCE-contaminated site. Cultures amended with hydrogen and acetate readily dechlorinated PCE and cis-DCE; however, this transformation was incomplete and resulted in the accumulation of chlorinated intermediates and only small amounts of ethene within 60 days of incubation. Conversely, microbial PCE and cis-DCE dechlorination in cultures with benzoate and acetate resulted in the complete transformation to ethene within 30 days. Community fingerprinting by denaturing gradient gel electrophoresis (DGGE) revealed the predominance of phylotypes closely affiliated with Desulfitobacterium, Dehalococcoides, and Syntrophus species. The Dehalococcoides culture VZ, obtained from small whitish colonies in cis-DCE dechlorinating agarose cultures, revealed an irregular cell diameter between 200 and 500 nm, and a spherical or biconcave disk-shaped morphology. These organisms were identified as responsible for the dechlorination of cis-DCE to ethene in the PCE-dechlorinating consortia, operating together with the Desulfitobacterium as PCE-to-cis-DCE dehalogenating bacterium and with a Syntrophus species as potential hydrogen-producing partner in cultures with benzoate. (orig.)

Bioremediation of 1,2-dichloroethane contaminated groundwater: Microcosm and microbial diversity studies

International Nuclear Information System (INIS)

Wang, S.Y.; Kuo, Y.C.; Huang, Y.Z.; Huang, C.W.; Kao, C.M.

2015-01-01

In this study, the effectiveness of bioremediating 1,2-dichloroethane (DCA)-contaminated groundwater under different oxidation–reduction processes was evaluated. Microcosms were constructed using indigenous bacteria and activated sludge as the inocula and cane molasses and a slow polycolloid-releasing substrate (SPRS) as the primary substrates. Complete DCA removal was obtained within 30 days under aerobic and reductive dechlorinating conditions. In anaerobic microcosms with sludge and substrate addition, chloroethane, vinyl chloride, and ethene were produced. The microbial communities and DCA-degrading bacteria in microcosms were characterized by 16S rRNA-based denatured-gradient-gel electrophoresis profiling and nucleotide sequence analyses. Real-time polymerase chain reaction was applied to evaluate the variations in Dehalococcoides spp. and Desulfitobacterium spp. Increase in Desulfitobacterium spp. indicates that the growth of Desulfitobacterium might be induced by DCA. Results indicate that DCA could be used as the primary substrate under aerobic conditions. The increased ethene concentrations imply that dihaloelimination was the dominate mechanism for DCA biodegradation. - Highlights: • DCA can be used as the primary substrate and degraded by the indigenous microbial consortia. • Reductive dechlorination of DCA can be enhanced by the supplement of substrates and sludge. • Dihaloelimination is the dominant mechanism for DCA dechlorination and ethene is the end product. • SPRS can serve as the primary substrate and creates anaerobic conditions for DCA dechlorination. • Reductive dechlorination is a feasible option for DCA-contaminated groundwater remediation. - DCA can serve as the primary substrate and degraded by indigenous bacteria aerobically. Dihaloelimination is the dominant mechanism and ethene is the end product via dechlorination

Effect of reaction environments on the reactivity of PCB (2-chlorobiphenyl) over activated carbon impregnated with palladized iron

Energy Technology Data Exchange (ETDEWEB)

Choi, Hyeok [Department of Civil Engineering, University of Texas at Arlington, 416 Yates Drive, Arlington, TX 76019-0308 (United States); Al-Abed, Souhail R., E-mail: al-abed.souhail@epa.gov [National Risk Management Research Laboratory, U.S. Environmental Protection Agency, 26 West Martin Luther King Drive, Cincinnati, OH 45268 (United States)

2010-07-15

Reactive activated carbon (RAC) impregnated with palladized iron nanoparticles has been developed to treat polychlorinated biphenyls (PCBs). In this study, we evaluated the effects of various reaction environments on the adsorption-mediated dechlorination of 2-chlorobiphenyl (2-ClBP) in the RAC system. The results were discussed in close connection to the implementation issue of the RAC system for the remediation of contaminated sites with PCBs. Adsorption event of 2-ClBP onto RAC limited the overall performance under condition with a 2-ClBP/RAC mass ratio of less than 1.0 x 10{sup -4} above which dechlorination of 2-ClBP adsorbed to RAC was the reaction rate-determining step. Acidic and basic conditions were harmful to 2-ClBP adsorption and iron stability while neutral pH showed the highest adsorption-promoted dechlorination of 2-ClBP and negligible metal leaching. Coexisting natural organic matter (NOM) slightly inhibited 2-ClBP adsorption onto RAC due to the partial partitioning of 2-ClBP into NOM in the liquid phase while the 2-ClBP absorbed into NOM, which also tended to adsorb onto RAC, was less available for the dechlorination reaction. Common anions slowed down 2-ClBP adsorption but adsorbed 2-ClBP was almost simultaneously dechlorinated. Some exceptions included strong inhibitory effect of carbonate species on 2-ClBP adsorption and severe detrimental effect of sulfite on 2-ClBP dechlorination. Results on treatment of 2-ClBP spiked to actual sediment supernatants implied site-specific reactivity of RAC.

Enhanced dissolution of TCE in NAPL by TCE-degrading bacteria in wetland soils

International Nuclear Information System (INIS)

Lee, Sangjin

2007-01-01

The influence of trichloroethene (TCE) dechlorinating mixed cultures in dissolution of TCE in nonaqueous phase liquid (NAPL) via biodegradation was observed. Experiments were conducted in batch reactor system with and without marsh soils under 10 and 20 deg. C for 2 months. The dissolution phenomenon in biotic reactors containing mixed cultures was showed temporal increases compared to abiotic reactors treated with biocide. Effective NAPL-water transfer rate (K m ) calculated in this study showed more than four times higher in biotic reactors than that in abiotic reactors. The results might be attributed to the biologically enhanced dissolution process via dechlorination in reactors. Temperature would be a factor to determine the dissolution rate by controlling bacterial activity. The TCE dechlorination occurred even in an interface of TCE-NAPL that demonstrated no previous TCE biodegradation, suggesting that microbes may be useful in developing source-zone bioremediation system. In conclusion, dechlorinating mixed culture could enhance dissolution in NAPL that may be useful in the application of source zone bioremediation

Integrated Nanozero Valent Iron and Biosurfactant-Aided Remediation of PCB-Contaminated Soil

Directory of Open Access Journals (Sweden)

He Zhang

2016-01-01

Full Text Available Polychlorobiphenyls (PCBs have been identified as environmental hazards for years. Due to historical issues, a considerable amount of PCBs was released deep underground in Canada. In this research, a nanoscale zero valent iron- (nZVI- aided dechlorination followed by biosurfactant enhanced soil washing method was developed to remove PCBs from soil. During nZVI-aided dechlorination, the effects of nZVI dosage, initial pH level, and temperature were evaluated, respectively. Five levels of nZVI dosage and two levels of initial pH were experimented to evaluate the PCB dechlorination rate. Additionally, the temperature changes could positively influence the dechlorination process. In soil washing, the presence of nanoiron particles played a key role in PCB removal. The crude biosurfactant was produced using a bacterial stain isolated from the Atlantic Ocean and was applied for soil washing. The study has led to a promising technology for PCB-contaminated soil remediation.

Electrodeposition of palladium and reduced graphene oxide nanocomposites on foam-nickel electrode for electrocatalytic hydrodechlorination of 4-chlorophenol

International Nuclear Information System (INIS)

Liu, Yong; Liu, Lan; Shan, Jun; Zhang, Jingdong

2015-01-01

Highlights: • Pd and reduced graphene oxide are deposited on foam-Ni via electrodeposition. • Pd particles supported on RGO possess large active surface area. • Pd/RGO/foam-Ni shows high electrocatalytic activity for dechlorination of 4-CP. • 100% 4-CP can be removed on Pd/RGO/foam-Ni under optimum ECH conditions. - Abstract: A high-performance palladium (Pd) and reduced graphene oxide (RGO) composite electrode was prepared on foam-nickel (foam-Ni) via two-step electrodeposition processes. The scanning electron microscopic (SEM) observation showed that the obtained Pd/RGO/foam-Ni composite electrode displayed a uniform and compact morphology. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopic (XPS) analysis confirmed the successful deposition of Pd and RGO on nickel substrate. The cyclic voltammetric (CV) measurements indicated that the presence of RGO greatly enhanced the active surface area of Pd particles deposited on foam-Ni. The as-deposited Pd/RGO/foam-Ni electrode was applied to electrocatalytic hydrodechlorination (ECH) of 4-chlorophenol (4-CP). Various factors influencing the dechlorination of 4-CP such as dechlorination current, initial concentration of 4-CP, Na 2 SO 4 concentration and initial pH were systematically investigated. The thermodynamic analysis showed that the dechlorination reaction of 4-CP at different temperatures followed the first-order kinetics and the activation energy for 4-CP dechlorination on Pd/RGO/foam-Ni electrode was calculated to be 51.96 kJ mol −1 . Under the optimum conditions, the dechlorination efficiency of 4-CP could reach 100% after 60-min ECH treatment. Moreover, the prepared Pd/RGO/foam-Ni composite electrode showed good stability for recycling utilization in ECH of 4-CP

Reductive dehalogenation activity of indigenous microorganism in sediments of the Hackensack River, New Jersey.

Science.gov (United States)

Sohn, Seo Yean; Häggblom, Max M

2016-07-01

Organohalogen pollutants are of concern in many river and estuarine environments, such as the New York-New Jersey Harbor estuary and its tributaries. The Hackensack River is contaminated with various metals, hydrocarbons and halogenated organics, including polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins. In order to examine the potential for microbial reductive dechlorination by indigenous microorganisms, sediment samples were collected from five different estuarine locations along the Hackensack River. Hexachlorobenzene (HCB), hexabromobenzene (HBB), and pentachloroaniline (PCA) were selected as model organohalogen pollutants to assess anaerobic dehalogenating potential. Dechlorinating activity of HCB and PCA was observed in sediment microcosms for all sampling sites. HCB was dechlorinated via pentachlorobenzene (PeCB) and trichlorobenzene (TriCB) to dichlorobenzene (DCB). PCA was dechlorinated via tetrachloroaniline (TeCA), trichloroanilines (TriCA), and dichloroanilines (DCA) to monochloroaniline (MCA). No HBB debromination was observed over 12 months of incubation. However, with HCB as a co-substrate slow HBB debromination was observed with production of tetrabromobenzene (TeBB) and tribromobenzene (TriBB). Chloroflexi specific 16S rRNA gene PCR-DGGE followed by sequence analysis detected Dehalococcoides species in sediments of the freshwater location, but not in the estuarine site. Analysis targeting 12 putative reductive dehalogenase (rdh) genes showed that these were enriched concomitant with HCB or PCA dechlorination in freshwater sediment microcosms. Copyright © 2016 Elsevier Ltd. All rights reserved.

Project to aid development of an oil substituting fuel manufacturing technology in fiscal 1998. Report on the result of developing a technology to make cable covering materials into fuel; 1998 nendo sekiyu daitai nenryo seizo gijutsu kaihatsu hojo jigyo. Densen hifukuzai nenryoka gijutsu kaihatsu

Energy Technology Data Exchange (ETDEWEB)

NONE

1999-03-01

Research and development have been carried out with an objective to re-utilize waste cable covering materials as oil substituting energy. The research has been performed on behavior of chlorine and lead being substances that impede making the cable covering materials into fuel, development of a technology to remove chlorine, lead and copper, and pelletizing properties for fuel making. In the study of behavior of chlorine and lead, the following matters were made clear: dechlorination reaction completes within 30 minutes if pyrolysis temperature is higher than 300 degrees C; the more the amount of filler CaCO3 in test samples, the less the dechlorination amount; and secular deterioration does not affect the dechlorination amount. A technology has been developed successfully to remove the substances that hinder making the cover materials into fuel, achieving the target values of copper at 0.2% or less, lead at 0.3% or less, and chlorine at 5% or less. In developing the pelletizing technology that puts the cover materials into raw materials for blast furnaces, dechlorination rate of 90% was achieved by mixing coke/PVC at a ratio of 1/1 and dechlorinating it by using a rotary kiln. It was verified that the product is free of problems in particle size as the blast furnace raw material. (NEDO)

Treatment characteristics of various sediment components spiked with 2-chlorobiphenyl using reactive activated carbon.

Science.gov (United States)

Choi, Hyeok

2018-04-05

Previously, the concept of reactive activated carbon (RAC), where the porous structure of activated carbon (AC) is impregnated with palladized zerovalent iron, has been proposed to be effective to adsorb and dechlorinate polychlorinated biphenyls (PCBs). To explain the low dechlorination of PCBs bound to actual aquatic sediments under remediation with RAC, this study investigated the role of various solid organic and inorganic sediment components in adsorbing and desorbing PCBs. Detailed fate and transport mechanism of 2-chlorinated biphenyl (2-ClBP) spiked to sediment components, including kaolin, montmorillonite (MMT), coal, graphite, AC, and their mixture, was revealed. Adsorption and holding capability of sediment components toward 2-ClBP strongly influenced amount of spiked 2-ClBP, amount of desorbed 2-ClBP, overall dechlorination of 2-ClBP to biphenyl (BP), and eventual partitioning of 2-ClBP and BP to water, sediment component, and RAC. Order of the amount of spiked 2-ClBP to sediment components after drying, following AC > mixture > coal > graphite > kaolin > MMT, was in agreements (in opposite direction) with order of the amount of desorbed 2-ClBP and order of overall 2-ClBP dechlorination. Substantial role of organic components in aquatic sediments for holding 2-ClBP and thus preventing it from dechlorination on RAC was proven. Copyright © 2017 Elsevier B.V. All rights reserved.

Investigating the biogeochemical interactions involved in simultaneous TCE and Arsenic in situ bioremediation

Science.gov (United States)

Cook, E.; Troyer, E.; Keren, R.; Liu, T.; Alvarez-Cohen, L.

2016-12-01

The in situ bioremediation of contaminated sediment and groundwater is often focused on one toxin, even though many of these sites contain multiple contaminants. This reductionist approach neglects how other toxins may affect the biological and chemical conditions, or vice versa. Therefore, it is of high value to investigate the concurrent bioremediation of multiple contaminants while studying the microbial activities affected by biogeochemical factors. A prevalent example is the bioremediation of arsenic at sites co-contaminated with trichloroethene (TCE). The conditions used to promote a microbial community to dechlorinate TCE often has the adverse effect of inducing the release of previously sequestered arsenic. The overarching goal of our study is to simultaneously evaluate the bioremediation of arsenic and TCE. Although TCE bioremediation is a well-understood process, there is still a lack of thorough understanding of the conditions necessary for effective and stable arsenic bioremediation in the presence of TCE. The objective of this study is to promote bacterial activity that stimulates the precipitation of stable arsenic-bearing minerals while providing anaerobic, non-extreme conditions necessary for TCE dechlorination. To that end, endemic microbial communities were examined under various conditions to attempt successful sequestration of arsenic in addition to complete TCE dechlorination. Tested conditions included variations of substrates, carbon source, arsenate and sulfate concentrations, and the presence or absence of TCE. Initial arsenic-reducing enrichments were unable to achieve TCE dechlorination, probably due to low abundance of dechlorinating bacteria in the culture. However, favorable conditions for arsenic precipitation in the presence of TCE were eventually discovered. This study will contribute to the understanding of the key species in arsenic cycling, how they are affected by various concentrations of TCE, and how they interact with the key

Effect of groundwater geochemistry on pentachlorophenol remediation by smectite-templated nanosized Pd0/Fe0.

Science.gov (United States)

Jia, Hanzhong; Gu, Cheng; Li, Hui; Fan, Xiaoyun; Li, Shouzhu; Wang, Chuanyi

2012-09-01

Zero-valent iron holds great promise in treating groundwater, and its reactivity and efficacy depend on many surrounding factors. In the present work, the effects of solution chemistry such as pH, humic acid (HA), and inorganic ions on pentachlorophenol (PCP) dechlorination by smectite-templated Pd(0)/Fe(0) were systematically studied. Smectite-templated Pd(0)/Fe(0) was prepared by saturating the negatively charged sites of smectite clay with Fe(III) and a small amount of Pd(II), followed by borohydride reduction to convert Fe(III) and Pd(II) into zero-valent metal clusters. Batch experiments were conducted to investigate the effects of water chemistry on PCP remediation. The PCP dechlorination rate critically depends on the reaction pH over the range 6.0~10.0; the rate constant (k (obs)) increases with decreasing the reaction pH value. Also, the PCP remediation is inhibited by HA, which can be attributed to the electron competition of HA with H(+). In addition, the reduction of PCP can be accelerated by various anions, following the order: Cl(-) > HCO (3) (-) > SO (4) (2-) ~no anion. In the case of cations, Ca(2+) and Mg(2+) (10 mM) decrease the dechlorination rate to 0.7959 and 0.7798 from 1.315 h(-1), respectively. After introducing HA into the reaction systems with cations or/and anions, the dechlorination rates are similar to that containing HA alone. This study reveals that low pH and the presence of some anions such as Cl(-) facilitate the PCP dechlorination and induce the rapid consumption of nanosized zero-valent iron simultaneously. However, the dechlorination rate is no longer correlated to the inhibitory or accelerating effects by cations and anions in the presence of 10 mg/L HA.

Use of γ-hexachlorocyclohexane as a terminal electron acceptor by an anaerobic enrichment culture

International Nuclear Information System (INIS)

Elango, Vijai; Kurtz, Harry D.; Anderson, Christina; Freedman, David L.

2011-01-01

Highlights: ► Use of γ-hexachlorocyclohexane as a terminal electron acceptor was demonstrated. ► H 2 served as the electron donor for an enrichment culture that dechlorinated γ-HCH. ► H 2 consumption for acetogenesis and methanogenesis stopped in HEPES media. ► Addition of vancomycin significantly slowed the rate of γ-HCH dechlorination. ► Previously identified chlororespiring microbes were not detected in the enrichment. - Abstract: The use of γ-hexachlorocyclohexane (HCH) as a terminal electron acceptor via organohalide respiration was demonstrated for the first time with an enrichment culture grown in a sulfate-free HEPES-buffered anaerobic mineral salts medium. The enrichment culture was initially developed with soil and groundwater from an industrial site contaminated with HCH isomers, chlorinated benzenes, and chlorinated ethenes. When hydrogen served as the electron donor, 79–90% of the electron equivalents from hydrogen were used by the enrichment culture for reductive dechlorination of the γ-HCH, which was provided at a saturation concentration of approximately 10 mg/L. Benzene and chlorobenzene were the only volatile transformation products detected, accounting for 25% and 75% of the γ-HCH consumed (on a molar basis), respectively. The enrichment culture remained active with only hydrogen as the electron donor and γ-HCH as the electron acceptor through several transfers to fresh mineral salts medium for more than one year. Addition of vancomycin to the culture significantly slowed the rate of γ-HCH dechlorination, suggesting that a Gram-positive organism is responsible for the reduction of γ-HCH. Analysis of the γ-HCH dechlorinating enrichment culture did not detect any known chlororespiring genera, including Dehalobacter. In bicarbonate-buffered medium, reductive dechlorination of γ-HCH was accompanied by significant levels of acetogenesis as well as methanogenesis.

The interactive biotic and abiotic processes of DDT transformation under dissimilatory iron-reducing conditions.

Science.gov (United States)

Jin, Xin; Wang, Fang; Gu, Chenggang; Yang, Xinglun; Kengara, Fredrick O; Bian, Yongrong; Song, Yang; Jiang, Xin

2015-11-01

The objective of the study was to elucidate the biotic and abiotic processes under dissimilatory iron reducing conditions involved in reductive dechlorination and iron reduction. DDT transformation was investigated in cultures of Shewanella putrefaciens 200 with/without α-FeOOH. A modified first-order kinetics model was developed and described DDT transformation well. Both the α-FeOOH reduction rate and the dechlorination rate of DDT were positively correlated to the biomass. Addition of α-FeOOH enhanced reductive dechlorination of DDT by favoring the cell survival and generating Fe(II) which was absorbed on the surface of bacteria and iron oxide. 92% of the absorbed Fe(II) was Na-acetate (1M) extractable. However, α-FeOOH also played a negative role of competing for electrons as reflected by the dechlorination rate of DDT was inhibited when increasing the α-FeOOH from 1 g L(-1) to 5 g L(-1). DDT was measured to be toxic to S. putrefaciens 200. The metabolites DDD, DDE and DDMU were recalcitrant to S. putrefaciens 200. The results suggested that iron oxide was not the key factor to promote the dissipation of DDX (DDT and the metabolites), whereas the one-electron reduction potential (E1) of certain organochlorines is the main factor and that the E1 higher than the threshold of the reductive driving forces of DIRB probably ensures the occur of reductive dechlorination. Copyright © 2015 Elsevier Ltd. All rights reserved.

Assessing the Feasibility of DNAPL Source Zone Remediation: Review of Case Studies

Science.gov (United States)

2004-05-01

such as sugars, alcohols, fatty acids that are fermented to hydrogen and used for reductive dechlorination) are more soluble than the chlorinated...addition because a greater percentage of the hydrogen produced during the fermentation of added electron donors is consumed by dechlorinating...Battelle, 2002; Stegemeier and Vinegar , 2001; Roote, 2003; USEPA, 1999): i) increasing vapor pressure and volatilization rates of low boiling point

Diagnostic Tools for Performance Evaluation of Innovative In-Situ Remediation Technologies at Chlorinated Solvent-Contaminated Sites

Science.gov (United States)

2011-11-01

Electronic down-hole sensors with data loggers, or fiber optic sensors, can also provide information on the pore pressure, temperature, conductivity...of a dechlorinating community resulting from in-situ biostimulation in a trichloroethene-contaminated deep, fractured basalt aquifer and comparison to...dechlorinating community resulting from in-situ biostimulation in a trichloroethene-contaminated deep, fractured basalt aquifer and comparison to a

Applications of compound-specific carbon isotope ratios in organic contaminant studies

International Nuclear Information System (INIS)

Aravena, R.; Hunkeler, D.; Bloom, Y.; Frape, S.K.; Butler, B.; Edwards, E.; Cox, E.

1999-01-01

In this paper results are presented on the application of compound-specific isotope ratios measurements to assess biodegradation of chlorinated solvents, in particularly on microbial dechlorination of tetrachloroethene (PCE) and trichloroethene (TCE). Analytical aspects and isotope data from laboratory and field studies are discussed. The analytical tests showed that both headspace and SPME techniques provide accurate δ 13 C values with a similar precision for a wide range of chlorinated solvents. However, the SPME method is generally more sensitive. The microcosm experiments show that a significant isotopic fractionation occurs during dechlorination of PCE and TCE to ethene. The largest fractionation factors are observed in the steps DCE-VC and VC-Ethene. In general, the δ 13 C of each dechlorination product was always more negative than the δ 13 C of the corresponding precursor. In addition, the δ 13 C values of each compound increased with time. A similar pattern was observed for dechlorination of PCE at a field site. These results show that compound-specific carbon isotope ratios technology is a very sensitive tool for evaluation of natural attenuation of chlorinated solvents in groundwater. (author)

Effects of microbial inhibitors on anaerobic degradation of DDT

Energy Technology Data Exchange (ETDEWEB)

Wang, Y.S.; Chiu, T.C.; Yen, J.H. [National Taiwan Univ., Taipei (Taiwan)

2004-09-15

Chlorinated insecticide DDT [1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane] was extensively used for controlling pests in the agricultural field and human-being living environments in the past several decades. Due to the chemical stability, DDT was extremely persistent and recalcitrant in soils and sediments and it was banned by nations. Microorganisms usually play important roles in reducing organochlorine compounds in the environments. Under low-oxygen conditions, microbial dechlorination is thought as the onset of highly chlorinated compounds. Methanogenic and sulfate-reducing bacteria participate in microbial dechlorination under anaerobic condition has been reported. In this study, a mixed anaerobic culture enabling to dechlorinate DDT was obtained from river sediment in Taiwan. In order to understand the effect of these microorganisms on DDT dechlorination, microbial inhibitors BESA (2-bromoethanesulfonate) and molybdate, for inhibiting methanogenic and sulfate-reducing bacteria, respectively, were chosen to investigate the interaction between specific microbial communities and their degradation activities. Besides, a molecular technique, denaturing gradient gel electrophoresis (DGGE), based on analyzing the 16S rDNA of bacteria, was used for monitoring the bacterial community structure in this study.

Wheat straw biochar-supported nanoscale zerovalent iron for removal of trichloroethylene from groundwater.

Directory of Open Access Journals (Sweden)

Hui Li

Full Text Available This study synthesized the wheat straw biochar-supported nanoscale zerovalent iron (BC-nZVI via in-situ reduction with NaBH4 and biochar pyrolyzed at 600°C. Wheat straw biochar, as a carrier, significantly enhanced the removal of trichloroethylene (TCE by nZVI. The pseudo-first-order rate constant of TCE removal by BC-nZVI (1.079 h-1 within 260 min was 1.4 times higher and 539.5 times higher than that of biochar and nZVI, respectively. TCE was 79% dechlorinated by BC-nZVI within 15 h, but only 11% dechlorinated by unsupported nZVI, and no TCE dechlorination occurred with unmodified biochar. Weakly acidic solution (pH 5.7-6.8 significantly enhanced the dechlorination of TCE. Chloride enhanced the removal of TCE, while SO42-, HCO3- and NO3- all inhibited it. Humic acid (HA inhibited BC-nZVI reactivity, but the inhibition decreased slightly as the concentration of HA increased from 40 mg∙L-1 to 80 mg∙L-1, which was due to the electron shutting by HA aggregates. Results suggest that BC-nZVI was promising for remediation of TCE contaminated groundwater.

Physiological and molecular genetic evaluation of the dechlorination agent, pyridine-2,6-bis(monothiocarboxylic acid) (PDTC) as a secondary siderophore of Pseudomonas.

Science.gov (United States)

Lewis, Thomas A; Leach, Lynne; Morales, Sergio; Austin, Paula R; Hartwell, Hadley J; Kaplan, Benjamin; Forker, Cynthia; Meyer, Jean-Marie

2004-02-01

The bacterial metabolite and transition metal chelator pyridine-2,6-dithiocarboxylic acid (PDTC), promotes a novel and effective means of dechlorination of the toxic and carcinogenic pollutant, carbon tetrachloride. Pyridine-2,6-dithiocarboxylic acid has been presumed to act as a siderophore in the Pseudomonas strains known to produce it. To explore further the physiological function of PDTC production, we have examined its regulation, the phenotype of PDTC-negative (pdt) mutants, and envelope proteins associated with PDTC in P. putida strain DSM 3601. Aspects of the regulation of PDTC production and outer membrane protein composition were consistent with siderophore function. Pyridine-2,6-dithiocarboxylic acid production was coordinated with production of the well-characterized siderophore pyoverdine; exogenously added pyoverdine led to decreased PDTC production, and added PDTC led to decreased pyoverdine production. Positive regulation of a chromosomal pdtI-xylE transcriptional fusion, and of a 66 kDa outer membrane protein (IROMP), was seen in response to exogenous PDTC. Tests with transition metal chelators indicated that PDTC could provide a benefit under conditions of metal limitation; the loss of PDTC biosynthetic capacity caused by a pdtI transposon insertion resulted in increased sensitivity to 1,10-phenanthroline, a chelator that has high affinity for a range of divalent transition metals (e.g. Fe(2+), Cu(2+), Zn(2+)). Exogenously added PDTC could also suppress a phenotype of pyoverdine-negative (Pvd-) mutants, that of sensitivity to EDDHA, a chelator with higher affinity and specificity for Fe(3+). Measurement of 59Fe incorporation showed uptake from 59Fe:PDTC by DSM 3601 grown in low-iron medium, but not by cells grown in high iron medium, or by the pdtI mutant, which did not show expression of the 66 kDa envelope protein. These data verified a siderophore function for PDTC, and have implicated it in the uptake of transition metals in addition to iron.

Anaerobic degradation of tetrachloroethylene; Anaerober Abbau von Tetrachlorethylen

Energy Technology Data Exchange (ETDEWEB)

Diekert, G. [Stuttgart Univ. (Germany). Inst. fuer Mikrobiologie; Scholz-Muramatsu, H. [Stuttgart Univ. (Germany). Inst. fuer Siedlungswasserbau

1996-12-31

Dehalospirillum multivorans, a tetrachloroethylene-dechlorinating bacterium, was isolated in activated sludge. This organism is able to grow on a defined medium with hydrogen and tetrachloroethylene (PCE) as its only energy source. The organism was characterised and the physiology of dechlorination was studied. In this process PCE is dechlorinated to cis-1,2-dichloroethene (DCE) via trichloroethene (TCE). A fluidized-bed reactor which reduces PCE to DCE at a high rate (15 nmol/min/mg of protein at 5 {mu}M PCE) was inoculated with the bacterium. Meanwhile a reactor inoculated with D. multivorans and a fully dechlorinating mixed culture has become available which catalyses the complete dechlorination of PCE to ethene at just as high rates. Tetrachloroethene dehalogenase was purified from D. multivorans (unpublished results) and characterised. (orig./SR) [Deutsch] Aus Belebtschlamm wurde ein Tetrachlorethen-dechlorierendes Bakterium, Dehalospirillum multivorans, isoliert. Der Organismus waechst auf definiertem Medium mit Wasserstoff und Tetrachlorethen (PCE) als einziger Energiequelle. Der Organismus wurde charakterisiert und die Physiologie der Dechlorierung wurde untersucht. PCE wird dabei ueber Trichlorethen (TCE) bis zum cis-1,2-Dichlorethen (DCE) dechloriert. Mit diesem Bakterium wurde ein Wirbelschichtreaktor inokuliert, der mit hohen Raten (15 nmol/min/mg Protein bei 5 {mu}M PCE) PCE zu DCE reduziert. Inzwischen steht ein Reaktor zur Verfuegung, der mit D. multivorans und einer voellig dechlorierenden Mischkultur inokuliert wurde und der mit ebenso hohen Raten eine vollstaendige Dechlorierung von PCE bis zum Ethen katalysiert. Aus D. multivorans wurde die Tetrachlorethen-Dehalogenase gereinigt (unveroeffentlichte Ergebnisse) und charakterisiert. (orig./SR)

Anaerobic degradation of tetrachloroethylene; Anaerober Abbau von Tetrachlorethylen

Energy Technology Data Exchange (ETDEWEB)

Diekert, G [Stuttgart Univ. (Germany). Inst. fuer Mikrobiologie; Scholz-Muramatsu, H [Stuttgart Univ. (Germany). Inst. fuer Siedlungswasserbau

1997-12-31

Dehalospirillum multivorans, a tetrachloroethylene-dechlorinating bacterium, was isolated in activated sludge. This organism is able to grow on a defined medium with hydrogen and tetrachloroethylene (PCE) as its only energy source. The organism was characterised and the physiology of dechlorination was studied. In this process PCE is dechlorinated to cis-1,2-dichloroethene (DCE) via trichloroethene (TCE). A fluidized-bed reactor which reduces PCE to DCE at a high rate (15 nmol/min/mg of protein at 5 {mu}M PCE) was inoculated with the bacterium. Meanwhile a reactor inoculated with D. multivorans and a fully dechlorinating mixed culture has become available which catalyses the complete dechlorination of PCE to ethene at just as high rates. Tetrachloroethene dehalogenase was purified from D. multivorans (unpublished results) and characterised. (orig./SR) [Deutsch] Aus Belebtschlamm wurde ein Tetrachlorethen-dechlorierendes Bakterium, Dehalospirillum multivorans, isoliert. Der Organismus waechst auf definiertem Medium mit Wasserstoff und Tetrachlorethen (PCE) als einziger Energiequelle. Der Organismus wurde charakterisiert und die Physiologie der Dechlorierung wurde untersucht. PCE wird dabei ueber Trichlorethen (TCE) bis zum cis-1,2-Dichlorethen (DCE) dechloriert. Mit diesem Bakterium wurde ein Wirbelschichtreaktor inokuliert, der mit hohen Raten (15 nmol/min/mg Protein bei 5 {mu}M PCE) PCE zu DCE reduziert. Inzwischen steht ein Reaktor zur Verfuegung, der mit D. multivorans und einer voellig dechlorierenden Mischkultur inokuliert wurde und der mit ebenso hohen Raten eine vollstaendige Dechlorierung von PCE bis zum Ethen katalysiert. Aus D. multivorans wurde die Tetrachlorethen-Dehalogenase gereinigt (unveroeffentlichte Ergebnisse) und charakterisiert. (orig./SR)

In situ TCE degradation mediated by complex dehalorespiring communities during biostimulation processes

OpenAIRE

DUGAT-BONY, ERIC; Biderre-Petit, Corinne; Jaziri, Faouzi; David, Maude M; Denonfoux, Jérémie; Lyon, Delina Y; Richard, Jean-Yves; Curvers, Cyrille; Boucher, Delphine; Vogel, Timothy M; Peyretaillade, Eric; Peyret, Pierre

2012-01-01

Summary The bioremediation of chloroethene contaminants in groundwater polluted systems is still a serious environmental challenge. Many previous studies have shown that cooperation of several dechlorinators is crucial for complete dechlorination of trichloroethene to ethene. In the present study, we used an explorative functional DNA microarray (DechloArray) to examine the composition of specific functional genes in groundwater samples in which chloroethene bioremediation was enhanced by del...

Dechlorination of the dietary nona-chlorinated toxaphene congeners 62 and 50 into the octa-chlorinated toxaphene congeners 44 and 40 in zebrafish (Danio rerio) and Atlantic salmon (Salmo salar)

Energy Technology Data Exchange (ETDEWEB)

Berntssen, M.H.G., E-mail: marc.berntssen@nifes.no [National Institute of Nutrition and Seafood Research (NIFES), Postbox 2029 Nordnes, 5817 Bergen (Norway); Lundebye, A.-K.; Hop-Johannessen, L.; Lock, E.-J. [National Institute of Nutrition and Seafood Research (NIFES), Postbox 2029 Nordnes, 5817 Bergen (Norway)

2012-05-15

Graphical abstract: - Abstract: The relative feed-to-fish accumulation and possible biotransformation of the nona-chlorinated toxaphene congeners currently included in EU-legislation (CHB-50 and -62) and the octa-chlorinated congeners recommended by the European Food Safety Authority to be included in future surveillance of fish samples (CHB-40, 41, and 44) were investigated in the present study. Model fish Danio rerio were fed either (a) diets spiked with a combination as well as the pure individual toxaphene congeners CHB-50 or 62 or (b) diets spiked with the combination of CHB N-Ary-Summation 50 + 62 and/or CHB N-Ary-Summation 40 + 41 + 44. In addition, seawater adapted Atlantic salmon smolts were fed technical toxaphene enriched feeds for 62 days. Zebrafish fed a diet containing CHB-50 and CHB-62 accumulated newly formed CHB-40 and 41 and CHB-44, respectively. The biomagnifications factors (BMF) of the toxaphene congeners in Atlantic salmon muscle from the feeds spiked with technical toxaphene were significantly correlated with their relative lipophilicity (expressed as log K{sub ow}). An exception was CHB-44 which had a higher BMF than could be expected from its specific log K{sub ow}, reflecting that CHB-44 is a metabolite formed under dietary exposure to CHB-62. This paper reports the in vivo dechlorination of nona-chlorinated toxaphene congeners into octa-chlorinated congeners in feeding trials with a model fish (zebrafish) and an oily food fish (Atlantic salmon).

Dechlorination of the dietary nona-chlorinated toxaphene congeners 62 and 50 into the octa-chlorinated toxaphene congeners 44 and 40 in zebrafish (Danio rerio) and Atlantic salmon (Salmo salar)

International Nuclear Information System (INIS)

Berntssen, M.H.G.; Lundebye, A.-K.; Hop-Johannessen, L.; Lock, E.-J.

2012-01-01

Graphical abstract: - Abstract: The relative feed-to-fish accumulation and possible biotransformation of the nona-chlorinated toxaphene congeners currently included in EU-legislation (CHB-50 and -62) and the octa-chlorinated congeners recommended by the European Food Safety Authority to be included in future surveillance of fish samples (CHB-40, 41, and 44) were investigated in the present study. Model fish Danio rerio were fed either (a) diets spiked with a combination as well as the pure individual toxaphene congeners CHB-50 or 62 or (b) diets spiked with the combination of CHB ∑50 + 62 and/or CHB ∑40 + 41 + 44. In addition, seawater adapted Atlantic salmon smolts were fed technical toxaphene enriched feeds for 62 days. Zebrafish fed a diet containing CHB-50 and CHB-62 accumulated newly formed CHB-40 and 41 and CHB-44, respectively. The biomagnifications factors (BMF) of the toxaphene congeners in Atlantic salmon muscle from the feeds spiked with technical toxaphene were significantly correlated with their relative lipophilicity (expressed as log K ow ). An exception was CHB-44 which had a higher BMF than could be expected from its specific log K ow , reflecting that CHB-44 is a metabolite formed under dietary exposure to CHB-62. This paper reports the in vivo dechlorination of nona-chlorinated toxaphene congeners into octa-chlorinated congeners in feeding trials with a model fish (zebrafish) and an oily food fish (Atlantic salmon).

Reactive transport modeling of chemical and isotope data to identify degradation processes of chlorinated ethenes in a diffusion-dominated media

DEFF Research Database (Denmark)

Chambon, Julie Claire Claudia; Damgaard, Ida; Jeannottat, Simon

. Degradation and transport processes of chlorinated ethenes are not well understood in such geological settings, therefore risk assessment and remediation at these sites are particularly challenging. In this work, a combined approach of chemical and isotope analysis on core samples, and reactive transport...... the source zone (between 6 and 12 mbs). Concentrations and stable isotope ratios of the mother compounds and their daughter products, as well as redox parameters, fatty acids and microbial data, were analyzed with discrete sub-sampling along the cores. More samples (each 5 mm) were collected around...... of dechlorination and degradation pathways (biotic reductive dechlorination or abiotic β-elimination with iron minerals) in three core profiles. The model includes diffusion in the matrix, sequential reductive dechlorination, abiotic degradation, isotope fractionation due to degradation and due to diffusion...

Improving Effectiveness of Bioremediation at DNAPL Source Zone Sites by Applying Partitioning Electron Donors (PEDs)

Science.gov (United States)

2014-07-01

at an effective concentration at the DNAPL:water interface for the growth of and consumption by dechlorinating biomass . In heterogeneous geological...the promotion of dechlorinating biomass growth close to the DNAPL, which results in sustained enhanced DNAPL dissolution rates. This approach...fine- grained sands with varying amounts of shell fragments, with a hydraulic conductivity of 3 ft/day in the 30 to 45 ft BLS interval; • 45 to 48 ft

FY1998 report on the achievements on the research and development of a quickly effective and innovative energy environment technology, and development of a technology to re-use wastes as resources and fuel; Sokkoteki kakushinteki energy kankyo gijutsu kenkyu kaihatsu, kanen gomi saishigen nenryoka gijutsu kaihatsu 1998 nendo seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

1999-03-01

With objectives to realize a recycling society and protect global environment, development will be made on solidified fuel using waste papers and waste plastics as the raw materials. This paper describes the achievements in fiscal 1998. To develop a pretreatment technology, analyses and discussions were given on functions required to separate and remove such foreign materials contained in combustible wastes as metals, ceramics, and glasses, and to pulverize the combustibles removed of non-combustible materials. A bench-scale testing equipment of 0.5 ton per hour was installed and operated on a trial basis. In order to identify dechlorination properties of waste papers and plastics to develop a dechlorination technology, basic dechlorination and pyrolysis tests were performed by using cellulose powder and polyvinyl chloride powder as raw materials. Detailed design, fabrication, installation and trial operation were carried out on a dechlorination device to be assembled into the bench-scale testing equipment. Investigations were given on the actual status of discharge and collection of waste papers and plastics to discuss the practical use of the fuel. The current status of discharge of general wastes was identified, which will be the object of the container package recycling law. The range of LCA was discussed, and technical data of wastes electric power generation were collected. (NEDO)

Biotransformation of chlorinated aliphatic solvents in the presence of aromatic compounds under methanogenic conditions

International Nuclear Information System (INIS)

Liang, L.N.; Grbic-Galic, D.

1993-01-01

Transformation of carbon tetrachloride (CT) and tetrachloroethylene (PCE) was studied under methanogenic conditions, in the presence or absence of toluene, ethylbenzene, phenol, and benzoate. Microbial inoculate for the experiments were derived from three groundwater aquifers contaminated by jet fuel or creosote. CT and PCE were reductively dechlorinated in all the examined castes (CT to chloroform [CF]; PCE to trichloroethylene [TCE], trans-1,2-dichloroethylene [DCE], and vinyl chloride [VC]). In the aquifer microcosms, the electron donors used for the reductive transformations were most likely the unidentified organic compounds present on aquifer solids, or storage materials in microorganisms. Alternatively, molecular hydrogen from the anaerobic incubator atmosphere could have been used. The addition of benzoate caused a decrease in rates of dechlorination if benzoate was transformed. Phenol and ethylbenzene were not degraded and did not influence the transformation of CT or PCE. Toluene, in most of the studied cases, had no influence on reductive dechlorination of either CT or PCE. Only in microcosms derived from a JP-4 jet fuel-contaminated aquifer did the anaerobic degradation of toluene occur simultaneously with reductive dechlorination of PCE, suggesting that toluene might possibly have been used as an electron donor for reductive transformation of chlorinated solvents

Application of a long-lasting colloidal substrate with pH and hydrogen sulfide control capabilities to remediate TCE-contaminated groundwater.

Science.gov (United States)

Sheu, Y T; Chen, S C; Chien, C C; Chen, C C; Kao, C M

2015-03-02

A long-lasting emulsified colloidal substrate (LECS) was developed for continuous carbon and nanoscale zero-valent iron (nZVI) release to remediate trichloroethylene (TCE)-contaminated groundwater under reductive dechlorinating conditions. The developed LECS contained nZVI, vegetable oil, surfactants (Simple Green™ and lecithin), molasses, lactate, and minerals. An emulsification study was performed to evaluate the globule droplet size and stability of LECS. The results show that a stable oil-in-water emulsion with uniformly small droplets (0.7 μm) was produced, which could continuously release the primary substrates. The emulsified solution could serve as the dispensing agent, and nZVI particles (with diameter 100-200 nm) were distributed in the emulsion evenly without aggregation. Microcosm results showed that the LECS caused a rapid increase in the total organic carbon concentration (up to 488 mg/L), and reductive dechlorination of TCE was significantly enhanced. Up to 99% of TCE (with initial concentration of 7.4 mg/L) was removed after 130 days of operation. Acidification was prevented by the production of hydroxide ion by the oxidation of nZVI. The formation of iron sulfide reduced the odor from produced hydrogen sulfide. Microbial analyses reveal that dechlorinating bacteria existed in soils, which might contribute to TCE dechlorination. Copyright © 2014 Elsevier B.V. All rights reserved.

The Pd-catalyzed hydrodechlorination of chlorophenols in aqueous solutions under mild conditions: A promising approach to practical use in wastewater

International Nuclear Information System (INIS)

Xia Chuanhai; Liu Ying; Zhou Shiwei; Yang Cuiyun; Liu Sujing; Xu Jie; Yu Junbao; Chen Jiping; Liang Xinmiao

2009-01-01

Catalytic hydrotreating of chlorophenols was carried out in water with Pd/C at 25 deg. C under atmospheric pressure. 1.0% (w/w) monocholophenols was completely dechlorinated within 60 min. Phenol, cyclohexanone and cyclohexanol were formed. In contrast to the dechlorination of monochlorophenols, the hydrogenation reaction of polychlorinated phenols became difficult and reaction rates were strongly dependent upon the number of the chlorine atoms. The solvent property had a considerably important influence on the dechlorination reaction. Water as a solvent showed more advantages than organic solvents. It was much easier to be hydrodechlorinated for chlorophenols in aqueous solutions. However, the presence of THF, dioxane, DMSO or DMF in water was disadvantageous to the reaction and easily to cause Pd/C deactivation. Additionally, when different halogenated organic compounds were present in aqueous solution, the dehalogenation reaction was the competitive hydrogenation process.

The Pd-catalyzed hydrodechlorination of chlorophenols in aqueous solutions under mild conditions: A promising approach to practical use in wastewater

Energy Technology Data Exchange (ETDEWEB)

Xia Chuanhai, E-mail: chuanhaixia@gmail.com [Yantai Institute of Coastal Zone Research for Sustainable Development, CAS, Yantai 264003 (China); Liu Ying; Zhou Shiwei; Yang Cuiyun; Liu Sujing [Yantai Institute of Coastal Zone Research for Sustainable Development, CAS, Yantai 264003 (China); Xu Jie [Dalian Institute of Chemical Physics, CAS, Dalian, 116021 (China); Yu Junbao [Yantai Institute of Coastal Zone Research for Sustainable Development, CAS, Yantai 264003 (China); Chen Jiping; Liang Xinmiao [Dalian Institute of Chemical Physics, CAS, Dalian, 116021 (China)

2009-09-30

Catalytic hydrotreating of chlorophenols was carried out in water with Pd/C at 25 deg. C under atmospheric pressure. 1.0% (w/w) monocholophenols was completely dechlorinated within 60 min. Phenol, cyclohexanone and cyclohexanol were formed. In contrast to the dechlorination of monochlorophenols, the hydrogenation reaction of polychlorinated phenols became difficult and reaction rates were strongly dependent upon the number of the chlorine atoms. The solvent property had a considerably important influence on the dechlorination reaction. Water as a solvent showed more advantages than organic solvents. It was much easier to be hydrodechlorinated for chlorophenols in aqueous solutions. However, the presence of THF, dioxane, DMSO or DMF in water was disadvantageous to the reaction and easily to cause Pd/C deactivation. Additionally, when different halogenated organic compounds were present in aqueous solution, the dehalogenation reaction was the competitive hydrogenation process.

Quantifying Enhanced Microbial Dehalogenation Impacting the Fate and Transport of Organohalide Mixtures in Contaminated Sediments

Science.gov (United States)

2012-02-01

dechlorinated in samples that had been exposed to oxygen for one week. The reason for this rapid dechlorination could be the formation of biofilms in micro...samples might be the result of heterogeneous moisture content affecting formation of biofilms and anaerobic micro-niches that support communities of... stainless steel extraction cell containing 0.6 g Cu and 2.4 g fluorisil between two cellulose filters on the bottom of the cell and the remaining cell

Dechlorination and Stabilization of Molten Salt Waste by Using xSiO2-yAl2O3- zP2O5 at Melting Temperature

International Nuclear Information System (INIS)

Park, Hwanseo; Kim, Intae; Kim, Hwanyoung; Kim, Joonhyung

2007-01-01

Molten salt waste, which is generated from the pyroprocess to separate uranium and trans-uranium elements from spent nuclear fuel, has been interested to researchers in the radioactive waste management. For its final disposal, direct immobilization into a suitable host matrix or indirect solidification by other chemical routes requires the control of chlorides and its volatility since molten salt wastes mainly consist of volatile metal chlorides. Glass-bonded sodalite (Na 6 M 2 Al 6 Si 6 O 24 Cl 2 , 1-5) suggested by Argonne National Laboratory (ANL), to the present, could be a practical solution to the immobilization of this waste, where waste form can be fabricated at about 915 .deg., lower than the melting temperature of many borosilicate glasses ( -1150 .deg.). A wet dechlorination to oxides or a thermal conversion into borate glass was suggested to remove Cl from salt waste (6-7) and it seemed that the preference of radionuclides for the intended chemical conversions or immobilizations described above could be hardly accomplished or failed, except the phosphate precipitation method suggested by Volkovich and his co-workers (8). Our research group suggested a novel method to treat molten salt waste, named GRSS (Gel-Route Stabilization/Solidification) using Si-P-Al system as a gel-forming system. This showed little vaporization during high temperature process and good leach resistance on Cs and Sr. As another method, this study suggested a method to stabilize molten salt wastes by using xSiO 2 -yAl 2 O 3 - zP 2 O 5 material. GRSS method is considered as a 'reaction system' to completely convert salt waste into stable product while the inorganic material used in this study is a stabilizer for salt wastes. Using this material, this study investigated the reactivity on different metal chlorides, thermal stability, leach-resistance and etc

Coexistence of two distinct Sulfurospirillum populations respiring tetrachloroethene - genomic and kinetic considerations

DEFF Research Database (Denmark)

Buttet, Géraldine Florence; Murray, Alexandra Marie; Goris, Tobias

2018-01-01

Two anaerobic bacterial consortia, each harboring a distinct Sulfurospirillum population, were derived from a ten year old consortium, SL2, previously characterized for the stepwise dechlorination of tetrachloroethene (PCE) to cis-dichloroethene (cis-DCE) via accumulation of trichloroethene (TCE......). Population SL2-1 dechlorinated PCE to TCE exclusively, while SL2-2 produced cis-DCE from PCE without substantial TCE accumulation. The reasons explaining the long-term coexistence of the populations were investigated. Genome sequencing revealed a novel Sulfurospirillum species, designated 'Candidatus...

Decomposition of PCBs in oils using gamma radiolysis

International Nuclear Information System (INIS)

Mincher, B.J.; Arbon, R.E.; Schwendiman, G.L.

1996-01-01

This paper investigates the radiolysis of the polychlorinated biphenyls (PCBs) in several oil matrices. The results of mechanism and kinetic studies in isooctane are presented. The decomposition of PCBs in isooctane is shown to occur by reductive dechlorination due to electron capture and to proceed with pseudo-first-order kinetics. The rate is dependent on the initial PCB concentration. Electron capture detection gas chromatograms confirm that dechlorination also occurs with commercial Aroclor PCBs in irradiated transformer and hydraulic oils. The results of a demonstration experiment involving PCB contaminated waste hydraulic oils are presented

Interaction of 2,4,6-trichlorophenol with high carbon iron filings: Reaction and sorption mechanisms

Energy Technology Data Exchange (ETDEWEB)

Sinha, Alok [Environmental Engineering and Management Programme, Department of Civil Engineering, Indian Institute of Technology Kanpur, Kanpur 208016 (India); Bose, Purnendu [Environmental Engineering and Management Programme, Department of Civil Engineering, Indian Institute of Technology Kanpur, Kanpur 208016 (India)], E-mail: pbose@iitk.ac.in

2009-05-15

Reductive dehalogenation of 2,4,6-trichlorophenol (2,4,6-TCP) by two types of high carbon iron filings (HCIF), HCIF-1 and HCIF-2 was studied in batch reactors. While the iron, copper, manganese and carbon content of the two types of HCIF was similar, the specific surface area of HCIF-1 and HCIF-2 were 1.944 and 3.418 m{sup 2} g{sup -1}, respectively. During interaction with HCIF-1, 2,4,6-TCP adsorbed on HCIF-1 surface resulting in rapid reduction of aqueous phase 2,4,6-TCP concentration. However, reductive dehalogenation of 2,4,6-TCP was negligible. During interaction between 2,4,6-TCP and HCIF-2, both 2,4,6-TCP adsorption on HCIF-2, and 2,4,6,-TCP dechlorination was observed. 2,4,6-TCP partitioning between solid and aqueous phase could be described by a Freundlich isotherm, while 2,4,6-TCP dechlorination could be described by an appropriate rate expression. A mathematical model was developed for describing the overall interaction of 2,4,6-TCP with HCIF-2, incorporating simultaneous adsorption/desorption and dechlorination reactions of 2,4,6-TCP with the HCIF surface. 2,4-Dichlorophenol (2,4-DCP), 2-chlorophenol (2-CP) and minor amounts of 4-chlorophenol (4-CP) evolved as 2,4,6-TCP dechlorination by-products. The evolved 2,4-DCP partitioned strongly to the HCIF surface. 4-CP and 2-CP accumulated in the aqueous phase. No transformation of 2-CP or 4-CP to phenol was observed.

Fenton-like oxidation of 2,4-DCP in aqueous solution using iron-based nanoparticles as the heterogeneous catalyst.

Science.gov (United States)

Li, Renchao; Gao, Ying; Jin, Xiaoying; Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravendra

2015-01-15

In this report, various iron-based nanoparticles (nZVI, n-Ni/Fe, n-Pd/Fe) were used for both heterogeneous Fenton oxidation of 2,4-dichlorophenol (2,4-DCP) and reductive dechlorination of 2,4-DCP in order to understand their roles in the Fenton oxidation and the reductive degradation of 2,4-DCP. The dechlorination efficiency of 2,4-DCP using nZVI, n-Ni/Fe, n-Fe/Pd and Fe(2)(+) was 6.48%, 6.80%, 15.95%, 5.02%, while Fenton oxidation efficiency of 2,4-DCP was 57.87%, 34.23%, 27.94%, 19.61% after 180 min, respectively. The new findings included a higher dechlorination using n-Fe/Pd due to Pd effective catalysis and the effective heterogeneous Fenton oxidation using nZVI depending on reductive dechlorination and heterogeneous Fenton oxidation occurs simultaneously. However, nZVI as the potential catalyst for heterogeneous Fenton was observed, and SEM, EDS and XRD demonstrate that change on the nZVI surface occurred due to the Fe(2+) leaching, and Total Organic Carbon (TOC) (30.71%) shows that 2,4-DCP was degraded. Furthermore, the experiment indicates that the pH values and concentration of 2,4-DCP significantly impacted on the heterogeneous Fenton oxidation of 2,4-DCP and the data fits well with the pseudo first-order kinetic model, which was a diffusion-controlled reaction. Finally, a possible mechanism for degradation of 2,4-DCP was proposed. Copyright © 2014 Elsevier Inc. All rights reserved.

To what extent can isotopes help substantiate natural attenuation of chlorinated ethenes?

DEFF Research Database (Denmark)

Badin, A.; Broholm, Mette Martina; Hunkeler, D.

to which isotopes could help substantiate natural attenuation of chlorinated ethenes at the field scale. Our work hence aims at exploring the latter based on data acquired in 2006 in a site located in Denmark which is contaminated with PCE and its end-products TCE, cDCE, and VC. Previous work on this site...... has enabled to demonstrate that PCE and TCE were undergoing reductive dechlorination while cDCE would be at least partially degraded through reductive dechlorination1. However, the magnitude of the contaminants attenuation by biodegradation was not evaluated. Based on simple modeling including...

Photodegradation of the azole fungicide climbazole by ultraviolet irradiation under different conditions: Kinetics, mechanism and toxicity evaluation

Energy Technology Data Exchange (ETDEWEB)

Liu, Wang-Rong; Ying, Guang-Guo, E-mail: guang-guo.ying@gig.ac.cn; Zhao, Jian-Liang; Liu, You-Sheng; Hu, Li-Xin; Yao, Li; Liang, Yan-Qiu; Tian, Fei

2016-11-15

Highlights: • Climbazole (CZ) could be effectively degraded under UV-254 irradiation. • CZ underwent direct and self-sensitized photolysis involving ROS. • The main photodegradation by-products of CZ were identified and semi-quantitated. • Pathway includes hydroxylative dechlorination, dechlorination, and de-pinacolone. • The toxicity of the photodegradation system reduced after UV-254 irradiation. - Abstract: Climbazole (CZ) has been known to persist in various environmental media, and may cause potential risks to aquatic organisms. This study investigated the photodegradation of CZ by ultraviolet (UV, 254 nm) under different conditions. The results revealed that CZ could be effectively degraded in aqueous solutions under UV-254 irradiation with a half-life of 9.78 min (pH = 7.5), and the photodegradation followed pseudo-first-order kinetics. pH had almost no effect on its rate constants and quantum yields; but the water quality of natural waters could affect the photolysis of CZ, and the coexisting constituents such as Fe{sup 3+}, NO{sub 3}{sup −}, and HA obviously inhibited its photolysis. The addition of different radical scavengers also inhibited the photodegradation of CZ due to the reduction of reactive oxygen species (ROS). CZ underwent direct and self-sensitized photolysis involving ROS. Based on the identified photodegradation by-products, the proposed pathways included hydroxylative dechlorination, dechlorination and de-pinacolone. Moreover, toxicity evaluation using duckweed found significant toxicity reduction in the photodegradation system of CZ after the irradiation of UV-254, and the remaining by-products did not pose extra toxicity compared with CZ itself. These findings from present study suggest that CZ in effluent could be further reduced by applying UV photolysis treatment.

Monitoring biodegradation of ethene and bioremediation of chlorinated ethenes at a contaminated site using compound-specific isotope analysis (CSIA).

Science.gov (United States)

Mundle, Scott O C; Johnson, Tiffany; Lacrampe-Couloume, Georges; Pérez-de-Mora, Alfredo; Duhamel, Melanie; Edwards, Elizabeth A; McMaster, Michaye L; Cox, Evan; Révész, Kinga; Sherwood Lollar, Barbara

2012-02-07

Chlorinated ethenes are commonly found in contaminated groundwater. Remediation strategies focus on transformation processes that will ultimately lead to nontoxic products. A major concern with these strategies is the possibility of incomplete dechlorination and accumulation of toxic daughter products (cis-1,2-dichloroethene (cDCE), vinyl chloride (VC)). Ethene mass balance can be used as a direct indicator to assess the effectiveness of dechlorination. However, the microbial processes that affect ethene are not well characterized and poor mass balance may reflect biotransformation of ethene rather than incomplete dechlorination. Microbial degradation of ethene is commonly observed in aerobic systems but fewer cases have been reported in anaerobic systems. Limited information is available on the isotope enrichment factors associated with these processes. Using compound-specific isotope analysis (CSIA) we determined the enrichment factors associated with microbial degradation of ethene in anaerobic microcosms (ε = -6.7‰ ± 0.4‰, and -4.0‰ ± 0.8‰) from cultures collected from the Twin Lakes wetland area at the Savannah River site in Georgia (United States), and in aerobic microcosms (ε = -3.0‰ ± 0.3‰) from Mycobacterium sp. strain JS60. Under anaerobic and aerobic conditions, CSIA can be used to determine whether biotransformation of ethene is occurring in addition to biodegradation of the chlorinated ethenes. Using δ(13)C values determined for ethene and for chlorinated ethenes at a contaminated field site undergoing bioremediation, this study demonstrates how CSIA of ethene can be used to reduce uncertainty and risk at a site by distinguishing between actual mass balance deficits during reductive dechlorination and apparent lack of mass balance that is related to biotransformation of ethene.

Humin as an electron donor for enhancement of multiple microbial reduction reactions with different redox potentials in a consortium.

Science.gov (United States)

Zhang, Dongdong; Zhang, Chunfang; Xiao, Zhixing; Suzuki, Daisuke; Katayama, Arata

2015-02-01

A solid-phase humin, acting as an electron donor, was able to enhance multiple reductive biotransformations, including dechlorination of pentachlorophenol (PCP), dissimilatory reduction of amorphous Fe (III) oxide (FeOOH), and reduction of nitrate, in a consortium. Humin that was chemically reduced by NaBH4 served as an electron donor for these microbial reducing reactions, with electron donating capacities of 0.013 mmol e(-)/g for PCP dechlorination, 0.15 mmol e(-)/g for iron reduction, and 0.30 mmol e(-)/g for nitrate reduction. Two pairs of oxidation and reduction peaks within the humin were detected by cyclic voltammetry analysis. 16S rRNA gene sequencing-based microbial community analysis of the consortium incubated with different terminal electron acceptors, suggested that Dehalobacter sp., Bacteroides sp., and Sulfurospirillum sp. were involved in the PCP dechlorination, dissimilatory iron reduction, and nitrate reduction, respectively. These findings suggested that humin functioned as a versatile redox mediator, donating electrons for multiple respiration reactions with different redox potentials. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Substrate interactions in dehalogenation of 1,2-dichloroethane, 1,2-dichloropropane, and 1,1,2-trichloroethane mixtures by Dehalogenimonas spp.

Science.gov (United States)

Dillehay, Jacob L; Bowman, Kimberly S; Yan, Jun; Rainey, Fred A; Moe, William M

2014-04-01

When chlorinated alkanes are present as soil or groundwater pollutants, they often occur in mixtures. This study evaluated substrate interactions during the anaerobic reductive dehalogenation of chlorinated alkanes by the type strains of two Dehalogenimonas species, D. lykanthroporepellens and D. alkenigignens. Four contaminant mixtures comprised of combinations of the chlorinated solvents 1,2-dichloroethane (1,2-DCA), 1,2-dichloropropane (1,2-DCP), and 1,1,2-trichloroethane (1,1,2-TCA) were assessed for each species. Chlorinated solvent depletion and daughter product formation determined as a function of time following inoculation into anaerobic media revealed preferential dechlorination of 1,1,2-TCA over both 1,2-DCA and 1,2-DCP for both species. 1,2-DCA in particular was not dechlorinated until 1,1,2-TCA reached low concentrations. In contrast, both species concurrently dechlorinated 1,2-DCA and 1,2-DCP over a comparably large concentration range. This is the first report of substrate interactions during chlorinated alkane dehalogenation by pure cultures, and the results provide insights into the chlorinated alkane transformation processes that may be expected for contaminant mixtures in environments where Dehalogenimonas spp. are present.

Anaerobic Transformation of Chlorinated Aliphatic Hydrocarbons in a Sand Aquifer Based on Spatial Chemical Distributions

Science.gov (United States)

Semprini, Lewis; Kitanidis, Peter K.; Kampbell, Don H.; Wilson, John T.

1995-04-01

We estimated the distribution of chlorinated aliphatic hydrocarbons (CAHs) from groundwater samples collected along three transects in a sand aquifer. Trichloroethylene (TCE) leaked and contaminated the aquifer probably more than a decade before we collected the measurements. The data show significant concentrations of TCE, cis-l,2-dichloroethylene (c-DCE), vinyl chloride (VC), and ethene. We attributed DCE, VC, and ethene to the reductive dehalogenation of TCE. The CAH concentrations varied significantly with depth and correlate with sulfate and methane concentrations. Anoxic aquifer conditions exist with methane present at relatively high concentrations at depth. High concentrations of TCE correspond with the absence of methane or low methane concentrations, whereas products of TCE dehalogenation are associated with higher methane concentrations and low sulfate concentrations. Indications are that the dechlorination of TCE and DCE to VC and ethene is associated with sulfate reduction and active methanogenesis. TCE dechlorination to DCE is likely occurring under the less reducing conditions of sulfate reduction, with further reductions to VC and ethene occurring under methanogenic conditions. We estimated that about 20% of TCE has dechlorinated to ethene. The analysis of the data enhanced our knowledge of natural in situ transformation and transport processes of CAHs.

Electrocatalytic Reduction-oxidation of Chlorinated Phenols using a Nanostructured Pd-Fe Modified Graphene Catalyst

International Nuclear Information System (INIS)

Shi, Qin; Wang, Hui; Liu, Shaolei; Pang, Lei; Bian, Zhaoyong

2015-01-01

A Pd-Fe modified graphene (Pd-Fe/G) catalyst was prepared by the Hummers oxidation method and bimetallic co-deposition method. The catalyst was then characterized by various characterization techniques and its electrochemical property toward the electrocatalytic reduction-oxidation of chlorinated phenols was investigated by using cyclic voltammetry and differential pulse voltammetry. The results of the characterization show that the Pd-Fe/G catalyst in which the weight proportion of Pd and Fe is 1:1 has an optimal surface performance. The diameter of the Pd-Fe particles is approximately 5.2 ± 0.3 nm, with a uniform distribution on the supporting graphene. This is smaller than the Pd particles of a Pd-modified graphene (Pd/G) catalyst. The Pd-Fe/G catalyst shows a higher electrocatalytic activity than the Pd/G catalyst for reductive dechlorination when feeding with hydrogen gas. The reductive peak potentials of −0.188 V, −0.836 V and −0.956 V in the DPV curves are attributed to the dechlorination of ortho-Cl, meta-Cl, and para-Cl in 2-chlorophenol, 3-chlorophenol and 4-chlorophenol, respectively. In accordance with an analysis of the frontier orbital theory, the order of ease of dechlorination with Pd-Fe/G catalyst is 2-chlorophenol > 3-chlorophenol > 4-chlorophenol. The Pd-Fe/G catalyst has a greater activity than the Pd/G catalyst in accelerating the two-electron reduction of O_2 to H_2O_2, which is attributed to the higher current of the reduction peak at approximately −0.40 V when feeding with oxygen gas. Therefore, the Pd-Fe/G catalyst exhibits a higher electrocatalytic activity than the Pd/G catalyst for the reductive dechlorination and acceleration of the two-electron reduction of O_2 to H_2O_2.

Degradation of lindane by a novel embedded bio-nano hybrid system in aqueous environment.

Science.gov (United States)

Salam, Jaseetha Abdul; Das, Nilanjana

2015-03-01

The objective of this study was to evaluate the effect of an embedded bio-nano hybrid system using nanoscale zinc oxide (n-ZnO) and lindane-degrading yeast Candida VITJzN04 for lindane degradation. Nano-embedding of the yeast was done with chemically synthesized n-ZnO particles (50 mg/mL) and was visualized by atomic force microscope (AFM) and scanning electron microscope (SEM). Nanoparticles were embedded substantially on the surfaces of the yeast cells and translocated into the cell cytoplasm without causing any lethal effect to the cell until 50 mg/mL. Lindane (600 mg/L) degradation was studied both in the individual and hybrid system. Rapid reductive-dechlorination of lindane was attained with n-ZnO under illuminated conditions, with the generation of chlorobenzene and benzene as dechlorination products. The bio-nano hybrid was found to be more effective compared to the native yeasts for lindane degradation and resulted in complete removal within 3 days. The kinetic data analysis implied that the half-life of lindane was 9 h for bio-nano hybrid and 28 h for Candida VITJzN04. The enhanced lindane degradation by bio-nano hybrid might be due to increased porosity and permeability of the yeast cell membrane, facilitating the easy entry of lindane into cell cytoplasm and n-ZnO-mediated dechlorination. To the best of our knowledge, this report, for the first time, suggests the use of n-ZnO-mediated dechlorination of lindane and the novel bio-nano hybrid system that reduces the half-life to one third of the time taken by the yeast alone. The embedded bio-nano hybrid system may be exploited as an effective remediation tool for the treatment of lindane-contaminated wastewaters.

Uncovering the intrinsic relationship of electrocatalysis and molecular electrochemistry for dissociative electron transfer to polychloroethanes at silver cathode

International Nuclear Information System (INIS)

Huang, Binbin; Zhu, Yuanyuan; Li, Jing; Zeng, Guangming; Lei, Chao

2017-01-01

Highlights: • Thermodynamics of dissociative electron transfer to C–Cl bonds at Ag are studied. • The catalyzed dissociative electron transfer theory was proposed for the first time. • The adsorption of organic chlorides onto Ag plays a key role for dechlorination. • The catalytic property of Ag is ascribed to the lower of intrinsic barrier energy. • The relationship of electrocatalysis and molecular electrochemistry is indicated. - Abstract: The relationship between electrocatalysis and molecular electrochemistry for the reductive dechlorination of organic chlorides has been a central topic for decades. Herein, we try to reveal the catalytic property of silver electrode by investigating the thermodynamics of dissociative electron transfer (DET) to C–Cl bonds of polychloroethanes (PCAs) on both inert (GC) and catalytic (Ag) electrodes. By extending the “sticky” DET model reported by Savéant, we show that the catalyzed DET model can well describe the activation-driving force relationships for the electrocatalytic dechlorination on Ag, where in addition to the possible ion-dipole interations, the adsorption of chlorinated species onto Ag surface, which is found to play a fundamental role in the electrocatalysis process in this study, is introduced in the new developed DET model. In this work, we firstly report that the catalytic property of Ag electrode characterizing with drastically postive shift of reduction potential is ascribed to the lower of intrinsic barrier free energy, rather than the activation free energy, for the reductive dechlorination. Moreover, the intrinsic relationship of electrocatalysis and molecular electrochemistry is clearly indicated and quantitatively developed. These results may provide new insights in uncovering both the nature of catalytic property of Ag and the relationship of electrocatalysis and molecular electrochemistry for PCAs and other halocarbons.

Thermal degradation of hexachlorobenzene in the presence of calcium oxide at 340-400 °C.

Science.gov (United States)

Yin, Keqing; Gao, Xingbao; Sun, Yifei; Zheng, Lei; Wang, Wei

2013-11-01

Hexachlorobenzene (HCB) in the milligram range was co-heated with calcium oxide (CaO) powder in sealed glass ampoules at 340-400 °C. The heated samples were characterized and analyzed by Raman spectroscopy, elemental analysis, gas chromatography/mass spectrometry, ion chromatography, and thermal/optical carbon analysis. The degradation products of HCB were studied at different temperatures and heated times. The amorphous carbon was firstly quantitatively evaluated and was thought to be important fate of the C element of HCB. The yield of amorphous carbon in products increased with heating time, for samples treated for 8h at 340, 380 °C and 400 °C, the value were 17.5%, 34.8% and 50.2%, respectively. After identification of the dechlorination products, the HCB degradation on CaO at 340-400 °C was supposed to through dechlorination/polymerization pathway, which is induced by electron transfer, generate chloride ions and form high-molecular weight intermediates with significant levels of both hydrogen and chlorine, and finally form amorphous carbon. Higher temperature was beneficial for the dechlorination/polymerization efficiency. The results are helpful for clarifying the reaction mechanism for thermal degradation of chlorinated aromatics in alkaline matrices. Copyright © 2013 Elsevier Ltd. All rights reserved.

Hydrogeologic characterization and assessment of bioremediation of chlorinated benzenes and benzene in wetland areas, Standard Chlorine of Delaware, Inc. Superfund Site, New Castle County, Delaware, 2009-12

Science.gov (United States)

Lorah, Michelle M.; Walker, Charles W.; Baker, Anna C.; Teunis, Jessica A.; Emily Majcher,; Brayton, Michael J.; Raffensperger, Jeff P.; Cozzarelli, Isabelle M.

2015-01-01

desorption from the sediments.When highly reducing, methanogenic, or sulfate-reducing conditions existed in the wetland groundwater, molar composition of the volatile organic compounds (VOCs) showed that chlorobenzene and benzene were predominant, indicating biodegradation of the chlorinated benzenes through reductive dechlorination pathways. Temporal changes in redox conditions between 2009 and 2011–12 have shifted the locations in the wetland study area where reductive dechlorination is evident. Microbial community analyses of sediment showed relatively high cell numbers and diversity of populations (Dehalococcoides, Dehalobacter, Desulfitobacterium, and Geobacter) that are known to contain species capable of reductive dechlorination, confirming groundwater geochemistry evidence of the occurrence of reductive dechlorination. Natural attenuation was not sufficient, however, to reduce total VOC concentrations along upward groundwater flowpaths in the wetland sediments, most likely due to the additional source of contaminants in the upper sediments. In situ microcosms that were unamended except for the addition of 13C-labeled contaminants in some treatments, confirmed that the native microbial community was able to biodegrade the higher chlorinated benzenes through reductive dechlorination and that 1,2-dichlorobenzene, chlorobenzene, and benzene could be degraded to carbon dioxide through oxidation pathways. Microcosms that were bioaugmented with the anaerobic dechlorinating consortium WBC-2 and deployed in the wetland sediments showed reductive dechlorination of tri-, di-, and monochlorobenzene, and 13C-chlorobenzene treatments showed complete degradation of chlorobenzene to carbon dioxide under anaerobic conditions.Experiments with a continuous flow, fixed-film bioreactor seeded with native microorganisms in groundwater from the wetland area showed both aerobic and anaerobic biodegradation of dichlorobenzenes, monochlorobenzene, and benzene, although

Reductive Anaerobic Biological In Situ Treatment Technology Treatability Testing

National Research Council Canada - National Science Library

Alleman, Bruce

2002-01-01

Enhanced biological reductive dechlorination (EBRD) shows a great deal of promise for efficiently treating groundwater contaminated with chlorinated solvents, but demonstration sites around the country were reporting mixed results...

Cost and Performance Report for Reductive Anaerobic Biological in Situ Treatment Technology (RABITT) Treatability Testing

National Research Council Canada - National Science Library

Alleman, Bruce

2003-01-01

Enhanced biological reductive dechlorination (EBRD) shows a great deal of promise for efficiently treating groundwater contaminated with chlorinated solvents, but demonstration sites around the country were reporting mixed results...

Experimental design for assessment of electrokinetically enhanced delivery of lactate and bacteria in 1,2-cis-dichloroethylene contaminated limestone

DEFF Research Database (Denmark)

Hyldegaard, Bente Højlund; Nedergaard, L. W.; Ottosen, Lisbeth

2015-01-01

Bacterial dechlorination of chlorinated solvents often causes accumulation of the intermediate cis-DCE. Back diffusion of e.g. cis-DCE, due to the dual porosity of limestone, often limits the remediation efficiency. A remediation scheme capable of establishing contact between contaminant, degrading...... bacteria and electron donor within the low permeable limestone matrix is required. The technology EK-BIO, which combines enhanced reductive dechlorination and electrokinetics (EK), was assessed. This novel technology has not previously been tested in limestone. An experimental set-up was designed to meet...... that fermentative bacteria were distributed by electrophoresis. This study suggests that EK application can establish the essential contact and overcome back diffusion. Thereby, EK-BIO may be superior to advection-based technologies for bioremediation of chlorinated solvent contaminated limestone matrices....

New photodegradation products of chlorpyrifos and their detection on glass, soil, and leaf surfaces

International Nuclear Information System (INIS)

Walia, S.; Dureja, P.; Mukerjee, S.K.

1988-01-01

The organophosphate insecticide chlorpyrifos was irradiated under different photochemical conditions and the products characterized by gas chromatography, mass spectrometry, and NMR spectroscopy. Irradiation of chlorpyrifos in hexane yielded dechlorinated photoproducts and cleavage products. In methanol, besides these products, chlorpyrifos gave oxons. Several new photoproducts, the formation of which apparently occurs by the displacement of 5-chloro by a methoxy substituent in the pyridyl moiety. The possibility of formation of such products on glass, soil, and leaf surfaces under the influence of UV and solar simulated light have also been explored and many new products presumably formed due to simultaneous photo-dechlorination, oxidation and hydrolytic processes were detected. Photodegradation of chlorpyrifos was rapid on a soil surface but comparatively slow on glass and leaf surfaces

Reductive Dehalogenation of Trichloroacetic Acid by Trichlorobacter thiogenes gen. nov., sp. nov.

Science.gov (United States)

De Wever, Helene; Cole, James R.; Fettig, Michael R.; Hogan, Deborah A.; Tiedje, James M.

2000-01-01

A bacterium able to grow via reductive dechlorination of trichloroacetate was isolated from anaerobic soil enrichments. The isolate, designated strain K1, is a member of the δ proteobacteria and is related to other known sulfur and ferric iron reducers. In anaerobic mineral media supplemented with acetate and trichloroacetate, its doubling time was 6 h. Alternative electron donor and acceptors were acetoin and sulfur or fumarate, respectively. Trichloroacetate dehalogenation activity was constitutively present, and the dechlorination product was dichloroacetate and chloride. Trichloroacetate conversion seemed to be coupled to a novel sulfur-sulfide redox cycle, which shuttled electrons from acetate oxidation to trichloroacetate reduction. In view of its unique physiological characteristics, the name Trichlorobacter thiogenes is suggested for strain K1. PMID:10831402

Applications of surface analysis in the environmental sciences: dehalogenation of chlorocarbons with zero-valent iron and iron-containing mineral surfaces

Energy Technology Data Exchange (ETDEWEB)

McGuire, Molly M.; Carlson, Daniel L.; Vikesland, Peter J.; Kohn, Tamar; Grenier, Adam C.; Langley, Laura A.; Roberts, A. Lynn; Fairbrother, D. Howard

2003-10-31

Halogenated organic compounds are common pollutants in groundwater. Consequently, there is widespread interest in understanding the reactions of these compounds in the environment and developing remediation strategies. One area of ongoing research involves the reductive dechlorination of organohalides with zero-valent metals or metal sulfide minerals. These processes have been studied almost exclusively from the perspective of the aqueous phase. In this paper we illustrate the utility of surface analysis techniques, including electron spectroscopies, vibrational spectroscopies, and atomic force microscopy in elucidating the roles played by the surface. A dual analysis approach to the study of reductive dechlorination, combining traditional solution phase analysis with surface analytical techniques, also is demonstrated using a liquid cell coupled to an ultrahigh vacuum surface analysis chamber.

A Comparison of Modeling Approaches in Simulating Chlorinated Ethene Removal in a Constructed Wetland by a Microbial Consortia

National Research Council Canada - National Science Library

Campbell, Jason

2002-01-01

The purpose of this study is to compare different approaches to modeling the reductive dechlorination of chlorinated ethenes in the anaerobic region of an upward flow constructed wetland by microbial consortia...

Polychlorinated biphenyls and their interaction with the environment

Energy Technology Data Exchange (ETDEWEB)

Dickerson, K.S.; Korte, N.E.

1994-05-01

This document is a review of the existing technical literature regarding the physical and biological properties of polychlorinated biphenyls (PCBs) and their interaction with the environment. It is intended to be used when evaluating PCB-contaminated soil and the effects of specific environmental conditions on PCB degradation. PCBs are a class of chlorinated aromatic compounds with 209 possible structural arrangements. The composition of PCBs in the environment changes over time due to various physiochemical and biological properties and processes: vapor pressure, solubility, octanol-water partitioning, adsorption, and biodegradation. As the number of chlorine atoms increases, both vapor pressure and water solubility decrease, while adsorption and the octanol-water partitioning coefficient increase. Dechlorination of PCBs occurs primarily through aerobic and anaerobic microbial degradation. Aerobic bacteria preferentially dechlorinate less-chlorinated PCBs, while anaerobic bacteria preferentially dechlorinate more highly chlorinated PCBs. The less-chlorinated PCB congeners are less persistent in the environment due to volatilization, solubility, and aerobic biodegradation, while the more-chlorinated PCBs are more persistent in the environment due to adsorption. The composition of an original PCB mixture in the environment can be expected to change due to a combination of processes described above. Any attempt to determine the source of PCBs or Aroclors identified in an environment sample must be approached with caution to avoid inaccurate conclusions.

DDE in sediments of the Palos Verdes shelf, California: In situ transformation rates and geochemical fate

Science.gov (United States)

Eganhouse, R.P.; Pontolillo, J.

2008-01-01

From 1947 to 1971 the world's largest manufacturer of DDT discharged process wastes into the sewers of Los Angeles County. Roughly 870-1450 t of DDT were released to the ocean off Palos Verdes, CA, a portion of which (???100 t) resides in sediments on the continental shelf and slope. The most abundant DDT compound in the sediments, p,p???-DDE, is degrading by reductive dechlorination, butthe rate of transformation and factors controlling it are not well understood. In order to estimate in situ transformation rates and predict the long-term fate of p,p???-DDE, box cores were collected in 1992 and 2003 from a single location on the Palos Verdes Shelf and analyzed for 8 DDT compounds and 84 polychlorinated biphenyl (PCB) congeners. The PCBs show no evidence of dechlorination, and inventories did not change between 1992 and 2003. By contrast, the inventory of p,p???-DDE decreased by 43%, whereas that of p,p???-DDMU, the putative reductive dechlorination product increased by 34%. The first-order transformation rate for p,p???-DDE at the study site is 0.051 ?? 0.006 yr-1. A multistep reaction model suggests that inventories of p,p???-DDE and p,p???-DDMU will continue to decline, whereas that of p,p???-DDNU will reach a maximum around 2014.

Field Evidence for Co-Metabolism of Trichloroethene Stimulated by Addition of Electron Donor to Groundwater

Energy Technology Data Exchange (ETDEWEB)

Conrad, Mark E.; Brodie, Eoin L.; Radtke, Corey W.; Bill, Markus; Delwiche, Mark E.; Lee, M. Hope; Swift, Dana L.; Colwell, Frederick S.

2010-05-17

For more than 10 years, electron donor has been injected into the Snake River aquifer beneath the Test Area North site of the Idaho National Laboratory for the purpose of stimulating microbial reductive dechlorination of trichloroethene (TCE) in groundwater. This has resulted in significant TCE removal from the source area of the contaminant plume and elevated dissolved CH4 in the groundwater extending 250 m from the injection well. The delta13C of the CH4 increases from 56o/oo in the source area to -13 o/oo with distance from the injection well, whereas the delta13C of dissolved inorganic carbon decreases from 8 o/oo to -13 o/oo, indicating a shift from methanogenesis to methane oxidation. This change in microbial activity along the plume axis is confirmed by PhyloChip microarray analyses of 16S rRNA genes obtained from groundwater microbial communities, which indicate decreasing abundances of reductive dechlorinating microorganisms (e.g., Dehalococcoides ethenogenes) and increasing CH4-oxidizing microorganisms capable of aerobic co-metabolism of TCE (e.g., Methylosinus trichosporium). Incubation experiments with 13C-labeled TCE introduced into microcosms containing basalt and groundwater from the aquifer confirm that TCE co-metabolism is possible. The results of these studies indicate that electron donor amendment designed to stimulate reductive dechlorination of TCE may also stimulate co-metabolism of TCE.

Chloroethene Biodegradation Potential, ADOT/PF Peger Road Maintenance Facility, Fairbanks, Alaska

Science.gov (United States)

Bradley, Paul M.; Chapelle, Frances H.

2004-01-01

A series of 14C-radiotracer-based microcosm experiments were conducted to assess: 1) the extent, rate and products of microbial dechlorination of trichloroethene (TCE), cis-dichloroethene (cis-DCE) and vinyl chloride (VC) in sediments at the Peger Road site; 2) the effect of three electron donor amendments (molasses, shrimp and crab chitin, and 'Hydrogen Release Compound' (HRC)) on microbial degradation of TCE in three Peger Road sediments; and 3) the potential significance at the site of chloroethene biodegradation processes other than reductive dechlorination. In these experiments, TCE biodegradation yielded the reduced products, DCE and VC, and the oxidation product CO 2. Biodegradation of DCE and VC involved stoichiometric oxidation to CO 2. Both laboratory microcosm study and field redox assessment results indicated that the predominant terminal electron accepting process in Peger Road plume sediments under anoxic conditions was Mn/Fe-reduction. The rates of chloroethene biodegradation observed in Peger Road sediment microcosms under low temperature conditions (4?C) were within the range of those observed in sediments from temperate (20?C) aquifer systems. This result confirmed that biodegradation can be a significant mechanism for in situ contaminant remediation even in cold temperature aquifers. The fact that CO2 was the sole product of cis-DCE and VC biodegradation detected in Peger Road sediments indicated that a natural attenuation assessment based on reduced daughter product accumulation may significantly underestimate the potential for DCE and VC biodegradation at the Peger Road. Neither HRC nor molasses addition stimulated TCE reductive dechlorination. The fact that molasses and HRC amendment did stimulate Mn/Fe-reduction suggests that addition of these electron donors favored microbial Mn/Fe-reduction to the detriment of microbial TCE dechlorinating activity. In contrast, amendment of sediment microcosms with shrimp and crab chitin resulted in the

Model Parameter Variability for Enhanced Anaerobic Bioremediation of DNAPL Source Zones

Science.gov (United States)

Mao, X.; Gerhard, J. I.; Barry, D. A.

2005-12-01

The objective of the Source Area Bioremediation (SABRE) project, an international collaboration of twelve companies, two government agencies and three research institutions, is to evaluate the performance of enhanced anaerobic bioremediation for the treatment of chlorinated ethene source areas containing dense, non-aqueous phase liquids (DNAPL). This 4-year, 5.7 million dollars research effort focuses on a pilot-scale demonstration of enhanced bioremediation at a trichloroethene (TCE) DNAPL field site in the United Kingdom, and includes a significant program of laboratory and modelling studies. Prior to field implementation, a large-scale, multi-laboratory microcosm study was performed to determine the optimal system properties to support dehalogenation of TCE in site soil and groundwater. This statistically-based suite of experiments measured the influence of key variables (electron donor, nutrient addition, bioaugmentation, TCE concentration and sulphate concentration) in promoting the reductive dechlorination of TCE to ethene. As well, a comprehensive biogeochemical numerical model was developed for simulating the anaerobic dehalogenation of chlorinated ethenes. An appropriate (reduced) version of this model was combined with a parameter estimation method based on fitting of the experimental results. Each of over 150 individual microcosm calibrations involved matching predicted and observed time-varying concentrations of all chlorinated compounds. This study focuses on an analysis of this suite of fitted model parameter values. This includes determining the statistical correlation between parameters typically employed in standard Michaelis-Menten type rate descriptions (e.g., maximum dechlorination rates, half-saturation constants) and the key experimental variables. The analysis provides insight into the degree to which aqueous phase TCE and cis-DCE inhibit dechlorination of less-chlorinated compounds. Overall, this work provides a database of the numerical

Indirect Evidence Link PCB Dehalogenation with Geobacteraceae in Anaerobic Sediment-Free Microcosms

Czech Academy of Sciences Publication Activity Database

Pravečková, Martina; Brennerová, Mária; Holliger, Ch.; De Alencastro, F.; Rossi, P.

2016-01-01

Roč. 7, June (2016), s. 933 ISSN 1664-302X Institutional support: RVO:61388971 Keywords : polychlorinated biphenyl congeners * Delor 103 * reductive dechlorination Subject RIV: EE - Microbiology, Virology Impact factor: 4.076, year: 2016

Kinetics of photocatalytic removal of 2-amino-5-chloropyridine from water

Directory of Open Access Journals (Sweden)

Abramović Biljana F.

2004-01-01

Full Text Available Titanium dioxide sensitized photocatalytic degradation of a pyridine pesticide analogue, 2-amino-5-chloropyridine, was investigated by monitoring the pyridine moiety degradation, as well as by monitoring the chloride generated in the process. Effect of the initial substrate concentration on the rate of its degradation is reported. Here we show that the kinetics of both reactions are of the zero-order in the entire investigated concentration range. The Langmuir-Hinshelwood kinetic model successfully described the influence of the initial substrate concentration on the rate of the pyridine moiety degradation. It was found that dechlorination of the substrate takes place by direct photolysis. The differences in the kinetics of pyridine moiety degradation and dechlorination were explained on the basis of the electrostatic potential for the investigated compound.

Annual Reporting of Monitoring at Morrill, Kansas in 2015

Energy Technology Data Exchange (ETDEWEB)

LaFreniere, Lorraine M. [Argonne National Lab. (ANL), Argonne, IL (United States)

2016-06-01

In September 2005, the CCC/USDA initiated periodic sampling of groundwater, in accord with a program (Argonne 2005b) approved by the KDHE (2005), to monitor carbon tetrachloride concentrations in the groundwater. Under the KDHE-approved monitoring plan (Argonne 2005b), groundwater was sampled twice yearly for VOCs analyses through 2011. During the initial two years of monitoring, analysis for selected geochemical parameters was also conducted to aid in the evaluation of possible natural contaminant degradation (reductive dechlorination) processes in the subsurface environment. Consistently low levels of dissolved oxygen (DO) and oxidation-reduction potential (ORP) at monitoring well MW1D (in the deepest portion of the contaminated aquifer) and the presence of chloroform (the primary degradation product of carbon tetrachloride) suggested that some degree of reductive dechlorination was occurring.

Toxicological Response of Poecilia reticulata, Hyla species and ...

African Journals Online (AJOL)

PROF HORSFALL

response of Poecilia reticulata, Hyla and Culex species was investigated using acute and chronic toxicity tests. ... responses over a 28 day period. .... sample. A control with only de-chlorinated tap water ..... landfills using luminescent bacteria.

Electrokinetic-enhanced bioaugmentation for remediation of chlorinated solvents contaminated clay

International Nuclear Information System (INIS)

Mao, Xuhui; Wang, James; Ciblak, Ali; Cox, Evan E.; Riis, Charlotte; Terkelsen, Mads; Gent, David B.; Alshawabkeh, Akram N.

2012-01-01

Highlights: ► Simultaneous delivery of electron donors and bacteria into low permeability clays. ► Bacteria injection, growth and consequent transformation of contaminants are viable. ► EK injection is more effective than advection-based injection for clay soil. ► Electroosmosis appears to be the driving mechanism for bacteria injection. ► Both EK transport and biodegradation contribute the removal of VOCs in clay. - Abstract: Successful bioremediation of contaminated soils is controlled by the ability to deliver bioremediation additives, such as bacteria and/or nutrients, to the contaminated zone. Because hydraulic advection is not practical for delivery in clays, electrokinetic (EK) injection is an alternative for efficient and uniform delivery of bioremediation additive into low-permeability soil and heterogeneous deposits. EK-enhanced bioaugmentation for remediation of clays contaminated with chlorinated solvents is evaluated. Dehalococcoides (Dhc) bacterial strain and lactate ions are uniformly injected in contaminated clay and complete dechlorination of chlorinated ethene is observed in laboratory experiments. The injected bacteria can survive, grow, and promote effective dechlorination under EK conditions and after EK application. The distribution of Dhc within the clay suggests that electrokinetic transport of Dhc is primarily driven by electroosmosis. In addition to biodegradation due to bioaugmentation of Dhc, an EK-driven transport of chlorinated ethenes is observed in the clay, which accelerates cleanup of chlorinated ethenes from the anode side. Compared with conventional advection-based delivery, EK injection is significantly more effective for establishing microbial reductive dechlorination capacity in low-permeability soils.

Comparison of PCE and TCE disappearance in heated volatile organic analysis vials and flame-sealed ampules.

Science.gov (United States)

Costanza, Jed; Pennell, Kurt D

2008-02-01

The rates of hydrolysis reported for tetrachloroethylene (PCE) and trichloroethylene (TCE) at elevated temperatures range over two orders-of-magnitude, where some of the variability may be due to the presence of a gas phase. Recent studies suggest that volatile organic analysis (VOA) vials provide a low-cost and readily available zero headspace system for measuring aqueous-phase hydrolysis rates. This work involved measuring rates of PCE and TCE disappearance and the corresponding appearance of dechlorination products in water-filled VOA vials and flame-sealed ampules incubated at 21 and 55 degrees C for up to 95.5 days. While PCE and TCE concentrations readily decreased in the VOA vials to yield first-order half lives of 11.2 days for PCE and 21.1 days for TCE at 55 degrees C, concentrations of anticipated dechlorination products, including chloride, remained constant or were not detected. The rate of PCE disappearance was 34 times faster in VOA vials at 55 degrees C compared to values obtained with flame-sealed ampules containing PCE-contaminated water. In addition, the concentration of TCE increased slightly in flame-sealed ampules incubated at 55 degrees C, while a decrease in TCE levels was observed in the VOA vials. The observed losses of PCE and TCE in the VOA vials were attributed to diffusion and sorption in the septa, rather than to dechlorination. These findings demonstrate that VOA vials are not suitable for measuring rates of volatile organic compound hydrolysis at elevated temperatures.

The cooperative electrochemical oxidation of chlorophenols in anode-cathode compartments

International Nuclear Information System (INIS)

Wang Hui; Wang Jianlong

2008-01-01

By using a self-made carbon/polytetrafluoroethylene (C/PTFE) O 2 -fed as the cathode and Ti/IrO 2 /RuO 2 as the anode, the degradation of three organic compounds (phenol, 4-chlorophenol, and 2,4-dichlorophenol) was investigated in the diaphragm (with terylene as diaphragm material) electrolysis device by electrochemical oxidation process. The result indicated that the concentration of hydrogen peroxide (H 2 O 2 ) was 8.3 mg/L, and hydroxyl radical (HO·) was determined in the cathodic compartment by electron spin resonance spectrum (ESR). The removal efficiency for organic compounds reached about 90% after 120 min, conforming to the sequence of phenol, 4-chlorophenol, and 2,4-dichlorophenol. And the dechlorination degree of 4-chlorophenol exceeded 90% after 80 min. For H 2 O 2 , HO· existed in the catholyte and reduction dechlorination at the cathode, the mineralization of organics in the cathodic compartment was better than that in the anodic compartment. The degradation of organics was supposed to be cooperative oxidation by direct or indirect electrochemical oxidation at the anode and H 2 O 2 , HO· produced by oxygen reduction at the cathode. High-performance liquid chromatography (HPLC) allowed identifying phenol as the dechlorination product of 4-chlorophenol in the cathodic compartment, and hydroquinone, 4-chlorocatechol, benzoquinone, maleic, fumaric, oxalic, and formic acids as the main oxidation intermediates in the cathodic and anodic compartments. A reaction scheme involving all these intermediates was proposed

Reductive destruction and decontamination of aqueous solutions of chlorinated antimicrobial agent using bimetallic systems

Energy Technology Data Exchange (ETDEWEB)

Ghauch, Antoine, E-mail: antoine.ghauch@aub.edu.lb [American University of Beirut, Faculty of Arts and Sciences, Department of Chemistry, P.O. Box 11-0236 Riad El Solh, 1107-2020 Beirut (Lebanon); Tuqan, Almuthanna [American University of Beirut, Faculty of Arts and Sciences, Department of Chemistry, P.O. Box 11-0236 Riad El Solh, 1107-2020 Beirut (Lebanon)

2009-05-30

Palladium, ruthenium and silver were investigated as catalysts for the dechlorination of dichlorophen (DCP, 2,2'-methylenebis(4-chlorophenol)), an antimicrobial and anthelmintic agent largely used as algicide, fungicide and bactericide. Experiments were undertaken under oxic and anoxic conditions for experimental durations up to 180 min (3 h). The anoxic conditions were achieved by purging the solutions with nitrogen gas. Reactions were performed in a 12 {+-} 0.5 mg L{sup -1} DCP solution (V = 20 mL) using 0.8 g of Fe{sup 0} (40 g L{sup -1}). Along with micrometric Fe{sup 0}, five Fe{sup 0}-plated systems were investigated: Pd (1%), Ru (0.01%), Ru (0.1%), Ru (1%) and Ag (1%). Metal plating was controlled by atomic absorption spectroscopy. DCP degradation was monitored using: (i) two HPLC devices, (ii) ion chromatography, (iii) UV and fluorescence spectrophotometry. Results indicated: (i) total dechlorination with Fe/Pd, (ii) partial dechlorination (40%) with Fe/Ru, and no reaction with Fe/Ag. DCP is vanished completely after 90 min of contact with Fe/Pd following a first order kinetic. The observed degradation rate k{sub obs} was about (3.98 {+-} 0.10) x 10{sup -2} min{sup -1}, the calculated half-life t{sub 1/2} about 17.4 {+-} 0.9 min and a t{sub 50} about 10.1 {+-} 0.5 min. A DCP degradation pathway map was also proposed.

A study of chlorinated solvent contamination of the aquifers of an industrial area in central Italy: a possibility of bioremediation

Directory of Open Access Journals (Sweden)

FEDERICA eMATTEUCCI

2015-09-01

Full Text Available Perchloroethene, Trichloroethene, and other chlorinated solvents are widespread groundwater pollutants. They form Dense Non Aqueous Phase Liquids (DNAPLs that sink through permeable groundwater aquifers until non-permeable zone is reached. In Italy there are many situations of serious contamination of groundwater that might compromise their use in industry, agriculture, private, as the critical case of a Central Italy valley located in the province of Teramo (Val Vibrata, characterized by a significant chlorinated solvents contamination. Data from the various monitoring campaigns that have taken place over time were collected, and new samplings were carried out, resulting in a complete database. The data matrix was processed with a multivariate statistic analysis (in particular Principal Components Analysis, PCA and was then imported into Geographic Information System (GIS, to obtain a model of the contamination. A microcosm anaerobic study was utilized to assess the potential for in situ natural or enhanced bioremediation. Most of the microcosms were positive for dechlorination, particularly those inoculated with a mineral medium. This indicate the presence of an active native dechlorinating population in the subsurface, probably inhibited by co-contaminants in the groundwater, or more likely by the absence or lack of nutritional factors. Among the tested electron donors (i.e., yeast extract, lactate, and butyrate lactate and butyrate enhanced dechlorination of chlorinated compounds. PCA and GIS studies allowed delimiting the contamination; the microcosm study helped to identify the conditions to promote the bioremediation of the area.

Generation and characterization of a stable red fluorescent ...

African Journals Online (AJOL)

AJL

Germ-line transmitted transgenic T. ... transgenic expression may vary across different sites of transgenic ... containing dechlorinated tap water under fluorescent lighting on a. 12L: 12D ..... presence of “hot spot” for DNA integration. Indeed, a ...

Integrated characterization of natural attenuation of a PCE plume after thermal remediation of the source zone - incl. dual isotope and microbial techniques

DEFF Research Database (Denmark)

Broholm, Mette Martina

dechlorination 1-1.5 km downstream the source area, where the plume descends into more reduced groundwater. The objective of the new (2014) study is to evaluate how the source remediation has impacted the plume and in particular the natural attenuation within the plume. A large monitoring campaign including...... down-gradient which co-inside with the reduction in redox conditions. The findings document a significant increase in cDCE degradation without accumulation of VC. This reduces the risk posed by the contaminant plume to the drinking water resource. This project is unique in the integrated...... area, resulted in the release of dissolved organic matter and some geochemical changes. This has had an effect on redox conditions and biodegradation by reductive dechlorination particularly in the near source area. However, also in the further downstream area of the plume redox and contaminant levels...

Comparison of different chlorophenols degradation in aqueous solutions by gamma irradiation under reducing conditions

International Nuclear Information System (INIS)

Peng, Yunxia; He, Shijun; Wang, Jianlong; Gong, Wenqi

2012-01-01

The reductive degradation of chlorophenols (CPs), including 2-CP, 4-CP and 2,4-DCP by gamma irradiation was investigated and compared. The results showed that the most efficient degradation took place with 2,4-DCP, followed by 2-CP and then 4-CP. This confirmed that the number and position of chlorine atoms existing in the benzene ring have significant impact on dechlorination and decomposition of CPs. The G-values of decomposition of CPs, the formation of intermediate products and chloride ion, and the degradation rate (K CPs and K Cl −1 ) were also determined. - Highlights: ► Reductive degradation of 2-CP, 4-CP and 2,4-DCP by γ radiation was compared. ► Number and position of chlorine affect their dechlorination and decomposition. ► G-values of CPs decomposition, intermediate formation and chloride release were determined.

Biodegradation of Polychlorinated Biphenyls and Volatile Chlorinated Hydrocarbons in Contaminated Soils and Ground Water in Field Condition

Czech Academy of Sciences Publication Activity Database

Kaštánek, František; Demnerová, K.; Pazlarová, J.; Burkhard, J.; Maléterová, Ywetta

1999-01-01

Roč. 44, č. 1 (1999), s. 39-47 ISSN 0964-8305 Institutional research plan: CEZ:AV0Z4072921 Keywords : reductive dechlorination * river sediments * enrichment Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 0.568, year: 1999

HIGH-RATE DISINFECTION TECHNIQUES FOR COMBIND SEWER OVERFLOW

Science.gov (United States)

This paper presents high-rate disinfection technologies for combined sewer overflow (CSO). The high-rate disinfection technologies of interest are: chlorination/dechlorination, ultraviolet light irradiation (UV), chlorine dioxide (ClO2 ), ozone (O3), peracetic acid (CH3COOOH )...

Transformation of carbon tetrachloride in an anaerobic packed-bed reactor without addition of another electron donor

NARCIS (Netherlands)

de Best, JH; Hunneman, P; Doddema, HJ; Janssen, DB; Harder, W; Doddema, Hans J.

1999-01-01

Carbon tetrachloride (52 mu M) was biodegraded for more than 72% in an anaerobic packed-bed reactor without addition of an external electron donor. The chloride mass balance demonstrated that all carbon tetrachloride transformed was completely dechlorinated. Chloroform and dichloromethane were

Comparison of corrosion scales in full and partially replaced lead service lines after changes in water quality

Science.gov (United States)

Preliminary results from scales formed 38 weeks following the LSL replacement simulations revealed differences in scale formations amongst varying water qualities and pipe sequence. Rigs fed with dechlorinated tap water show distinct pH gradients between the galvanic and the back...

Bacterial communities in tetrachloroethene-polluted groundwaters: A case study

Czech Academy of Sciences Publication Activity Database

Kotík, Michael; Davidová, Anna; Voříšková, Jana; Baldrian, Petr

2013-01-01

Roč. 454, JUN 2013 (2013), s. 517-527 ISSN 0048-9697 R&D Projects: GA ČR GAP504/10/0137 Institutional support: RVO:61388971 Keywords : Tetrachloroethene * Chloroethenes * Dechlorination Subject RIV: CE - Biochemistry Impact factor: 3.163, year: 2013

High-Rate Disinfection Techniques for Combined Sewer Overflow (Proceedings Paper)

Science.gov (United States)

This paper presents high-rate disinfection technologies for combined sewer overflow (CSO). The high-rate disinfection technologies of interest are: chlorination/dechlorination, ultraviolet light irradiation (UV), chlorine dioxide (ClO2 ), ozone (O3), peracetic acid (CH3COOOH ), a...

Design requirements for ERD and ISCO: How close and how fast to achieve an effective remediation?

DEFF Research Database (Denmark)

Chambon, Julie Claire Claudia; Lemming, Gitte; Manoli, Gabriele

2011-01-01

Clayey tills contaminated with chlorinated solvents are a threat to groundwater and are difficult to remediate. Full scale Enhanced Reductive Dechlorination (ERD) and In-Situ Chemical Oxidation (ISCO) are promising remediation technologies for such sites, but the delivery of reactants...

Transformation of carbon tetrachloride in an anaerobic packed-bed reactor without addition of another electron donor

NARCIS (Netherlands)

Best, J.H. de; Hunneman, P.; Doddema, H.J.; Janssen, D.B.; Harder, W.

1999-01-01

Carbon tetrachloride (52 μM) was biodegraded for more than 72% in an anaerobic packed-bed reactor without addition of an external electron donor. The chloride mass balance demonstrated that all carbon tetrachloride transformed was completely dechlorinated. Chloroform and dichloromethane were

Cyclodextrin-Enhanced In Situ Removal of Organic Contaminants from Groundwater at Department of Defense Sites

Science.gov (United States)

2004-05-01

Advantage Nontoxic to humans and resident microbial populations Cyclodextrins are widely used in pharmaceuticals, food processing, and cosmetics ...dechlorination of tetrachloroethene by the Fenton reaction. Environ. Sci. Technol., 17 (9): 1689-1694. 25. Yin, Y., Allen, H.E., 1999: In situ chemical

ADVANCED OXIDATION PROCESS TECHNOLOGY (ULTRAVIOLET RADIATION/OZONE TREATMENT) FOR REMOVAL OF METHYL TERTIARY BUTYL ETHER (MTBE) IN GROUND WATER SUPPLIES.

Science.gov (United States)

U.S. EPA’s Office of Research and Development in Cincinnati, Ohio has been testing and evaluating MTBE removal in dechlorinated tap water using three oxidant combinations: hydrogen peroxide/ozone, ultraviolet irradiation (UV)/ozone, and UV/ozone/hydrogen peroxide. Pilot-scale st...

Inactivation of Escherichia coli by titanium dioxide photocatalytic oxidation.

Science.gov (United States)

Titanium dioxide in the anatase crystalline form was used as a photocatalyst to generate hydroxyl radicals in a flowthrough water reactor. Experiments were performed on pure cultures of Escherichia coli in dechlorinated tap water and a surface water sample to evaluate the disinfe...

Transformation of tetrachloroethene in an upflow anaerobic sludgeblanket reactor

DEFF Research Database (Denmark)

Christiansen, N.; Christensen, S.R.; Arvin, E.

1997-01-01

Reductive dechlorination of tetrachloroethene was studied in a mesophilic upflow anaerobic sludge blanket reactor. Operating the reactor in batch mode the dynamic transformation of tetrachloroethene, trichloroethene and dichloroethene (DCE) was monitored. Tetrachloroethene was reductively...... methane-producing bacteria were inhibited by the chlorinated ethenes....

Characterization of ornidazole metabolites in human bile after intraveneous doses by ultraperformance liquid chromatography/quadrupole time-of-flight mass spectrometry

Directory of Open Access Journals (Sweden)

Jiangbo Du

2012-04-01

Full Text Available Ultraperformance liquid chromatography/quadrupole time-of-flight mass spectrometry (UPLC/Q-TOF MS was used to characterize ornidazole metabolites in human bile after intravenous doses. A liquid chromatography tandem mass spectrometry (LC–MS/MS assay was developed for the determination of the bile level of ornidazole. Bile samples, collected from four patients with T-tube drainage after biliary tract surgery, were prepared by protein precipitation with acetonitrile before analysis. A total of 12 metabolites, including 10 novel metabolites, were detected and characterized. The metabolites of ornidazole in human bile were the products of hydrochloride (HCl elimination, oxidative dechlorination, hydroxylation, sulfation, diastereoisomeric glucuronation, and substitution of NO2 or Cl atom by cysteine or N-acetylcysteine, and oxidative dechlorination followed by further carboxylation. The bile levels of ornidazole at 12 h after multiple intravenous infusions were well above its minimal inhibitory concentration for common strains of anaerobic bacteria.

Reductive dehalogenation of chlorophenols by Desulfomonile tiedjei DCB-1.

Science.gov (United States)

Mohn, W W; Kennedy, K J

1992-01-01

Reductive dehalogenation of chlorophenols has been reported in undefined anaerobic cultures but never before in an anaerobic pure culture. We found that the sulfate-reducing bacterium Desulfomonile tiedjei DCB-1 reductively dehalogenates pentachlorophenol (PCP) and other chlorophenols. The maximum rate of PCP dechlorination observed was 54 mu mol of Cl- h-1 g of protein-1. 3-Chlorobenzoate appeared to serve as a required inducer for PCP dehalogenation; however, neither PCP nor 3-chlorophenol induced dehalogenation. Dehalogenation was catalyzed by living cells, and formate served as a required electron donor. D. tiedjei dehalogenated meta-chlorine substituents of chlorophenols (i.e., PCP was degraded to 2,4,6-trichlorophenol). Generally, more highly chlorinated phenol congeners were more readily dechlorinated, and 3-chlorophenol was not dehalogenated. Growing cultures dehalogenated PCP, but greater than 10 microM PCP (approximately 1.7 mmol g of protein-1) reversibly inhibited growth. PMID:1599254

The effect of ammonium chloride and urea application on soil bacterial communities closely related to the reductive transformation of pentachlorophenol.

Science.gov (United States)

Yu, Huan-Yun; Wang, Yong-kui; Chen, Peng-cheng; Li, Fang-bai; Chen, Man-jia; Hu, Min

2014-05-15

Pentachlorophenol (PCP) is widely distributed in the soil, and nitrogen fertilizer is extensively used in agricultural production. However, studies on the fate of organic contaminants as affected by nitrogen fertilizer application have been rare and superficial. The present study aimed to examine the effect of ammonium chloride (NH4Cl) and urea (CO(NH2)2) application on the reductive transformation of PCP in a paddy soil. The study showed that the addition of low concentrations of NH4Cl/CO(NH2)2 enhanced the transformation of PCP, while the addition of high concentrations of NH4Cl/CO(NH2)2 had the opposite effect. The variations in the abundance of soil microbes in response to NH4Cl/CO(NH2)2 addition showed that both NH4Cl and CO(NH2)2 had inhibitory effects on the growth of dissimilatory iron-reducing bacteria (DIRB) of the genus Comamonas. In contrast, for the genus Shewanella, low concentrations of NH4Cl inhibited growth, and high concentrations of NH4Cl enhanced growth, whereas all concentrations of CO(NH2)2 showed enhancement effects. In addition, consistent patterns of variation were found between the abundances of dechlorinating bacteria in the genus Dehalobacter and PCP transformation rates under NH4Cl/CO(NH2)2 addition. In conclusion, nitrogen application produced variations in the structure of the soil microbial community, especially in the abundance of dissimilatory iron-reducing bacteria and dechlorinating bacteria, which, in turn, affected PCP dechlorination. Copyright © 2014 Elsevier B.V. All rights reserved.

Simultaneous adsorption and degradation of {gamma}-HCH by nZVI/Cu bimetallic nanoparticles with activated carbon support

Energy Technology Data Exchange (ETDEWEB)

Chang Chun; Lian Fei [Key Laboratory of Pollution Process and Environmental Criteria, Ministry of Education, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Key Laboratory of Urban Ecology Environmental Remediation and Pollution Control, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Zhu Lingyan, E-mail: zhuly@nankai.edu.cn [Key Laboratory of Pollution Process and Environmental Criteria, Ministry of Education, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Key Laboratory of Urban Ecology Environmental Remediation and Pollution Control, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China)

2011-10-15

Cu amended zero valent iron bimetallic nanoparticles were synthesized by doping Cu on the surface of iron. They were incorporated with granular activated carbon (AC) to prepare supported particles (AC-Fe{sup 0}-Cu), which were used to remove {gamma}-HCH. Cu on the surface of iron enhanced the dechlorination activity of Fe{sup 0}. The dechlorination rate constant (k{sub obs}) increased with the Cu loading on the surface of iron and the maximum was achieved with 6.073% Cu. AC as a support was effective for increasing the dispersion of the nanoparticles and avoiding the agglomeration of the metallic nanoparticles. The simultaneous adsorption of {gamma}-HCH on AC accelerated the degradation rate of {gamma}-HCH by the bimetals. After reaction for 165 min, around 99% of {gamma}-HCH was removed by the solids of AC-Fe{sup 0}-Cu. In addition, AC could adsorb the degradation products. The degradation of {gamma}-HCH was mainly through dehydrochlorination and dichloroelmination based on the intermediate products detected by GC/MS. - Highlights: > Deposition of Cu on the surface of Fe enhances its dechlorination efficiency toward {gamma}-HCH. > Incorporation of the bimetallic nanoparticles with activated carbon (AC) reduces their agglomeration. > AC support increases the contact of {gamma}-HCH with the nanoparticles and enhances the degradation efficiency. > The AC support adsorbs {gamma}-HCH and its degradation products, reducing their ecological risks in water. - Impregnation of Cu amended iron on AC enhances the removal efficiency of {gamma}-HCH and reduces the concentrations of its intermediates in aqueous solution.

Assessment of 1-chloro-4-[2,2-dichloro-1-(4-chlorophenyl)ethenyl]benzene (DDE) Transformation Rates on the Palos Verdes Shelf, CA

Science.gov (United States)

Eganhouse, Robert P.; Pontolillo, James

2008-01-01

In 1953, the world's largest producer of DDT, Montrose Chemical Corporation, began to discharge process wastes into sewers of the Los Angeles County Sanitation Districts (LACSD), California. By 1971, when the sewer connection was terminated, approximately 1,500-2,000 metric tons of DDT had been introduced to the LACSD treatment plant in Carson, CA. After treatment, effluent from this plant was released to the ocean through a submarine outfall system on the Palos Verdes Shelf (PVS) near Los Angeles, resulting in the accumulation of highly contaminated marine sediments. Numerous investigations of the PVS have been undertaken since the late 1960s, but few have focused on the biogeochemical fate of DDT and its transformation products. In the early 1990s, it was shown that DDE, the major DDT compound in the sediments, was being reductively dechlorinated by microorganisms resident in sediments on the PVS. The U.S. Geological Survey undertook a study in cooperation with the U.S. Environmental Protection Agency to provide a better understanding of the range of reductive dechlorination rates on the PVS and the environmental factors that control them. Existing data show that rates of reductive dechlorination are variable spatially. A comparison of data from two cores collected approximately 7 kilometers downcurrent from the outfall systems in 1992 and 2003 yielded an average first-order transformation rate of approximately 0.05 yr-1. A multistep reaction model suggests that inventories of DDE in PVS sediments at the study site will continue to decline, whereas the inventory of the metabolite DDNU will reach a maximum around 2014.

Selecting of a cytochrome P450cam SeSaM library with 3-chloroindole and endosulfan – Identification of mutants that dehalogenate 3-chloroindole

DEFF Research Database (Denmark)

Kammoonah, Shaima; Prasad, Brinda; Balaraman, Priyadarshini

2018-01-01

; the wild-type did not accommodate 3-chloroindole in the active site, whereas all the mutants did. We propose two potential reaction pathways for dechlorination of 3-chloroindole. This article is part of a Special Issue entitled: Cytochrome P450 biodiversity and biotechnology, edited by Erika Plettner...

Permeable Reactive Barrier: Technology Update

Science.gov (United States)

2011-06-01

Vukovic 1998; Taylor et al. 2002; Waybrant, Blowes, and Ptacek 1998; Robertson, Vogan, and Lombardo 2008; Hulshof et al. 2003). Solid substrates used...Reductive Dechlorination of Tetrachloroethene to Growth,” Applied Environmental Microbiology 59: 2991–97. Hulshof , A. M. H., D. W. Blowes, C. J

Highly organic natural media as permeable reactive barriers: TCE partitioning and anaerobic degradation profile in eucalyptus mulch and compost.

Science.gov (United States)

Öztürk, Zuhal; Tansel, Berrin; Katsenovich, Yelena; Sukop, Michael; Laha, Shonali

2012-10-01

Batch and column experiments were conducted with eucalyptus mulch and commercial compost to evaluate suitability of highly organic natural media to support anaerobic decomposition of trichloroethylene (TCE) in groundwater. Experimental data for TCE and its dechlorination byproducts were analyzed with Hydrus-1D model to estimate the partitioning and kinetic parameters for the sequential dechlorination reactions during TCE decomposition. The highly organic natural media allowed development of a bioactive zone capable of decomposing TCE under anaerobic conditions. The first order TCE biodecomposition reaction rates were 0.23 and 1.2d(-1) in eucalyptus mulch and compost media, respectively. The retardation factors in the eucalyptus mulch and compost columns for TCE were 35 and 301, respectively. The results showed that natural organic soil amendments can effectively support the anaerobic bioactive zone for remediation of TCE contaminated groundwater. The natural organic media are effective environmentally sustainable materials for use in permeable reactive barriers. Copyright © 2012 Elsevier Ltd. All rights reserved.

Groundwater Hydrology and Chemistry in and near an Emulsified Vegetable-Oil Injection Zone, Solid Waste Management Unit 17, Naval Weapons Station Charleston, North Charleston, South Carolina, 2004-2009

Science.gov (United States)

Vroblesky, Don A.; Petkewich, Matthew D.; Lowery, Mark A.; Conlon, Kevin J.; Casey, Clifton C.

2010-01-01

The U.S. Geological Survey and the Naval Facilities Engineering Command Southeast investigated the hydrology and groundwater chemistry in the vicinity of an emulsified vegetable-oil injection zone at Solid Waste Management Unit (SWMU) 17, Naval Weapons Station Charleston, North Charleston, South Carolina. In May 2004, Solutions-IES initiated a Phase-I pilot-scale treatability study at SWMU17 involving the injection of an edible oil emulsion into the aquifer near wells 17PS-01, 17PS-02, and 17PS-03 to treat chlorinated solvents. The Phase-I injection of emulsified vegetable oil resulted in dechlorination of trichloroethene (TCE) to cis-1,2-dichloroethene (cDCE), but the dechlorination activity appeared to stall at cDCE, with little further dechlorination of cDCE to vinyl chloride (VC) or to ethene. The purpose of the present investigation was to examine the groundwater hydrology and chemistry in and near the injection zone to gain a better understanding of the apparent remediation stall. It is unlikely that the remediation stall was due to the lack of an appropriate microbial community because groundwater samples showed the presence of Dehalococcoides species (sp.) and suitable enyzmes. The probable causes of the stall were heterogeneous distribution of the injectate and development of low-pH conditions in the injection area. Because groundwater pH values in the injection area were below the range considered optimum for dechlorination activity, a series of tests was done to examine the effect on dechlorination of increasing the pH within well 17PS-02. During and following the in-well pH-adjustment tests, VC concentrations gradually increased in some wells in the injection zone that were not part of the in-well pH-adjustment tests. These data possibly reflect a gradual microbial acclimation to the low-pH conditions produced by the injection. In contrast, a distinct increase in VC concentration was observed in well 17PS-02 following the in-well pH increase. Adjustment

Integrating Stable Isotope - Reactive Transport Model Approach for Assessment of Chlorinated Solvent Degradation

Science.gov (United States)

2016-06-01

aerobic cometabolism, reductive dechlorination evidence was reported from the toe of the plume, where TCE enters the Lower Lithologic Unit. The CSM of the...modeling in reactive transport: 50 years of artificial recharge in the Amsterdam Water Supply Dunes . J. Hydrology 454: 7-25. Khan, F. I., et al

Nucleophilic Substitution and Redox Reactions with alpha-Chloro beta-Oxo Sulfenyl Chlorides

DEFF Research Database (Denmark)

El-Essawy, Farag A.G.; Yassin, Salah M.; El-Sakka, Ibrahim A.

1998-01-01

Alpha-Chloro sulfenyl chlorides such as 1 and 4 could not be reduced to the corresponding disulfides. Under reducing conditions they are instead dechlorinated to the corresponding thiocarbonyl compounds. Starting from the chroman-4-one derivatives 1 a number of 1,3,4-oxadithiins 3 have been prepa...

Impacts of Residual Surfactant on Tetrachloroethene (PCE) Degradation Following Pilot-Scale SEAR Treatment at a Chloroethene-Impacted Site

Science.gov (United States)

Ramsburg, C. A.; Abriola, L. M.; Pennell, K. D.; Löffler, F. E.; Gamache, M.; Petrovskis, E. A.

2003-04-01

A pilot-scale surfactant-enhanced aquifer remediation (SEAR) demonstration was completed during the summer of 2000 at the Bachman Road site (Oscoda, MI USA). For this test, an aqueous solution of 60 g/L Tween 80 (polyoxyethylene (20) sorbitan monooleate) was used to recover tetrachloroethene (PCE) from a suspected source zone, located underneath a former dry-cleaning facility. Tween 80 was selected for use based upon its demonstrated capacity to solubilize PCE, “food-grade” status, and biodegradative potential. Hydraulic control was maintained throughout the test, with 95% of the injected surfactant mass recovered by a single extraction well. Source-zone monitoring conducted 15 months after SEAR treatment revealed the presence of previously undetected volatile fatty acids (acetate and formate) and PCE degradation products (trichloroethene, cis-1,2-dichloroethene, trans-1,2-dichlorethene, and vinyl chloride), in conjunction with PCE concentration reductions of approximately two orders-of-magnitude. The detection of volatile fatty acids is relevant, as they are likely fermentation products of residual Tween 80. Microbial reductive dechlorination is limited by available electron donors, and microcosm studies demonstrated that both acetate and formate support reductively dechlorinating populations present at the oligotrophic Bachman Road site aquifer. Surfactant transport simulations, using a regional flow model developed for the site, were employed to determine appropriate down-gradient monitoring locations. Drive point samples taken 15 months post-treatment in the vicinity of the simulated residual surfactant plume, contained elevated concentrations of acetate and PCE daughter products. Ongoing efforts include continued site-monitoring, and microcosm studies to corroborate a causal relationship between Tween 80 fermentation and PCE dechlorination.

Self-inhibition can limit biologically enhanced TCE dissolution from a TCE DNAPL.

Science.gov (United States)

Haest, P J; Springael, D; Seuntjens, P; Smolders, E

2012-11-01

Biodegradation of trichloroethene (TCE) near a Dense Non Aqueous Phase Liquid (DNAPL) can enhance the dissolution rate of the DNAPL by increasing the concentration gradient at the DNAPL-water interface. Two-dimensional flow-through sand boxes containing a TCE DNAPL and inoculated with a TCE dechlorinating consortium were set up to measure this bio-enhanced dissolution under anaerobic conditions. The total mass of TCE and daughter products in the effluent of the biotic boxes was 3-6 fold larger than in the effluent of the abiotic box. However, the mass of daughter products only accounted for 19-55% of the total mass of chlorinated compounds in the effluent, suggesting that bio-enhanced dissolution factors were maximally 1.3-2.2. The enhanced dissolution most likely primarily resulted from variable DNAPL distribution rather than biodegradation. Specific dechlorination rates previously determined in a stirred liquid medium were used in a reactive transport model to identify the rate limiting factors. The model adequately simulated the overall TCE degradation when predicted resident microbial numbers approached observed values and indicated an enhancement factor for TCE dissolution of 1.01. The model shows that dechlorination of TCE in the 2D box was limited due to the short residence time and the self-inhibition of the TCE degradation. A parameter sensitivity analysis predicts that the bio-enhanced dissolution factor for this TCE source zone can only exceed a value of 2 if the TCE self-inhibition is drastically reduced (when a TCE tolerant dehalogenating community is present) or if the DNAPL is located in a low-permeable layer with a small Darcy velocity. Copyright © 2012 Elsevier Ltd. All rights reserved.

Resilience and recovery of Dehalococcoides mccartyi following low pH exposure.

Science.gov (United States)

Yang, Yi; Cápiro, Natalie L; Yan, Jun; Marcet, Tyler F; Pennell, Kurt D; Löffler, Frank E

2017-12-01

Bioremediation treatment (e.g. biostimulation) can decrease groundwater pH with consequences for Dehalococcoides mccartyi (Dhc) reductive dechlorination activity. To explore the pH resilience of Dhc, the Dhc-containing consortium BDI was exposed to pH 5.5 for up to 40 days. Following 8- and 16-day exposure periods to pH 5.5, dechlorination activity and growth recovered when returned to pH 7.2; however, the ability of the culture to dechlorinate vinyl chloride (VC) to ethene was impaired (i.e. decreased rate of VC transformation). Dhc cells exposed to pH 5.5 for 40 days did not recover the ethene-producing phenotype upon transfer to pH 7.2 even after 200 days of incubation. When returned to pH 7.2 conditions after an 8-, a 16- and a 40-day low pH exposure, tceA and vcrA genes showed distinct fold increases, suggesting Dhc strain-specific responses to low pH exposure. Furthermore, a survey of Dhc biomarker genes in groundwater samples revealed the average abundances of Dhc 16S rRNA, tceA and vcrA genes in pH 4.5-6 groundwater were significantly lower (P-value pH 6-8.3 groundwater. Overall, the results of the laboratory study and the assessment of field data demonstrate that sustained Dhc activity should not be expected in low pH groundwater, and the duration of low pH exposure affects the ability of Dhc to recover activity at circumneutral pH. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Polyhydroxyalkanoate as a slow-release carbon source for in situ bioremediation of contaminated aquifers: From laboratory investigation to pilot-scale testing in the field.

Science.gov (United States)

Pierro, Lucia; Matturro, Bruna; Rossetti, Simona; Sagliaschi, Marco; Sucato, Salvatore; Alesi, Eduard; Bartsch, Ernst; Arjmand, Firoozeh; Papini, Marco Petrangeli

2017-07-25

A pilot-scale study aiming to evaluate the potential use of poly-3-hydroxy-butyrate (PHB) as an electron donor source for in situ bioremediation of chlorinated hydrocarbons in groundwater was conducted. Compared with commercially available electron donors, PHB offers a restricted fermentation pathway (i.e., through acetic acid and molecular hydrogen) by avoiding the formation of any residual carbon that could potentially spoil groundwater quality. The pilot study was carried out at an industrial site in Italy, heavily contaminated by different chlorinated aliphatic hydrocarbons (CAHs). Prior to field testing, PHB was experimentally verified as a suitable electron donor for biological reductive dechlorination processes at the investigated site by microcosm studies carried out on site aquifer material and measuring the quantitative transformation of detected CAHs to ethene. Owing to the complex geological characteristics of the aquifer, the use of a groundwater circulation well (GCW) was identified as a potential strategy to enable effective delivery and distribution of electron donors in less permeable layers and to mobilise contaminants. A 3-screened, 30-m-deep GCW coupled with an external treatment unit was installed at the site. The effect of PHB fermentation products on the in situ reductive dechlorination processes were evaluated by quantitative real-time polymerase chain reaction (qPCR). The results from the first 4 months of operation clearly demonstrated that the PHB fermentation products were effectively delivered to the aquifer and positively influenced the biological dechlorination activity. Indeed, an increased abundance of Dehalococcoides mccartyi (up to 6.6 fold) and reduced CAH concentrations at the installed monitoring wells were observed. Copyright © 2016 Elsevier B.V. All rights reserved.

Radiation-induced destruction of organic compounds in aqueous solutions by dual oxidation/reduction mechanism

Energy Technology Data Exchange (ETDEWEB)

Chaychiana, M.; Silverman, J.; Al-Sheikhly, M. [Department of Materials Science and Engineering, University of Maryland (United States); Poster, D.; Neta, P.; Huie, R. [Chemical Science and Technology Laboratory, National Institute of Standard and Technology (United States)

2011-07-01

This research presents the feasibility and mechanisms of using high energy electrons for the dechlorination of polychlorinated biphenyls (PCBs) in marine sediment, and hazardous organic compounds in waste water. The remediation of the organic contaminants by ionizing radiation is achieved by means of both reduction and oxidation processes. PCBs in marine sediment can be effectively dechlorinated by reduction, while toxic organic compounds in water are removed mainly by oxidation. Radiolytic degradation of aqueous suspensions of PCBs in marine sediments in the presence of isopropanol was also studied. Addition of isopropanol was necessary to enhance the radiolytic yield and the dechlorination of PCBs. Also presented are results from an examination of the oxidative and reductive effects of electron-beam irradiation on the concentrations of six organic solvents in water. The organic solvents in water were prepared to mimic a pharmaceutical waste stream. Radiation-induced destruction of benzene was also investigated using pulse radiolysis technique. Pulse radiolysis with spectrophotometric and conductometric detection was utilized to study the formation and reactions of radicals from benzene and dienes in aqueous solutions. The benzene OH adduct, {sup ●}C{sub 6}H{sub 6}OH, reacts with O{sub 2} (k = 3x10{sup 8} L mol{sup -1} s{sup -1}) in a reversible reaction. The peroxyl radical, HOC{sub 6}H{sub 6}O{sub 2}{sup ●}, undergoes O{sub 2}●- elimination, bimolecular decay, and reaction with benzene to initiate a chain reaction, depending on the dose rate, benzene concentration, and pH. The occurrence of the chain reaction is demonstrated in low-dose-rate gamma radiolysis experiments where the consumption of O{sub 2} was monitored. (author)

Biochars made from agro-industrial by-products remove chlorine from water and wastewater

Science.gov (United States)

Tzachristas, Andreas; Manariotis, Ioannis D.; Karapanagioti, Hrissi K.

2017-04-01

Chlorination is the most common disinfection process for water and wastewater. For the industrial use of water in food production, chlorine can add undesired taste and odor to the final product. For this reason, dechlorination is desired for food industries that use municipal tap water. For treated wastewater discharge or reuse, chlorine can be toxic to the receiving aqueous systems and to the irrigated plants. In both the above cases, dechlorination is also required. Traditionally activated carbon has been used as the ideal material for the removal of chlorine. The main mechanisms that describe the interaction between activated carbon and HOCl or OCl- are described by the following equations (AWWA, 1990): HOCl + C* → C*O + H+ + Cl- (1), OCl- + C* → C*O + Cl- (2) Where C* and C*O represent the activated carbon surface and a surface oxide, respectively. The present study proposes the use of agro-industrial by-products for the production of biochars that will be used for dechlorination of tap-water used for food-industry production. Different raw materials such as malt spent rootlets, coffee residue, olive and grape seeds, etc. are used for the production of biochar. Various temperatures and air-to-solid ratios are tested for optimizing biochar production. Batch tests as well as a column test are employed to study the dechlorination kinetics of the different raw and biochar materials as well as those of commercial activated carbons. The removal kinetics are faster during the first hour; then, removal continues but with a slower rate. Most of the biochars tested (with 3 mg of solid in 20 mL of chlorine solution at initial concentration Co=1.5 mg/L) demonstrated removal efficiencies with an average of 9.4 ± 0.5 mg/g. For the two commercial activated carbons, removal efficiencies were 11.4 ± 0.2 mg/g. The first-order constant k1 ranged between 0.001 and 0.014 (min-1) for the biosorbents and the biochars and it was equal to 0.017 (min-1) for the commercial

Degradation of chlorinated compounds in an anaerobic-aerobic process

Energy Technology Data Exchange (ETDEWEB)

Alfan-Guzman, R.; Guerrero-Barajas, C.; Garcia-Pena, I.

2009-07-01

Remediation technologies that involves gas transport (e.g., soil vapor extraction and air sparging of groundwater) cause the emission of gases contaminated with chlorinated solvents. Under anaerobic conditions, reductive dechlorination of trichloroethylene (TCE) proceeds via the formation of cis and trans dichloroethene (DCEs) and vinyl chloride (VC) as intermediates. (Author)

Dehalogenation Potential of Municipal Waste Incineration Fly Ash. I. General Principles

Czech Academy of Sciences Publication Activity Database

Pekárek, Vladimír; Karban, Jindřich; Fišerová, Eva; Bureš, M.; Pacáková, V.; Večerníková, Eva

2003-01-01

Roč. 10, č. 1 (2003), s. 39-43 ISSN 0944-1344 R&D Projects: GA AV ČR IAA4072206 Institutional research plan: CEZ:AV0Z4032918; CEZ:AV0Z4072921 Keywords : dechlorination * fly ash * hexachlorobenzene Subject RIV: CC - Organic Chemistry Impact factor: 1.216, year: 2003

Dehalogenation Potential of Municipal Waste Incineration Fly Ash. II. Comparison of Dehalogenation Pathways of Fly Ash and Model Fly Ash with Thermodynamic Calculations

Czech Academy of Sciences Publication Activity Database

Bureš, M.; Pekárek, Vladimír; Karban, Jindřich; Fišerová, Eva

2003-01-01

Roč. 10, č. 2 (2003), s. 121-125 ISSN 0944-1344 R&D Projects: GA AV ČR IAA4072901; GA AV ČR IBS4072108 Institutional research plan: CEZ:AV0Z4072921 Keywords : dechlorination * thermodynamics * hexachlorobenzene Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.216, year: 2003

The acute toxicity of lead nitrate on Daphnia magna Straus

African Journals Online (AJOL)

STORAGESEVER

2008-12-03

Dec 3, 2008 ... Aquaculture Research Institute (Antalya, Turkey) and introduced into 30 L aquariums with de-chlorinated tap water, which serves as holding tanks, and maintained with a 12 .... Principles of Toxicology. In: Gilman AG, Tall TW,. Nies AS, Taylor P (eds) Pharmacological Basis of Therapeutics,. McGraw-Hill, pp.

Selected Natural Attenuation Monitoring Data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, 2007 and 2008

Science.gov (United States)

Dinicola, R.S.; Huffman, R.L.

2009-01-01

Previous investigations indicate that natural attenuation and biodegradation of chlorinated volatile organic compounds (VOCs) are substantial in groundwater beneath the 9-acre former landfill at Operable Unit 1 (OU 1), Naval Undersea Warfare Center, Division Keyport, Washington. Phytoremediation combined with on-going natural attenuation processes was the preferred remedy selected by the Navy, as specified in the Record of Decision for the site. The Navy planted two hybrid poplar plantations on the landfill in spring 1999 to remove and to control the migration of chlorinated VOCs in shallow groundwater. The U.S. Geological Survey (USGS) has continued to monitor groundwater geochemistry to ensure that conditions remain favorable for contaminant biodegradation as specified in the Record of Decision. In this report are groundwater geochemical and selected VOC data collected at OU 1 by the USGS during June 18-21, 2007, and June 16-18, 2008, in support of long-term monitoring for natural attenuation. For 2007 and 2008, strongly reducing conditions (sulfate reduction and methanogenesis) most favorable for reductive dechlorination of VOCs were inferred for 9 of 16 upper-aquifer wells and piezometers in the northern and southern phytoremediation plantations. Predominant redox conditions in groundwater from the intermediate aquifer just downgradient from the landfill remained mildly reducing and somewhat favorable for reductive dechlorination of VOCs. Dissolved hydrogen (H2) concentrations measured in the upper aquifer during 2007 and 2008 generally have been lower than H2 concentrations measured before 2002. However, widespread and relatively high methane and sulfide concentrations indicate that the lower H2 concentrations measured do not support a trend from strongly to mildly reducing redox conditions because no widespread changes in groundwater redox conditions were identified that should result in less favorable conditions for the reductive dechlorination of the

Determination of Matrix Pore Size Distribution in Fractured Clayey Till and Assessment of Matrix Migration of Dechlorinationg Bacteria

DEFF Research Database (Denmark)

Cong, Lu; Broholm, Mette Martina; Fabricius, Ida Lykke

2014-01-01

The pore structure and pore size distribution (PSD) in the clayey till matrix from three Danish field sites were investigated by image analysis to assess the matrix migration of dechlorinating bacteria in clayey till. Clayey till samples had a wide range of pore sizes, with diameters of 0.1–100 μ...

Microbial Community Response of an Organohalide Respiring Enrichment Culture to Permanganate Oxidation.

Science.gov (United States)

Sutton, Nora B; Atashgahi, Siavash; Saccenti, Edoardo; Grotenhuis, Tim; Smidt, Hauke; Rijnaarts, Huub H M

2015-01-01

While in situ chemical oxidation is often used to remediate tetrachloroethene (PCE) contaminated locations, very little is known about its influence on microbial composition and organohalide respiration (OHR) activity. Here, we investigate the impact of oxidation with permanganate on OHR rates, the abundance of organohalide respiring bacteria (OHRB) and reductive dehalogenase (rdh) genes using quantitative PCR, and microbial community composition through sequencing of 16S rRNA genes. A PCE degrading enrichment was repeatedly treated with low (25 μmol), medium (50 μmol), or high (100 μmol) permanganate doses, or no oxidant treatment (biotic control). Low and medium treatments led to higher OHR rates and enrichment of several OHRB and rdh genes, as compared to the biotic control. Improved degradation rates can be attributed to enrichment of (1) OHRB able to also utilize Mn oxides as a terminal electron acceptor and (2) non-dechlorinating community members of the Clostridiales and Deltaproteobacteria possibly supporting OHRB by providing essential co-factors. In contrast, high permanganate treatment disrupted dechlorination beyond cis-dichloroethene and caused at least a 2-4 orders of magnitude reduction in the abundance of all measured OHRB and rdh genes, as compared to the biotic control. High permanganate treatments resulted in a notably divergent microbial community, with increased abundances of organisms affiliated with Campylobacterales and Oceanospirillales capable of dissimilatory Mn reduction, and decreased abundance of presumed supporters of OHRB. Although OTUs classified within the OHR-supportive order Clostridiales and OHRB increased in abundance over the course of 213 days following the final 100 μmol permanganate treatment, only limited regeneration of PCE dechlorination was observed in one of three microcosms, suggesting strong chemical oxidation treatments can irreversibly disrupt OHR. Overall, this detailed investigation into dose

Stabilization/Solidification of Radioactive LiCl-KCl Waste Salt by Using SiO2-Al2O3-P2O5(SAP) Inorganic Composite: Part 2. The Effect of SAP Composition on Stabilization/Solidification

International Nuclear Information System (INIS)

Ahn, Soo Na; Park, Hwan Seo; Cho, In Hak; Kim, In Tae; Cho, Yong Zun

2012-01-01

Metal chloride waste is generated as a main waste streams in a series of electrolytic processes of a pyrochemical process. Different from carbonate or nitrate salt, metal chloride is not decomposed into oxide and chlorine but it is just vaporized. Also, it has low compatibility with conventional silicate glasses. Our research group adapted the dechlorination approach for the immobilization of waste salt. In this study, the composition of SAP (SiO 2 -Al 2 O 3 -P 2 O 5 ) was adjusted to enhance the reactivity and to simplify the solidification process as a subsequent research. The addition of Fe 2 O 3 into the basic SAP decreased the SAP/Salt ratio in weight from 3 for SAP 1071 to 2.25 for M-SAP(Fe=0.1). The experimental results indicated that the addition of Fe 2 O 3 increased the reactivity of M-SAP with LiCl-KCl but the reactivity gradually decreased above Fe=0.1. Also, introducing B 2 O 3 into M-SAP requires no glass binder for the consolidation of reaction products. U-SAP (SiO 2 -Al 2 O 3 -P 2 O 5 ) could effectively dechlorinate the LiCl-KCl waste and its reaction product could be consolidated as a monolithic form without a glass binder. The leaching test result indicated that U-SAP 1071 was more durable than other SAPs wasteform. By using U-SAP, 1 g of waste salt could generated 3 - 4 g of wasteform for final disposal. The final volume would be about 3 - 4 times lower than the glass-bonded sodalite. From these results, it could be concluded that the dechlorination approach using U-SAP would be one of prospective methods to manage the volatile waste salt.

Interaction of perchlorate and trichloroethene bioreductions in mixed anaerobic culture

Energy Technology Data Exchange (ETDEWEB)

Wen, Li-Lian [Department of Environmental Engineering, College of Environmental and Resource Science, Zhejiang University, Hangzhou (China); Zhejiang Prov Key Lab Water Pollut Control & Envi, Zhejiang University, Hangzhou, Zhejiang (China); Yang, Qiang [Hangzhou Institute of Environmental Protection Science, Hangzhou (China); Zhang, Zhao-Xin; Yi, Yang-Yi [Department of Environmental Engineering, College of Environmental and Resource Science, Zhejiang University, Hangzhou (China); Tang, Youneng [Department of Civil and Environmental Engineering, FAMU-FSU College of Engineering, Florida State University, Tallahassee, FL 32310-6046 (United States); Zhao, He-Ping, E-mail: zhaohp@zju.edu.cn [Department of Environmental Engineering, College of Environmental and Resource Science, Zhejiang University, Hangzhou (China); Zhejiang Prov Key Lab Water Pollut Control & Envi, Zhejiang University, Hangzhou, Zhejiang (China); Hangzhou Institute of Environmental Protection Science, Hangzhou (China)

2016-11-15

This work evaluated the interaction of perchlorate and trichloroethene (TCE), two common co-contaminants in groundwater, during bioreduction in serum bottles containing synthetic mineral salts media and microbial consortia. TCE at concentrations up to 0.3 mM did not significantly affect perchlorate reduction; however, perchlorate concentrations higher than 0.1 mM made the reduction of TCE significantly slower. Perchlorate primarily inhibited the reduction of vinyl chloride (VC, a daughter product of TCE) to ethene. Mechanistic analysis showed that the inhibition was mainly because perchlorate reduction is thermodynamically more favorable than reduction of TCE and its daughter products and not because of toxicity due to accumulation of dissolved oxygen produced during perchlorate reduction. As the initial perchlorate concentration increased from 0 to 600 mg/L in a set of serum bottles, the relative abundance of Rhodocyclaceae (a putatively perchlorate-reducing genus) increased from 6.3 to 80.6%, while the relative abundance of Dehalococcoides, the only known genus that is able to reduce TCE all the way to ethene, significantly decreased. Similarly, the relative abundance of Proteobacteria (a phylum to which most known perchlorate-reducing bacteria belong) increased from 22% to almost 80%. - Graphical abstract: Fig. A plots the interaction of TCE and perchlorate bio-reduction under different concentrations of perchlorate and suggests that initial ethene wasn't formed until the perchlorate was completely reduced. B shows the electron donor utilization and oxygen generated during the experiment and indicates that it is perchlorate reduction over-competed for electron donor rather than oxygen generated that inhibits TCE reductive dechlorination. - Highlight: • Perchlorate slowed but did not inhibit the complete dechlorination of TCE. • The inhibition was mainly due to the thermodynamic preference of perchlorate to TCE. • The generated oxygen was consumed and

Oxidation-reduction processes in ground water at Naval Weapons Industrial Reserve Plant, Dallas, Texas

Science.gov (United States)

Jones, S.A.; Braun, Christopher L.; Lee, Roger W.

2003-01-01

Concentrations of trichloroethene in ground water at the Naval Weapons Industrial Reserve Plant in Dallas, Texas, indicate three source areas of chlorinated solvents?building 1, building 6, and an off-site source west of the facility. The presence of daughter products of reductive dechlorination of trichloroethene, which were not used at the facility, south and southwest of the source areas are evidence that reductive dechlorination is occurring. In places south of the source areas, dissolved oxygen concentrations indicated that reduction of oxygen could be the dominant process, particularly south of building 6; but elevated dissolved oxygen concentrations south of building 6 might be caused by a leaking water or sewer pipe. The nitrite data indicate that denitrification is occurring in places; however, dissolved hydrogen concentrations indicate that iron reduction is the dominant process south of building 6. The distributions of ferrous iron indicate that iron reduction is occurring in places south-southwest of buildings 6 and 1; dissolved hydrogen concentrations generally support the interpretation that iron reduction is the dominant process in those places. The generally low concentrations of sulfide indicate that sulfate reduction is not a key process in most sampled areas, an interpretation that is supported by dissolved hydrogen concentrations. Ferrous iron and dissolved hydrogen concentrations indicate that ferric iron reduction is the primary oxidation-reduction process. Application of mean first-order decay rates in iron-reducing conditions for trichloroethene, dichloroethene, and vinyl chloride yielded half-lives for those solvents of 231, 347, and 2.67 days, respectively. Decay rates, and thus half-lives, at the facility are expected to be similar to those computed. A weighted scoring method to indicate sites where reductive dechlorination might be likely to occur indicated strong evidence for anaerobic biodegradation of chlorinated solvents at six sites

Photolysis of polychlorinated dibenzo-p-dioxins and dibenzofurans dissolved in vegetable oils: influence of oil quality

International Nuclear Information System (INIS)

Isosaari, Pirjo; Laine, Olli; Tuhkanen, Tuula; Vartiainen, Terttu

2005-01-01

Sunlight or ultraviolet light irradiation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the presence of vegetable oil offers a potential method for the cleanup of contaminated soil. In this study, the effects of different types of vegetable oils on the photochemical degradation of 1,2,3,4,6,7,8-heptachlorodibenzofuran and heptachlorodibenzo-p-dioxin (1,2,3,4,6,7,8-HpCDF/HpCDD) were investigated in the laboratory. Using a blacklight lamp as a source of ultraviolet light, 93-100% of 1,2,3,4,6,7,8-HpCDF degraded in 60 min in rapeseed oil, extra virgin olive oil and olive oil. Less degradation occurred in palm oil (59%), toluene (39%) and hexane (20%). The better degradation in vegetable oils in comparison with organic solvents was attributed to the photooxidation of lipids producing hydrogen for PCDD/F dechlorination. In addition to the hydrogen donor capacity, permeability of ultraviolet light was involved in the differences between vegetable oils. α-Tocopherol and chlorophyll did not influence the performance of oil at concentrations normally present in vegetable oils, whereas β-carotene had an inhibitory effect on the degradation of 1,2,3,4,6,7,8-HpCDF. Up to 28% of the degradation products of 1,2,3,4,6,7,8-HpCDF were formed via the dechlorination pathway. Products included both toxic (2,3,7,8-chlorinated) and non-toxic PCDD/Fs, the toxic PCDD/Fs being more stable. Irradiation of 1,2,3,4,6,7,8-HpCDD yielded only non-toxic dechlorination products. Polychlorinated hydroxybiphenyls (OH-PCBs), polychlorinated dihydroxybiphenyls (DOH-PCBs) and polychlorinated hydroxydiphenylethers (OH-PCDEs) containing one to seven chlorine atoms were not detected in irradiated HpCDF/HpCDD samples

Photolysis of polychlorinated dibenzo-p-dioxins and dibenzofurans dissolved in vegetable oils: influence of oil quality

Energy Technology Data Exchange (ETDEWEB)

Isosaari, Pirjo [National Public Health Institute, Department of Environmental Health, P.O. Box 95, FI-70701 Kuopio (Finland)]. E-mail: pirjo.isosaari@ktl.fi; Laine, Olli [National Public Health Institute, Department of Environmental Health, P.O. Box 95, FI-70701 Kuopio (Finland); Tuhkanen, Tuula [Tampere University of Technology, Environmental Engineering and Biotechnology, P.O. Box 541, FI-33101 Tampere (Finland); Vartiainen, Terttu [National Public Health Institute, Department of Environmental Health, P.O. Box 95, FI-70701 Kuopio (Finland); University of Kuopio, Department of Environmental Sciences, P.O. Box 1627, Kuopio, FI-70211 Kuopio (Finland)

2005-03-20

Sunlight or ultraviolet light irradiation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the presence of vegetable oil offers a potential method for the cleanup of contaminated soil. In this study, the effects of different types of vegetable oils on the photochemical degradation of 1,2,3,4,6,7,8-heptachlorodibenzofuran and heptachlorodibenzo-p-dioxin (1,2,3,4,6,7,8-HpCDF/HpCDD) were investigated in the laboratory. Using a blacklight lamp as a source of ultraviolet light, 93-100% of 1,2,3,4,6,7,8-HpCDF degraded in 60 min in rapeseed oil, extra virgin olive oil and olive oil. Less degradation occurred in palm oil (59%), toluene (39%) and hexane (20%). The better degradation in vegetable oils in comparison with organic solvents was attributed to the photooxidation of lipids producing hydrogen for PCDD/F dechlorination. In addition to the hydrogen donor capacity, permeability of ultraviolet light was involved in the differences between vegetable oils. {alpha}-Tocopherol and chlorophyll did not influence the performance of oil at concentrations normally present in vegetable oils, whereas {beta}-carotene had an inhibitory effect on the degradation of 1,2,3,4,6,7,8-HpCDF. Up to 28% of the degradation products of 1,2,3,4,6,7,8-HpCDF were formed via the dechlorination pathway. Products included both toxic (2,3,7,8-chlorinated) and non-toxic PCDD/Fs, the toxic PCDD/Fs being more stable. Irradiation of 1,2,3,4,6,7,8-HpCDD yielded only non-toxic dechlorination products. Polychlorinated hydroxybiphenyls (OH-PCBs), polychlorinated dihydroxybiphenyls (DOH-PCBs) and polychlorinated hydroxydiphenylethers (OH-PCDEs) containing one to seven chlorine atoms were not detected in irradiated HpCDF/HpCDD samples.

Reclaimed water as a reservoir of antibiotic resistance genes: distribution system and irrigation implications

Directory of Open Access Journals (Sweden)

Nicole L Fahrenfeld

2013-05-01

Full Text Available Treated wastewater is increasingly being reused to achieve sustainable water management in arid regions. The objective of this study was to quantify the distribution of antibiotic resistance genes (ARGs in recycled water, particularly after it has passed through the distribution system, and to consider point-of-use implications for soil irrigation. Three separate reclaimed wastewater distribution systems in the western U.S. were examined. Quantitative polymerase chain reaction (qPCR was used to quantify ARGs corresponding to resistance to sulfonamides (sul1, sul2, macrolides (ermF, tetracycline (tet(A, tet(O, glycopeptides (vanA, and methicillin (mecA, in addition to genes present in waterborne pathogens Legionella pneumophila (Lmip, Escherichia coli (gadAB, and Pseudomonas aeruginosa (ecfx, gyrB. In a parallel lab study, the effect of irrigating an agricultural soil with secondary, chlorinated, or dechlorinated wastewater effluent was examined in batch microcosms. A broader range of ARGs were detected after the reclaimed water passed through the distribution systems, highlighting the importance of considering bacterial re-growth and the overall water quality at the point of use. Screening for pathogens with qPCR indicated presence of Lmip and gadAB genes, but not ecfx or gyrB. In the lab study, chlorination was observed to reduce 16S rRNA and sul2 gene copies in the wastewater effluent, while dechlorination had no apparent effect. ARGs levels did not change with time in soil slurries incubated after a single irrigation event with any of the effluents. However, when irrigated repeatedly with secondary wastewater effluent (not chlorinated or dechlorinated, elevated levels of sul1 and sul2 were observed. This study suggests that reclaimed water may be an important reservoir of ARGs, especially at the point of use, and that attention should be directed towards the fate of ARGs in irrigation water and the implications for human health.

Succession of microbial community and enhanced mechanism of a ZVI-based anaerobic granular sludge process treating chloronitrobenzenes wastewater

Energy Technology Data Exchange (ETDEWEB)

Zhu, Liang, E-mail: felix79cn@hotmail.com [Department of Environmental Engineering, Zhejiang University, Hangzhou 310058 (China); Zhejiang Province Key Laboratory for Water Pollution Control and Environmental Safety, Hangzhou 310058 (China); Jin, Jie [Department of Environmental Engineering, Zhejiang University, Hangzhou 310058 (China); Lin, Haizhuan [Department of Environmental Engineering, Zhejiang University, Hangzhou 310058 (China); Wenzhou Environmental Protection Design Scientific Institute, Wenzhou 325000 (China); Gao, Kaituo [Department of Environmental Engineering, Zhejiang University, Hangzhou 310058 (China); Xu, Xiangyang, E-mail: xuxy@zju.edu.cn [Department of Environmental Engineering, Zhejiang University, Hangzhou 310058 (China); Zhejiang Province Key Laboratory for Water Pollution Control and Environmental Safety, Hangzhou 310058 (China)

2015-03-21

Highlights: • The combined ZVI–UASB process was established for the degradation of chloronitrobenzenes. • There were the better shock resistance and buffering capacity for anaerobic acidification in the combined process. • Novel ZVI-based anaerobic granular sludge (ZVI–AGS) was successfully developed. • Adaptive shift of microbial community was significant in ZVI-based anaerobic granular sludge system. - Abstract: The combined zero-valent iron (ZVI) and upflow anaerobic sludge blanket (UASB) process is established for the treatment of chloronitrobenzenes (ClNBs) wastewater, and the succession of microbial community and its enhanced mechanism are investigated in the study. Results showed that compared with the control UASB (R1), the stable COD removal, ClNBs transformation, and dechlorination occurred in the combined system (R2) when operated at influent COD and 3,4-Dichloronitrobenzene (3,4-DClNB) loading rates of 4200–7700 g m{sup −3} d{sup −1} and 6.0–70.0 g m{sup −3} d{sup −1}, and R2 had the better shock resistance and buffering capacity for the anaerobic acidification. The dechlorination for the intermediate products of p-chloroanaline (p-ClAn) to analine (AN) occurred in R2 reactor after 45 days, whereas it did not occur in R1 after a long-term operation. The novel ZVI-based anaerobic granular sludge (ZVI–AGS) was successfully developed in the combined system, and higher microbial activities including ClNB transformation and H{sub 2}/CH{sub 4} production were achieved simultaneously. The dominant bacteria were closely related to the groups of Megasphaera, Chloroflexi, and Clostridium, and the majority of archaea were correlated with the groups of Methanosarcinalesarchaeon, Methanosaetaconcilii, and Methanothrixsoehngenii, which are capable of reductively dechlorinating PCB, HCB, and TCE in anaerobic niche and EPS secretion.

Indirect Evidence Link PCB Dehalogenation with Geobacteraceae in Anaerobic Sediment-Free Microcosms.

Science.gov (United States)

Praveckova, Martina; Brennerova, Maria V; Holliger, Christof; De Alencastro, Felippe; Rossi, Pierre

2016-01-01

Although polychlorinated biphenyls (PCBs) production was brought to a halt 30 years ago, recalcitrance to degradation makes them a major environmental pollutant at a global scale. Previous studies confirmed that organohalide-respiring bacteria (OHRB) were capable of utilizing chlorinated congeners as electron acceptor. OHRB belonging to the Phyla Chloroflexi and Firmicutes are nowadays considered as the main PCB-dechlorinating organisms. In this study, we aimed at exploring the involvement of other taxa in PCB dechlorination using sediment-free microcosms (SFMs) and the Delor PCB mixture. High rates of congener dehalogenation (up to 96%) were attained in long-term incubations of up to 692 days. Bacterial communities were dominated by Chloroflexi, Proteobacteria, and Firmicutes, among strictly simplified community structures composed of 12 major phyla only. In a first batch of SFMs, Dehalococcoides mccartyi closely affiliated with strains CG4 and CBDB1 was considered as the main actor associated with congener dehalogenation. Addition of 2-bromoethanesulfonate (BES), a known inhibitor of methanogenic activity in a second batch of SFMs had an adverse effect on the abundance of Dehalococcoides sp. Only two sequences affiliated to this Genus could be detected in two (out of six) BES-treated SFMs, contributing to a mere 0.04% of the communities. BES-treated SFMs showed very different community structures, especially in the contributions of organisms involved in fermentation and syntrophic activities. Indirect evidence provided by both statistical and phylogenetic analysis validated the implication of a new cluster of actors, distantly affiliated with the Family Geobacteraceae (Phylum δ-Proteobacteria), in the dehalogenation of low chlorinated PCB congeners. Members of this Family are known already for their dehalogenation capacity of chlorinated solvents. As a result, the present study widens the knowledge for the phylogenetic reservoir of indigenous PCB dechlorinating

Paddy field – A natural sequential anaerobic–aerobic bioreactor for polychlorinated biphenyls transformation

International Nuclear Information System (INIS)

Chen, Chen; Yu, Chunna; Shen, Chaofeng; Tang, Xianjin; Qin, Zhihui; Yang, Kai; Hashmi, Muhammad Zaffar; Huang, Ronglang; Shi, Huixiang

2014-01-01

The environmental pollution and health risks caused by the improper disposal of electric and electronic waste (e-waste) have become urgent issues for the developing countries. One of the typical pollutants, polychlorinated biphenyls (PCBs), is commonly found in farmland in Taizhou, a major hotspot of e-waste recycling in China. This study investigated the amount of PCB residue in local farmlands. Biotransformation of PCBs was further studied under different water management conditions in paddy field with or without rice cultivation, with a special focus on the alternating flooded and drying processes. It was found that paddy field improved the attenuation of PCBs, especially for highly chlorinated congeners. In the microcosm experiment, 40% or more of the initial total PCBs was removed after sequential flood–drying treatments, compared to less than 10% in the sterilized control and 20% in the constant-drying system. Variation in the quantity of PCBs degrading and dechlorinating bacterial groups were closely related to the alteration of anaerobic–aerobic conditions. These results suggested that alternating anoxic–oxic environment in paddy field led to the sequential aerobic–anaerobic transformation of PCBs, which provided a favorable environment for natural PCB attenuation. - Highlights: • Paddy fields hold significantly lower level of PCBs than drylands, especially highly-chlorinated PCBs. • Microbial dechlorination of PCBs is favored under flooded conditions in paddy field. • Aerobic biodegradation of PCBs is benefited under dry conditions in paddy field. • PCBs dechlorination rate is accelerated in rice planted paddy field compared to the unplanted one. • Alternating anoxic–oxic environment in paddy field led to the sequential aerobic–anaerobic transformation of PCBs. - Alternating anoxic–oxic environment led to the sequential aerobic–anaerobic transformation of PCBs in paddy field, which could act as a natural sequential anaerobic�

Metabolism of the synthetic cannabinoids AMB-CHMICA and 5C-AKB48 in pooled human hepatocytes and rat hepatocytes analyzed by UHPLC-(IMS)-HR-MSE.

Science.gov (United States)

Mardal, Marie; Dalsgaard, Petur Weihe; Qi, Bing; Mollerup, Christian Brinch; Annaert, Pieter; Linnet, Kristian

2018-04-15

The main analytical targets of synthetic cannabinoids are often metabolites. With the high number of new psychoactive substances entering the market, suitable workflows are needed for analytical target identification in biological samples. The aims of this study were to identify the main metabolites of the synthetic cannabinoids, AMB-CHMICA and 5C-AKB48, using an in silico-assisted workflow with analytical data acquired using ultra-high-performance liquid chromatography-(ion mobility spectroscopy)-high resolution-mass spectrometry in data-independent acquisition mode (UHPLC-(IMS)-HR-MS E ). The metabolites were identified after incubation with rat and pooled human hepatocytes using UHPLC-HR-MS E , followed by UHPLC-IMS-HR-MS E . Metabolites of AMB-CHMICA and 5C-AKB48 were predicted with Meteor (Lhasa Ltd) and imported to the UNIFI software (Waters). The predicted metabolites were assigned to analytical components supported by the UNIFI in silico fragmentation tool. The main metabolic pathway of AMB-CHMICA was O-demethylation and hydroxylation of the methylhexyl moiety. For 5C-AKB48, the main metabolic pathways were hydroxylation(s) of the adamantyl moiety and oxidative dechlorination with subsequent oxidation to the ω-COOH. The matrix components in the metabolite spectra were reduced with IMS, which improved the accuracy of the spectral interpretation; however, this left fewer fragment ions for assigning sites of metabolism. Meteor was able to predict the majority of the metabolites, with the most notable exception being the oxidative dechlorination and, consequently, all metabolites that underwent that transformation pathway. Oxidative dechlorination of ω-chloroalkanes in humans has not been previously reported in the literature. The postulated metabolites can be used for screening of biological samples, with four-dimensional identification based on retention time, collision cross section, precursor ion, and fragment ions. Copyright © 2018 Elsevier B.V. All

Stabilization/Solidification of Radioactive LiCl-KCl Waste Salt by Using SiO{sub 2}-Al{sub 2}O{sub 3}-P{sub 2}O{sub 5}(SAP) Inorganic Composite: Part 2. The Effect of SAP Composition on Stabilization/Solidification

Energy Technology Data Exchange (ETDEWEB)

Ahn, Soo Na; Park, Hwan Seo; Cho, In Hak; Kim, In Tae; Cho, Yong Zun [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2012-03-15

Metal chloride waste is generated as a main waste streams in a series of electrolytic processes of a pyrochemical process. Different from carbonate or nitrate salt, metal chloride is not decomposed into oxide and chlorine but it is just vaporized. Also, it has low compatibility with conventional silicate glasses. Our research group adapted the dechlorination approach for the immobilization of waste salt. In this study, the composition of SAP (SiO{sub 2}-Al{sub 2}O{sub 3}-P{sub 2}O{sub 5}) was adjusted to enhance the reactivity and to simplify the solidification process as a subsequent research. The addition of Fe{sub 2}O{sub 3} into the basic SAP decreased the SAP/Salt ratio in weight from 3 for SAP 1071 to 2.25 for M-SAP(Fe=0.1). The experimental results indicated that the addition of Fe{sub 2}O{sub 3} increased the reactivity of M-SAP with LiCl-KCl but the reactivity gradually decreased above Fe=0.1. Also, introducing B{sub 2}O{sub 3} into M-SAP requires no glass binder for the consolidation of reaction products. U-SAP (SiO{sub 2}-Al{sub 2}O{sub 3}-P{sub 2}O{sub 5}) could effectively dechlorinate the LiCl-KCl waste and its reaction product could be consolidated as a monolithic form without a glass binder. The leaching test result indicated that U-SAP 1071 was more durable than other SAPs wasteform. By using U-SAP, 1 g of waste salt could generated 3 - 4 g of wasteform for final disposal. The final volume would be about 3 - 4 times lower than the glass-bonded sodalite. From these results, it could be concluded that the dechlorination approach using U-SAP would be one of prospective methods to manage the volatile waste salt.

Transformation products and human metabolites of triclocarban and tricllosan in sewage sludge across the United States

Science.gov (United States)

Pycke, Benny F.G.; Roll, Isaac B.; Brownawell, Bruce J.; Kinney, Chad A.; Furlong, Edward T.; Kolpin, Dana W.; Halden, Rolf U.

2014-01-01

Removal of triclocarban (TCC) and triclosan (TCS) from wastewater is a function of adsorption, abiotic degradation, and microbial mineralization or transformation, reactions that are not currently controlled or optimized in the pollution control infrastructure of standard wastewater treatment. Here, we report on the levels of eight transformation products, human metabolites, and manufacturing byproducts of TCC and TCS in raw and treated sewage sludge. Two sample sets were studied: samples collected once from 14 wastewater treatment plants (WWTPs) representing nine states, and multiple samples collected from one WWTP monitored for 12 months. Time-course analysis of significant mass fluxes (α = 0.01) indicate that transformation of TCC (dechlorination) and TCS (methylation) occurred during sewage conveyance and treatment. Strong linear correlations were found between TCC and the human metabolite 2′-hydroxy-TCC (r = 0.84), and between the TCC-dechlorination products dichlorocarbanilide (DCC) and monochlorocarbanilide (r = 0.99). Mass ratios of DCC-to-TCC and of methyl-triclosan (MeTCS)-to-TCS, serving as indicators of transformation activity, revealed that transformation was widespread under different treatment regimes across the WWTPs sampled, though the degree of transformation varied significantly among study sites (α = 0.01). The analysis of sludge sampled before and after different unit operation steps (i.e., anaerobic digestion, sludge heat treatment, and sludge drying) yielded insights into the extent and location of TCC and TCS transformation. Results showed anaerobic digestion to be important for MeTCS transformation (37–74%), whereas its contribution to partial TCC dechlorination was limited (0.4–2.1%). This longitudinal and nationwide survey is the first to report the occurrence of transformation products, human metabolites, and manufacturing byproducts of TCC and TCS in sewage sludge.

Succession of microbial community and enhanced mechanism of a ZVI-based anaerobic granular sludge process treating chloronitrobenzenes wastewater

International Nuclear Information System (INIS)

Zhu, Liang; Jin, Jie; Lin, Haizhuan; Gao, Kaituo; Xu, Xiangyang

2015-01-01

Highlights: • The combined ZVI–UASB process was established for the degradation of chloronitrobenzenes. • There were the better shock resistance and buffering capacity for anaerobic acidification in the combined process. • Novel ZVI-based anaerobic granular sludge (ZVI–AGS) was successfully developed. • Adaptive shift of microbial community was significant in ZVI-based anaerobic granular sludge system. - Abstract: The combined zero-valent iron (ZVI) and upflow anaerobic sludge blanket (UASB) process is established for the treatment of chloronitrobenzenes (ClNBs) wastewater, and the succession of microbial community and its enhanced mechanism are investigated in the study. Results showed that compared with the control UASB (R1), the stable COD removal, ClNBs transformation, and dechlorination occurred in the combined system (R2) when operated at influent COD and 3,4-Dichloronitrobenzene (3,4-DClNB) loading rates of 4200–7700 g m −3 d −1 and 6.0–70.0 g m −3 d −1 , and R2 had the better shock resistance and buffering capacity for the anaerobic acidification. The dechlorination for the intermediate products of p-chloroanaline (p-ClAn) to analine (AN) occurred in R2 reactor after 45 days, whereas it did not occur in R1 after a long-term operation. The novel ZVI-based anaerobic granular sludge (ZVI–AGS) was successfully developed in the combined system, and higher microbial activities including ClNB transformation and H 2 /CH 4 production were achieved simultaneously. The dominant bacteria were closely related to the groups of Megasphaera, Chloroflexi, and Clostridium, and the majority of archaea were correlated with the groups of Methanosarcinalesarchaeon, Methanosaetaconcilii, and Methanothrixsoehngenii, which are capable of reductively dechlorinating PCB, HCB, and TCE in anaerobic niche and EPS secretion

Stable carbon isotope analysis to distinguish biotic and abiotic degradation of 1,1,1-trichloroethane in groundwater sediments

DEFF Research Database (Denmark)

Broholm, Mette Martina; Hunkeler, Daniel; Tuxen, Nina

2014-01-01

not appear to be reductive dechlorination via 1,1-DCA. In the biotic microcosms, the degradation of 1,1,1-TCA occurred under iron and sulfate reducing conditions. Biotic reduction of iron and sulfate likely resulted in formation of FeS, which can abiotically degrade 1,1,1-TCA. Hence, abiotic degradation of 1...

Spatial distribution and implications to sources of halogenated flame retardants in riverine sediments of Taizhou, an intense e-waste recycling area in eastern China.

Science.gov (United States)

Zhou, Shanshan; Fu, Jie; He, Huan; Fu, Jianjie; Tang, Qiaozhi; Dong, Minfeng; Pan, Yongqiang; Li, An; Liu, Weiping; Zhang, Limin

2017-10-01

Concentrations and spatial distribution pattern of organohalogen flame retardants were investigated in the riverine surface sediments from Taizhou, an intensive e-waste recycling region in China. The analytes were syn- and anti- Dechlorane Plus (DP), Dechloranes 602, 603, and 604, a DP monoadduct, two dechlorinated DPs and 8 congeners of polybrominated diphenyl ethers (PBDEs). The concentrations of Σ 8 PBDEs, ΣDP, ΣDec600s, and ΣDP-degradates ranged from recycling facilities. Such patterns were largely shared by Dec602 and dechlorinated DP, although their concentration levels were much lower. These major flame retardants significantly correlate with each other, and cluster together in the loading plot of principle component analysis. In contrast, most non-deca PBDE congeners do not correlate with DPs. Dec604 stood out having distinctly different spatial distribution pattern, which could be linked to historical use of mirex. Organic matter content of the sediment was not the dominant factor in determining the spatial pattern of pollution by halogenated flame retardants in the rivers of this study. Copyright © 2017 Elsevier Ltd. All rights reserved.

The little bacteria that can – diversity, genomics and ecophysiology of ‘Dehalococcoides’ spp. in contaminated environments

Science.gov (United States)

Taş, Neslihan; Van Eekert, Miriam H. A.; De Vos, Willem M.; Smidt, Hauke

2010-01-01

Summary The fate and persistence of chlorinated organics in the environment have been a concern for the past 50 years. Industrialization and extensive agricultural activities have led to the accumulation of these pollutants in the environment, while their adverse impact on various ecosystems and human health also became evident. This review provides an update on the current knowledge of specialized anaerobic bacteria, namely ‘Dehalococcoides’ spp., which are dedicated to the transformation of various chlorinated organic compounds via reductive dechlorination. Advances in microbiology and molecular techniques shed light into the diversity and functioning of Dehalococcoides spp. in several different locations. Recent genome sequencing projects revealed a large number of genes that are potentially involved in reductive dechlorination. Molecular approaches towards analysis of diversity and expression especially of reductive dehalogenase‐encoding genes are providing a growing body of knowledge on biodegradative pathways active in defined pure and mixed cultures as well as directly in the environment. Moreover, several successful field cases of bioremediation strengthen the notion of dedicated degraders such as Dehalococcoides spp. as key players in the restoration of contaminated environments. PMID:21255338

Remediation of trichloroethylene by bio-precipitated and encapsulated palladium nanoparticles in a fixed bed reactor.

Science.gov (United States)

Hennebel, Tom; Verhagen, Pieter; Simoen, Henri; De Gusseme, Bart; Vlaeminck, Siegfried E; Boon, Nico; Verstraete, Willy

2009-08-01

Trichloroethylene is a toxic and recalcitrant groundwater pollutant. Palladium nanoparticles bio-precipitated on Shewanella oneidensis were encapsulated in polyurethane, polyacrylamide, alginate, silica or coated on zeolites. The reactivity of these bio-Pd beads and zeolites was tested in batch experiments and trichloroethylene dechlorination followed first order reaction kinetics. The calculated k-values of the encapsulated catalysts were a factor of six lower compared to non-encapsulated bio-Pd. Bio-Pd, used as a catalyst, was able to dechlorinate 100 mgL(-1) trichloroethylene within a time period of 1h. The main reaction product was ethane; yet small levels of chlorinated intermediates were detected. Subsequently polyurethane cubes empowered with bio-Pd were implemented in a fixed bed reactor for the treatment of water containing trichloroethylene. The influent recycle configuration resulted in a cumulative removal of 98% after 22 h. The same reactor in a flow through configuration achieved removal rates up to 1059 mg trichloroethylene g Pd(-1)d(-1). This work showed that fixed bed reactors with bio-Pd polyurethane cubes can be instrumental for remediation of water contaminated with trichloroethylene.

Study on the thermal degradation of 3-MCPD esters in model systems simulating deodorization of vegetable oils.

Science.gov (United States)

Ermacora, Alessia; Hrncirik, Karel

2014-05-01

The establishment of effective strategies for the mitigation of 3-MCPD esters in refined vegetable oils is restricted by limited knowledge of their mechanisms of formation and decomposition. In order to gain better understanding on the thermal stability of these compounds, a model system for mimicking oil refining conditions was developed. Pure 3-MCPD esters (3-MCPD dipalmitate and 3-MCPD dilaurate) were subjected to thermal treatment (180-260°C) and the degradation products where monitored over time (0-24h). After 24h of treatment, both 3-MCPD esters showed a significant degradation (ranging from 30% to 70%), correlating with the temperature applied. The degradation pathway, similar for both compounds, was found to involve isomerisation (very rapid, equilibrium was reached within 2h at 260°C), dechlorination and deacylation reactions. The higher relative abundance of non-chlorinated compounds, namely acylglycerols, in the first stages of the treatment suggested that dechlorination is preferred over deacylation with the conditions applied in this study. Copyright © 2013 Elsevier Ltd. All rights reserved.

Skeletal and chlorine effects on 13C-NMR chemical shifts of chlorinated polycyclic systems

Directory of Open Access Journals (Sweden)

Costa V.E.U.

1999-01-01

Full Text Available In order to establish a comparative analysis of chemical shifts caused by ring compression effects or by the presence of a chlorine atom on strained chlorinated carbons, a series of the chlorinated and dechlorinated polycyclic structures derived from "aldrin" (5 and "isodrin" (14 was studied. Compounds were classified in four different groups, according to their conformation and number of ring such as: endo-exo and endo-endo tetracyclics, pentacyclics and hexacyclics. The 13C chemical shift comparison between the chlorinated and dechlorinated compounds showed that when C-9 and C-10 are olefinic carbons, it occurs a shielding of 0.5-2.4 ppm for endo-endo tetracyclics and of 4.7-7.6 ppm for endo-exo tetracyclic. The chemical shift variation for C-11 reaches 49-53 ppm for endo-exo and endo-endo tetracyclics, 54 ppm for pentacyclic and 56-59 ppm for hexacyclic compounds. From these data, it was possible to observe the influence of ring compression on the chemical shifts.

In situ remediation of chlorinated solvent-contaminated groundwater using ZVI/organic carbon amendment in China: field pilot test and full-scale application.

Science.gov (United States)

Yang, Jie; Meng, Liang; Guo, Lin

2018-02-01

Chlorinated solvents in groundwater pose threats to human health and the environment due to their carcinogenesis and bioaccumulation. These problems are often more severe in developing countries such as China. Thus, methods for chlorinated solvent-contaminated groundwater remediation are urgently needed. This study presents a technique of in situ remediation via the direct-push amendment injection that enhances the reductive dechlorination of chlorinated solvents in groundwater in the low-permeability aquifer. A field-based pilot test and a following real-world, full-scale application were conducted at an active manufacturing facility in Shanghai, China. The chlorinated solvents found at the clay till site included 1,1,1-trichloroethane (1,1,1-TCA), 1,1-dichloroethane (1,1-DCA), 1,1-dichloroethylene (1,1-DCE), vinyl chloride (VC), and chloroethane (CA). A commercially available amendment (EHC ® , Peroxychem, Philadelphia, PA) combining zero-valent iron and organic carbon was used to treat the above pollutants. Pilot test results showed that direct-push EHC injection efficiently facilitated the in situ reductive remediation of groundwater contaminated with chlorinated solvents. The mean removal rates of 1,1,1-TCA, 1,1-DCA, and 1,1-DCE at 270 days post-injection were 99.6, 99.3, and 73.3%, respectively, which were obviously higher than those of VC and CA (42.3 and 37.1%, respectively). Clear decreases in oxidation-reduction potential and dissolved oxygen concentration, and increases in Fe 2+ and total organic carbon concentration, were also observed during the monitoring period. These indicate that EHC promotes the anaerobic degradation of chlorinated hydrocarbons primarily via long-term biological reductive dechlorination, with instant chemical reductive dechlorination acting as a secondary pathway. The optimal effective time of EHC injection was 0-90 days, and its radius of influence was 1.5 m. In full-scale application, the maximum concentrations of 1,1,1-TCA

Verification of Methods for Assessing the Sustainability of Monitored Natural Attenuation (MNA)

Science.gov (United States)

2013-01-01

halorespiring bacteria , 2) Groundwater at levels of dissolved oxygen (DO) below threshold levels necessary for efficient reductive dechlorination, and 3...substrates for heterotrophic bacteria in the subsurface, and the consumption of electron acceptors (EAs) associated with aerobic and anaerobic respiration...approximately 20-25 feet thick and is comprised of Pleistocene deposits that are characterized by well-sorted, coarse sand with dispersed lenses of

Combining Low-Energy Electrical Resistance Heating with Biotic and Abiotic Reactions for Treatment of Chlorinated Solvent DNAPL Source Areas

Science.gov (United States)

2015-01-01

particles. Environ. Sci. Technol. 2000, 34, 1794-1805. Atlas , R.M., and R. Bartha . 1987. Microbial Ecology : Fundamentals and Applications. The... microbial processes ( Atlas , 1987; Empadinhas, 2004; Suyama, 2002), and for reductive dechlorination reactions in particular (Kohring, 1989; Holliger...dissolution of DNAPLs, but biological reaction rates also increase with increasing temperature Microbial activity is a function of temperature, and for

Bioassay using the water soluble fraction of a Nigerian Light Crude ...

African Journals Online (AJOL)

Summary: A 96-hour bioassay was conducted using the water soluble fraction of a Nigerian light crude oil sample on Clarias gariepinus fingerlings. 0, 2.5, 5.0, 7.5 and 10 mls of water soluble fractions (WSF) of the oil were added to 1000 litres of de-chlorinated tap water to form 0, 25, 50 , 75 and 100 parts per million ...

Application of Biofilm Covered Activated Carbon Particles as a Microbial Inoculum Delivery System for Enhanced Bioaugmentation of PCBs in Contaminated Sediment

Science.gov (United States)

2013-09-01

after anaerobic digestion at thermophilic conditions (60- 70C). Application of biofilm covered activated carbon particles as a microbial inoculum...Sludge Thickener; Sludge = Sludge after anaerobic digestion at thermophilic conditions (60- 70C). C3. Microscopic evaluation of dechlorinating...associated enzymes are capable of opening the biphenyl ring structure and transform the molecule into a linear structure, this changed structure was not

PALLADIUM/MAGNESIUM CORROSION NANO-CELLS FOR PCB DECHLORINATION

Science.gov (United States)

Polychlorinated biphenyls (PCBs) are toxic and recalcitrant environment pollutants that are prevalent in nation's submarine sediments. PCBs bioaccumulate and progressively move up the food chain to reach humans posing serious health hazards. Today, fish consumption is a major rou...

Hydrogen as indicator for redox conditions and dechlorination

NARCIS (Netherlands)

Meer, J. ter; Gerritse, J.; Mauro, C. di; Harkes, M.P.; Rijnaarts, H.H.M.

2000-01-01

The use of intrinsic degradation processes (natural attenuation) is becoming the basis for the restoration of many contaminated sites. Within this context, measuring concentrations of hydrogen in groundwater is important in two ways. Firstly, the hydrogen concentration can be used to characterize

Anaerobic transformation of DDT related to iron(III) reduction and microbial community structure in paddy soils.

Science.gov (United States)

Chen, Manjia; Cao, Fang; Li, Fangbai; Liu, Chengshuai; Tong, Hui; Wu, Weijian; Hu, Min

2013-03-06

We studied the mechanisms of microbial transformation in functional bacteria on 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) in two different field soils, Haiyan (HY) and Chenghai (CH). The results showed that microbial activities had a steady dechlorination effect on DDT and its metabolites (DDx). Adding lactate or glucose as carbon sources increased the amount of Desulfuromonas, Sedimentibacter, and Clostridium bacteria, which led to an increase in adsorbed Fe(II) and resulted in increased DDT transformation rates. The electron shuttle of anthraquinone-2,6-disulfonic disodium salt resulted in an increase in the negative potential of soil by mediating the electron transfer from the bacteria to the DDT. Moreover, the DDT-degrading bacteria in the CH soil were more abundant than those in the HY soil, which led to higher DDT transformation rates in the CH soil. The most stable compound of DDx was 1,1-dichloro-2,2-bis(p-chloro-phenyl)ethane, which also was the major dechlorination metabolite of DDT, and 1-chloro-2,2-bis-(p-chlorophenyl)ethane and 4,4'-dichlorobenzo-phenone were found to be the terminal metabolites in the anaerobic soils.

Sequential reductive and oxidative biodegradation of chloroethenes stimulated in a coupled bioelectro-process.

Science.gov (United States)

Lohner, Svenja T; Becker, Dirk; Mangold, Klaus-Michael; Tiehm, Andreas

2011-08-01

This article for the first time demonstrates successful application of electrochemical processes to stimulate sequential reductive/oxidative microbial degradation of perchloroethene (PCE) in mineral medium and in contaminated groundwater. In a flow-through column system, hydrogen generation at the cathode supported reductive dechlorination of PCE to cis-dichloroethene (cDCE), vinyl chloride (VC), and ethene (ETH). Electrolytically generated oxygen at the anode allowed subsequent oxidative degradation of the lower chlorinated metabolites. Aerobic cometabolic degradation of cDCE proved to be the bottleneck for complete metabolite elimination. Total removal of chloroethenes was demonstrated for a PCE load of approximately 1.5 μmol/d. In mineral medium, long-term operation with stainless steel electrodes was demonstrated for more than 300 days. In contaminated groundwater, corrosion of the stainless steel anode occurred, whereas DSA (dimensionally stable anodes) proved to be stable. Precipitation of calcareous deposits was observed at the cathode, resulting in a higher voltage demand and reduced dechlorination activity. With DSA and groundwater from a contaminated site, complete degradation of chloroethenes in groundwater was obtained for two months thus demonstrating the feasibility of the sequential bioelectro-approach for field application.

Effect of long-term fertilization on humic redox mediators in multiple microbial redox reactions.

Science.gov (United States)

Guo, Peng; Zhang, Chunfang; Wang, Yi; Yu, Xinwei; Zhang, Zhichao; Zhang, Dongdong

2018-03-01

This study investigated the effects of different long-term fertilizations on humic substances (HSs), humic acids (HAs) and humins, functioning as redox mediators for various microbial redox biotransformations, including 2,2',4,4',5,5'- hexachlorobiphenyl (PCB 153 ) dechlorination, dissimilatory iron reduction, and nitrate reduction, and their electron-mediating natures. The redox activity of HSs for various microbial redox metabolisms was substantially enhanced by long-term application of organic fertilizer (pig manure). As a redox mediator, only humin extracted from soils with organic fertilizer amendment (OF-HM) maintained microbial PCB 153 dechlorination activity (1.03 μM PCB 153 removal), and corresponding HA (OF-HA) most effectively enhanced iron reduction and nitrate reduction by Shewanella putrefaciens. Electrochemical analysis confirmed the enhancement of their electron transfer capacity and redox properties. Fourier transform infrared analysis showed that C=C and C=O bonds, and carboxylic or phenolic groups in HSs might be the redox functional groups affected by fertilization. This research enhances our understanding of the influence of anthropogenic fertility on the biogeochemical cycling of elements and in situ remediation ability in agroecosystems through microorganisms' metabolisms. Copyright © 2017 Elsevier Ltd. All rights reserved.

Accelerated remediation of pesticide-contaminated soil with zerovalent iron

Energy Technology Data Exchange (ETDEWEB)

Shea, P.J. [University of Nebraska-Lincoln, Lincoln, NE 68583-0915 (United States)]. E-mail: pshea@unl.edu; Machacek, T.A. [University of Nebraska-Lincoln, Lincoln, NE 68583-0915 (United States); Comfort, S.D. [University of Nebraska-Lincoln, Lincoln, NE 68583-0915 (United States)

2004-11-01

High pesticide concentrations in soil from spills or discharges can result in point-source contamination of ground and surface waters. Cost-effective technologies are needed for on-site treatment that meet clean-up goals and restore soil function. Remediation is particularly challenging when a mixture of pesticides is present. Zerovalent iron (Fe{sup 0}) has been shown to promote reductive dechlorination and nitro group reduction of a wide range of contaminants in soil and water. We employed Fe{sup 0} for on-site treatment of soil containing >1000 mg metolachlor, >55 mg alachlor, >64 mg atrazine, >35 mg pendimethalin, and >10 mg chlorpyrifos kg{sup -1}. While concentrations were highly variable within the windrowed soil, treatment with 5% (w/w) Fe{sup 0} resulted in >60% destruction of the five pesticides within 90 d and increased to >90% when 2% (w/w) Al{sub 2}(SO{sub 4}){sub 3} was added to the Fe{sup 0}. GC/MS analysis confirmed dechlorination of metolachlor and alachlor during treatment. Our observations support the use of Fe{sup 0} for ex situ treatment of pesticide-contaminated soil. - Capsule: Zerovalent iron promotes pesticide degradation in highly contaminated soil.

Microbial degradation pathways of the herbicide dichlobenil in soils with different history of dichlobenil-exposure

International Nuclear Information System (INIS)

Holtze, Maria S.; Hansen, Hans Christian B.; Juhler, Rene K.; Sorensen, Jan; Aamand, Jens

2007-01-01

This is the first detailed study of metabolite production during degradation of the herbicide 2,6-dichlorobenzonitrile (dichlobenil). Degradation of dichlobenil and three potential metabolites: 2,6-dichlorobenzamide (BAM), 2,6-dichlorobenzoic acid (2,6-DCBA) and ortho-chlorobenzamide (OBAM) was studied in soils either previously exposed or not exposed to dichlobenil using a newly developed HPLC method. Dichlobenil was degraded in all four soils; BAM and 2,6-DCBA were only degraded in soils previously exposed to dichlobenil (100% within 35-56 days and 85-100% in 56 days, respectively), and OBAM in all four soils (25-33% removal in 48 days). BAM produced from dichlobenil was either hydrolyzed to 2,6-DCBA or dechlorinated to OBAM, which was further hydrolyzed to ortho-chlorobenzoic acid. BAM was rapidly mineralized in previously exposed soils only. All potential metabolites and the finding that BAM was a dead-end metabolite of dichlobenil in soils not previously exposed to dichlobenil needs to be included in risk assessments of the use of dichlobenil. - BAM produced from dichlobenil was either hydrolyzed to 2,6-DCBA or dechlorinated to OBAM, which was further hydrolyzed to ortho-chlorobenzoic acid

Efficient 2,4-dichloronitrobenzene removal in the coupled BES-UASB reactor: Effect of external voltage mode.

Science.gov (United States)

Chen, Hui; Gao, Xinyi; Wang, Caiqin; Shao, Junjie; Xu, Xiangyang; Zhu, Liang

2017-10-01

In this study, bioelectrochemical-upflow anaerobic sludge blanket (BES-UASB) system was developed for treatment of 2,4-dichloronitrobenzen (DClNB) containing wastewater to investigate the effect of external voltage with different supplying modes. Results showed that 2,4-dichloroaniline (DClAN) was under detection limit in R1 (applied with intermittent voltage) and R2 (applied with continuous voltage) when the DClNB loading increased from 25 to 100gm 3 d -1 (hydraulic retention time (HRT) was decreased from 24 to 6h) while sudden accumulation of DClAN (1.7mgL -1 ) was observed in R0 (control). Dechlorination efficiency (DE) decreased to 32.7%, 45.0% and 45.3% in R0, R1 and R2 when HRT was further shortened to 4h. Microbial community analysis indicated the significant enrichment of dechlorination-related species in R1 and R2 compared with R0, e.g., Dehalobacter and Dehalococcoides. In summary, the BES-UASB system with intermittent voltage is an alternative process for efficient treatment of DClNB containing wastewater, and the energy input was reduced markedly. Copyright © 2017 Elsevier Ltd. All rights reserved.

Biotransformation of monoaromatic and chlorinated hydrocarbons at an aviation-gasoline spill site

International Nuclear Information System (INIS)

Wilson, B.H.; Wilson, J.T.; Kampbell, D.H.; Bledsoe, B.E.; Armstrong, J.M.

1991-01-01

Loss of petroleum products from underground storage tanks, pipelines, and accidental spills are major sources of contamination of unsaturated soils, aquifer solids, and a shallow water table aquifer under the U.S. Coast Guard Air Station at Traverse City, MI, has acclimated to the aerobic and anaerobic transformation of monoaromatic hydrocarbons (BTX) released from an aviation gasoline spill. The aquifer also exhibits reductive dechlorination of a chlorinated solvent spill adjacent to the aviation gasoline spill. The groundwater is buffered near neutrality. The aviation gasoline plume is methanogenic and the aquifer contains enough iron minerals to support significant iron solubilization. Field evidence of both aerobic and anaerobic biotransformation of monoaromatics was confirmed by laboratory studies of aquifer material obtained from the site. In the laboratory studies, the removal of the monoaromatics in the anaerobic material was rapid and compared favorable with removal in the aerobic material. The kinetics of anaerobic removal of monoaromatics in the laboratory were similar to the kinetics at field scale in the aquifer. Biotransformation of the chlorinated solvents was not observed until late in the study, when daughter products from reductive dechlorination of the chlorinated solvents were identified by GC/MS

Recycling of spent lithium-ion battery with polyvinyl chloride by mechanochemical process.

Science.gov (United States)

Wang, Meng-Meng; Zhang, Cong-Cong; Zhang, Fu-Shen

2017-09-01

In the present study, cathode materials (C/LiCoO 2 ) of spent lithium-ion batteries (LIBs) and waste polyvinyl chloride (PVC) were co-processed via an innovative mechanochemical method, i.e. LiCoO 2 /PVC/Fe was co-grinded followed by water-leaching. This procedure generated recoverable LiCl from Li by the dechlorination of PVC and also generated magnetic CoFe 4 O 6 from Co. The effects of different additives (e.g. alkali metals, non-metal oxides, and zero-valent metals) on (i) the conversion rates of Li and Co and (ii) the dechlorination rate of PVC were investigated, and the reaction mechanisms were explored. It was found that the chlorine atoms in PVC were mechanochemically transformed into chloride ions that bound to the Li in LiCoO 2 to form LiCl. This resulted in reorganization of the Co and Fe crystals to form the magnetic material CoFe 4 O 6 . This study provides a more environmentally-friendly, economical, and straightforward approach for the recycling of spent LIBs and waste PVC compared to traditional processes. Copyright © 2017. Published by Elsevier Ltd.

Development of high-efficiency wastes-burning electric power generating technology. Volume 2. Report for fiscal 1999; Kokoritsu haikibutsu hatsuden gijutsu kaihatsu 1999 nendo hokokusho. 2

Energy Technology Data Exchange (ETDEWEB)

NONE

2000-03-01

In high-efficiency power generation using general wastes and combustible industrial wastes as fuel, development has been performed on a wastes gasifying and melting power generation technology. This technology is capable of suppressing generation of dioxines, recovering slag that can be utilized effectively, and reducing ash volume, by thermally decomposing the wastes and melting combustion ash at elevated temperatures by using thermally decomposed gases. With regard to the evaluation on high temperature corrosiveness of SH materials and the development of a high temperature dust removing system, a steam heater was designed, fabricated, and installed in a model plant, wherein the operation test has been performed for about 1,620 hours. For the technology of dechlorination during a thermal decomposition process, dechlorination rate of 90% was confirmed at 425 degrees C or higher in a demonstration plant. In addition, developments were made on a low temperature denitration device to avoid re-heating of waste gases, a stable wastes supply system to reduce quantity of self-heated melt limiting heat generation, and a waste plastics blowing technology to reduce external fuel charge quantity. Furthermore, a survey was carried out on the trends in wastes electric power generation technologies. (NEDO)

Microbial degradation pathways of the herbicide dichlobenil in soils with different history of dichlobenil-exposure

Energy Technology Data Exchange (ETDEWEB)

Holtze, Maria S. [Department of Natural Sciences, Soil and Environmental Chemistry, Royal Veterinary and Agricultural University, Thorvaldsensvej 40, DK-1871 Frederiksberg C (Denmark) and Department of Geochemistry, Geological Survey of Denmark and Greenland, Oster Voldgade 10, DK-1350 Copenhagen K (Denmark) and Section of Genetics and Microbiology, Department of Ecology, Royal Veterinary and Agricultural University, Thorvaldsensvej 40, DK-1871 Frederiksberg C (Denmark)]. E-mail: msh@geus.dk; Hansen, Hans Christian B. [Department of Natural Sciences, Soil and Environmental Chemistry, Royal Veterinary and Agricultural University, Thorvaldsensvej 40, DK-1871 Frederiksberg C (Denmark); Juhler, Rene K. [Department of Geochemistry, Geological Survey of Denmark and Greenland, Oster Voldgade 10, DK-1350 Copenhagen K (Denmark); Sorensen, Jan [Section of Genetics and Microbiology, Department of Ecology, Royal Veterinary and Agricultural University, Thorvaldsensvej 40, DK-1871 Frederiksberg C (Denmark); Aamand, Jens [Department of Geochemistry, Geological Survey of Denmark and Greenland, Oster Voldgade 10, DK-1350 Copenhagen K (Denmark)

2007-07-15

This is the first detailed study of metabolite production during degradation of the herbicide 2,6-dichlorobenzonitrile (dichlobenil). Degradation of dichlobenil and three potential metabolites: 2,6-dichlorobenzamide (BAM), 2,6-dichlorobenzoic acid (2,6-DCBA) and ortho-chlorobenzamide (OBAM) was studied in soils either previously exposed or not exposed to dichlobenil using a newly developed HPLC method. Dichlobenil was degraded in all four soils; BAM and 2,6-DCBA were only degraded in soils previously exposed to dichlobenil (100% within 35-56 days and 85-100% in 56 days, respectively), and OBAM in all four soils (25-33% removal in 48 days). BAM produced from dichlobenil was either hydrolyzed to 2,6-DCBA or dechlorinated to OBAM, which was further hydrolyzed to ortho-chlorobenzoic acid. BAM was rapidly mineralized in previously exposed soils only. All potential metabolites and the finding that BAM was a dead-end metabolite of dichlobenil in soils not previously exposed to dichlobenil needs to be included in risk assessments of the use of dichlobenil. - BAM produced from dichlobenil was either hydrolyzed to 2,6-DCBA or dechlorinated to OBAM, which was further hydrolyzed to ortho-chlorobenzoic acid.

Biotransformation of a highly chlorinated PCB mixture in an activated sludge collected from a Membrane Biological Reactor (MBR) subjected to anaerobic digestion

International Nuclear Information System (INIS)

Bertin, Lorenzo; Capodicasa, Serena; Fedi, Stefano; Zannoni, Davide; Marchetti, Leonardo; Fava, Fabio

2011-01-01

The role of anaerobic digestion (AD) on the decontamination and biomethanization of a PCB-spiked sludge obtained from a Membrane Biological Reactor (MBR) pilot plant was investigated throughout a 10-month batch experiment. The study was carried out under mesophilic (35 deg. C) and thermophilic (55 deg. C) conditions and was monitored by means of an integrated chemical, microbiological and molecular biology strategy. Remarkable PCB depletions (higher than 50% of the overall spiked PCBs) and dechlorinations were achieved under methanogenic conditions. The process was not affected by yeast extract addition. Both acetoclastic and hydrogenotrophic methanogens, together with some fermentative eubacteria, were found to persist in all PCB biodegrading microcosms. This finding, together with those obtained from parallel microcosms where specific populations were selectively inhibited, suggested that native methanogens played a key role in the biodegradation and dechlorination of the spiked PCBs. Taken together, the results of this study indicate that AD is a feasible option for the decontamination and the efficient disposal (with the production of a CH 4 -rich biogas) of contaminated MBR sludge, which can be then employed as a fertilizer for agricultural purposes.

Military Smokes and Obscurants Fate and Effects: A Literature Review Relative to Threatened and Endangered Species

Science.gov (United States)

2004-12-01

aqueous phases indicated that hexachloroethane (HC) is dechlorinated to the same metabolites by sterilized and axenically cultivated aquatic plants and...Secondary poisoning of kestrels by white phosphorus. Ecotoxicology . 6(4):239-247. Since 1982, extensive waterfowl mortality due to white...D.W. and N.E. Federoff. 1997. Secondary poisoning of kestrels by white . Ecotoxicology . 6(4):239-247. WP T N Toxicity studies in waterfowl

Modeling Degradation Product Partitioning in Chlorinated-DNAPL Source Zones

Science.gov (United States)

Boroumand, A.; Ramsburg, A.; Christ, J.; Abriola, L.

2009-12-01

Metabolic reductive dechlorination degrades aqueous phase contaminant concentrations, increasing the driving force for DNAPL dissolution. Results from laboratory and field investigations suggest that accumulation of cis-dichloroethene (cis-DCE) and vinyl chloride (VC) may occur within DNAPL source zones. The lack of (or slow) degradation of cis-DCE and VC within bioactive DNAPL source zones may result in these dechlorination products becoming distributed among the solid, aqueous, and organic phases. Partitioning of cis-DCE and VC into the organic phase may reduce aqueous phase concentrations of these contaminants and result in the enrichment of these dechlorination products within the non-aqueous phase. Enrichment of degradation products within DNAPL may reduce some of the advantages associated with the application of bioremediation in DNAPL source zones. Thus, it is important to quantify how partitioning (between the aqueous and organic phases) influences the transport of cis-DCE and VC within bioactive DNAPL source zones. In this work, abiotic two-phase (PCE-water) one-dimensional column experiments are modeled using analytical and numerical methods to examine the rate of partitioning and the capacity of PCE-DNAPL to reversibly sequester cis-DCE. These models consider aqueous-phase, nonaqueous phase, and aqueous plus nonaqueous phase mass transfer resistance using linear driving force and spherical diffusion expressions. Model parameters are examined and compared for different experimental conditions to evaluate the mechanisms controlling partitioning. Biot number, a dimensionless number which is an index of the ratio of the aqueous phase mass transfer rate in boundary layer to the mass transfer rate within the NAPL, is used to characterize conditions in which either or both processes are controlling. Results show that application of a single aqueous resistance is capable to capture breakthrough curves when DNAPL is distributed in porous media as low

Environmental application of millimetre-scale sponge iron (s-Fe{sup 0}) particles (III): The effect of surface silver

Energy Technology Data Exchange (ETDEWEB)

Ju, Yongming [South China Institute of Environmental Sciences, Ministry of Environmental Protection (MEP), Guangzhou 510655 (China); South China Subcenter of State Environmental Dioxin Monitoring Center, Guangzhou 510655 (China); Innovative Laboratory for Environmental Functional Materials and Environmental Applications of Microwave Irradiation, Guangzhou 510655 (China); Yu, Yunjiang, E-mail: yuyunjiang@scies.org [South China Institute of Environmental Sciences, Ministry of Environmental Protection (MEP), Guangzhou 510655 (China); Wang, Xiaoyan [South China Institute of Environmental Sciences, Ministry of Environmental Protection (MEP), Guangzhou 510655 (China); Innovative Laboratory for Environmental Functional Materials and Environmental Applications of Microwave Irradiation, Guangzhou 510655 (China); Zhang, Sukun [South China Institute of Environmental Sciences, Ministry of Environmental Protection (MEP), Guangzhou 510655 (China); Liu, Runlong [South China Institute of Environmental Sciences, Ministry of Environmental Protection (MEP), Guangzhou 510655 (China); Innovative Laboratory for Environmental Functional Materials and Environmental Applications of Microwave Irradiation, Guangzhou 510655 (China); Fu, Jianping; Han, Jinglei; Fang, Jiande [South China Institute of Environmental Sciences, Ministry of Environmental Protection (MEP), Guangzhou 510655 (China); Dionysiou, Dionysios D., E-mail: dionysios.d.dionysiou@uc.edu [Environmental Engineering and Science Program, Department of Biomedical, Chemical and Environmental Engineering (DBCEE), University of Cincinnati, Cincinnati, OH 45221-0012 (United States)

2015-12-15

Highlights: • Direct reductive deposition reaction achieves surfaced decoration of s-Fe{sup 0} particles. • Ag{sup 0}-s-Fe{sup 0} displays similar removal efficiency of PCP as compared to bimetal of nZVI. • Ag{sup 0}-s-Fe{sup 0} can be utilized under mild reaction condition compared to bimetal of nZVI. • The catalytic mechanism over Ag{sup 0}-s-Fe{sup 0} under US condition is elucidated. - Abstract: To enhance the dechlorination reactivity of millimetric sponge iron (s-Fe{sup 0}), a facile one-pot method was used to decorate s-Fe{sup 0} with Ag{sup +} ions under ambient conditions. The results recorded by X-ray diffraction patterns, X-ray photoelectron spectra and high-resolution transmission electron microscopy demonstrated that the growth of Ag{sup 0} was dominated primarily by (1 1 1) plane with a mean length of ∼20 nm. The roles of Ag{sup 0} loading, catalyst dosage, particle size, initial pH and contaminant concentration were assessed during the removal of pentachlorophenol (PCP). Catalyst recyclability was also studied. The results revealed that 3–5 mm s-Fe{sup 0} particles with 5 wt% Ag{sup 0} loading exhibited the best performance with a dose of 3.0 g per 60 mL PCP solution. In addition, the dechlorination of PCP followed two-step, pseudo-first-order reaction kinetics, and Ag{sup 0}-s-Fe{sup 0} was advantageous compared with bimetals of nanoscale zero-valent iron, iron power and iron flakes. The dechlorination mechanism of PCP over Ag{sup 0}-s-Fe{sup 0} was attributed to the surface Ag{sup 0} decoration, which catalyzed the formation of reactive hydrogen atoms for indirect reaction, and the direct electron transfer via Fe–Ag{sup 0} galvanic cells for direct reaction. This suggests that Ag-based bimetals of s-Fe{sup 0} have great potential in the pretreatment of organic halogen compounds in aqueous solution.

Identification of active dehalorespiring microbial populations in anoxic river sediment by RNA-based stable isotope probing

Science.gov (United States)

Kittelmann, S.; Friedrich, M. W.

2005-12-01

Tetrachloroethene (perchloroethylene, PCE), a persistent contaminant in aquifers, soils and sediments, can be reductively dechlorinated by anaerobic microorganisms in a process referred to as dehalorespiration. However, the biodiversity of dehalorespiring microorganisms and their distribution especially in pristine environments is largely unexplored. Therefore, the aim of this study was to detect potentially novel PCE-dehalorespiring microorganisms by using stable isotope probing (SIP), a technique that allows to directly identify the function of uncultivated microbial populations. We simulated a PCE contamination by incubating pristine river sediment in the presence of PCE at a steady, low aqueous concentration (20 μM). Dehalogenation activity in microcosms (20 nmol cis-dichloroethene per ml slurry per day formed) was detected already after 4 weeks at 20°C with sediment indigenous electron donors. The microbial community in sediment incubations was probed with 13C-labelled acetate (0.5 mM) as electron donor and carbon source at 15°C for 3 days. After RNA extraction, "heavy" 13C-rRNA and light 12C-rRNA were separated by isopycnic centrifugation, and Bacteria-related populations in gradient fractions were characterised by terminal restriction fragment length polymorphism analysis and cloning. In heavy gradient fractions from the microcosm with PCE, we detected a prominent 506-bp terminal restriction fragment (T-RF) and a few minor T-RFs only. In contrast, in the control without PCE, Bacteria-specific rRNA was restricted to light gradient fractions, and the prominent T-RFs found in the PCE-dechlorinating microcosm were of minor importance. Apparently, 13C-acetate was incorporated into bacterial rRNA more effectively in PCE-respiring microcosms. Thus, rRNA-SIP provides strong evidence for the presence of PCE-dehalorespiring, 13C-acetate-utilising populations in river sediment microcosms. Cloning/sequencing analysis identified the prominent members of the heavy

Complementing approaches to demonstrate chlorinated solvent biodegradation in a complex pollution plume: Mass balance, PCR and compound-specific stable isotope analysis

Science.gov (United States)

Courbet, Christelle; Rivière, Agnès; Jeannottat, Simon; Rinaldi, Sandro; Hunkeler, Daniel; Bendjoudi, Hocine; de Marsily, Ghislain

2011-11-01

This work describes the use of different complementing methods (mass balance, polymerase chain reaction assays and compound-specific stable isotope analysis) to demonstrate the existence and effectiveness of biodegradation of chlorinated solvents in an alluvial aquifer. The solvent-contaminated site is an old chemical factory located in an alluvial plain in France. As most of the chlorinated contaminants currently found in the groundwater at this site were produced by local industries at various times in the past, it is not enough to analyze chlorinated solvent concentrations along a flow path to convincingly demonstrate biodegradation. Moreover, only a few data were initially available to characterize the geochemical conditions at this site, which were apparently complex at the source zone due to (i) the presence of a steady oxygen supply to the groundwater by irrigation canal losses and river infiltration and (ii) an alkaline pH higher than 10 due to former underground lime disposal. A demonstration of the existence of biodegradation processes was however required by the regulatory authority within a timeframe that did not allow a full geochemical characterization of such a complex site. Thus a combination of different fast methods was used to obtain a proof of the biodegradation occurrence. First, a mass balance analysis was performed which revealed the existence of a strong natural attenuation process (biodegradation, volatilization or dilution), despite the huge uncertainty on these calculations. Second, a good agreement was found between carbon isotopic measurements and PCR assays (based on 16S RNA gene sequences and functional genes), which clearly indicated reductive dechlorination of different hydrocarbons (Tetrachloroethene—PCE-, Trichloroethene—TCE-, 1,2- cisDichloroethene— cis-1,2-DCE-, 1,2- transDichloroethene— trans-1,2-DCE-, 1,1-Dichloroethene—1,1-DCE-, and Vinyl Chloride—VC) to ethene. According to these carbon isotope measurements

The DNAPL Remediation Challenge: Is There a Case for Source Depletion?

Science.gov (United States)

2003-12-01

fermentation products acting as electron donors to promote reductive dechlorination of chlorinated solvents (e.g., see discussion on Sages and Bachman...has been primarily used to remove organic contamination in the vadose zone (see e.g., Stegemeier and Vinegar , 2001). Signifi cant removals of...Stegemeier, G.L., and H.J. Vinegar . 2001. Thermal conduction heating for in-situ thermal desorption of soils. In: Hazardous and Radioactive Waste Treatment

Iron oxide nanoparticle synthesis in aqueous and membrane systems for oxidative degradation of trichloroethylene from water

Energy Technology Data Exchange (ETDEWEB)

Gui Minghui; Smuleac, Vasile [University of Kentucky, Department of Chemical and Materials Engineering (United States); Ormsbee, Lindell E. [University of Kentucky, Department of Civil Engineering (United States); Sedlak, David L. [University of California at Berkeley, Department of Civil and Environmental Engineering (United States); Bhattacharyya, Dibakar, E-mail: db@engr.uky.edu [University of Kentucky, Department of Chemical and Materials Engineering (United States)

2012-05-15

The potential for using hydroxyl radical (OH{sup Bullet }) reactions catalyzed by iron oxide nanoparticles (NPs) to remediate toxic organic compounds was investigated. Iron oxide NPs were synthesized by controlled oxidation of iron NPs prior to their use for contaminant oxidation (by H{sub 2}O{sub 2} addition) at near-neutral pH values. Cross-linked polyacrylic acid (PAA) functionalized polyvinylidene fluoride (PVDF) microfiltration membranes were prepared by in situ polymerization of acrylic acid inside the membrane pores. Iron and iron oxide NPs (80-100 nm) were directly synthesized in the polymer matrix of PAA/PVDF membranes, which prevented the agglomeration of particles and controlled the particle size. The conversion of iron to iron oxide in aqueous solution with air oxidation was studied based on X-ray diffraction, Moessbauer spectroscopy and BET surface area test methods. Trichloroethylene (TCE) was selected as the model contaminant because of its environmental importance. Degradations of TCE and H{sub 2}O{sub 2} by NP surface generated OH{sup Bullet} were investigated. Depending on the ratio of iron and H{sub 2}O{sub 2}, TCE conversions as high as 100 % (with about 91 % dechlorination) were obtained. TCE dechlorination was also achieved in real groundwater samples with the reactive membranes.

Iron oxide nanoparticle synthesis in aqueous and membrane systems for oxidative degradation of trichloroethylene from water

International Nuclear Information System (INIS)

Gui Minghui; Smuleac, Vasile; Ormsbee, Lindell E.; Sedlak, David L.; Bhattacharyya, Dibakar

2012-01-01

The potential for using hydroxyl radical (OH • ) reactions catalyzed by iron oxide nanoparticles (NPs) to remediate toxic organic compounds was investigated. Iron oxide NPs were synthesized by controlled oxidation of iron NPs prior to their use for contaminant oxidation (by H 2 O 2 addition) at near-neutral pH values. Cross-linked polyacrylic acid (PAA) functionalized polyvinylidene fluoride (PVDF) microfiltration membranes were prepared by in situ polymerization of acrylic acid inside the membrane pores. Iron and iron oxide NPs (80–100 nm) were directly synthesized in the polymer matrix of PAA/PVDF membranes, which prevented the agglomeration of particles and controlled the particle size. The conversion of iron to iron oxide in aqueous solution with air oxidation was studied based on X-ray diffraction, Mössbauer spectroscopy and BET surface area test methods. Trichloroethylene (TCE) was selected as the model contaminant because of its environmental importance. Degradations of TCE and H 2 O 2 by NP surface generated OH • were investigated. Depending on the ratio of iron and H 2 O 2 , TCE conversions as high as 100 % (with about 91 % dechlorination) were obtained. TCE dechlorination was also achieved in real groundwater samples with the reactive membranes.

Mechanisms, Chemistry, and Kinetics of Anaerobic Biodegradation of cis-Dichloroethene and Vinyl Chloride

Energy Technology Data Exchange (ETDEWEB)

McCarty, P.L.; Spormann, A.M.

2000-12-01

Anaerobic biological processes can result in PCE and TCE destruction through conversion to cis-dichloroethene (cDCE) then to vinyl chloride (VC), and finally to ethene. Here, the chlorinated aliphatic hydrocarbons (CAHs) serve as electron acceptors in energy metabolism, requiring electron donors such as hydrogen from an external source. The purpose of this study was to learn more about the biochemistry of cDCE and VC conversion to ethene, to better understand the requirements for electron donors, and to determine factors affecting the rates of CAH degradation and organism growth. The biochemistry of reductive dehalogenation of VC was studied with an anaerobic mixed culture enriched on VC. In other studies on electron donor needs for dehalogenation of cDCE and VC, competition for hydrogen was found to occur between the dehalogenators and other microorganisms such as methanogens and homoacetogens in a benzoate-acclimated dehalogenating methanogenic mixed culture. Factors affecting the relative rates of destruction of the solvents and their intermediate products were evaluated. Studies using a mixed PCE-dehalogenating culture as well as the VC enrichment for biochemical studies suggested that the same species was involved in both cDCE and VC dechlorination, and that cDCE and VC competitively inhibited each other's dechlorination rate.

Thermoactivated persulfate oxidation of pesticide chlorpyrifos in aquatic system: kinetic and mechanistic investigations.

Science.gov (United States)

Zhou, Lei; Zhang, Ya; Ying, Rongrong; Wang, Guoqing; Long, Tao; Li, Jianhua; Lin, Yusuo

2017-04-01

The widespread occurrence of organophosphorus pesticides (OPPs) in the environment poses risks to both ecologic system as well as human health. This study investigated the oxidation kinetics of chlorpyrifos (CP), one of the typical OPPs, by thermoactivated persulfate (PS) oxidation process, and evaluated the influence of key kinetic factors, such as PS concentrations, pH, temperature, bicarbonate, and chloride ions. The reaction pathways and mechanisms were also proposed based on products identification by LC-MS techniques. Our results revealed that increasing initial PS concentration and temperature favored the decomposition of CP, whereas the oxidation efficiency was not affected by pH change ranging from 3 to 11. Bicarbonate was found to play a detrimental role on CP removal rates, while chloride showed no effect. The oxidation pathways including initial oxidation of P=S bond to P=O, dechlorination, dealkylation, and the dechlorination-hydroxylation were proposed, and the detailed underlying mechanisms were also discussed. Molecular orbital (MO) calculations indicated that P=S bond was the most favored oxidation site of the molecule. The toxicity of reaction solution was believed to increase due to the formation of products with P=O structures. This work demonstrates that OPPs can readily react with SO 4 ·- and provides important information for further research on the oxidation of these contaminants.

Microbial mineralization of cis-dichloroethene and vinyl chloride as a component of natural attenuation of chloroethene contaminants under conditions identified in the field as anoxic

Science.gov (United States)

Bradley, Paul M.

2012-01-01

Chlororespiration is a key component of remediation at many chloroethene-contaminated sites. In some instances, limited accumulation of reductive dechlorination daughter products may suggest that natural attenuation is not adequate for site remediation. This conclusion is justified when evidence for parent compound (tetrachloroethene, PCE, or trichloroethene, TCE) degradation is lacking. For many chloroethene-contaminated shallow aquifer systems, however, non-conservative losses of the parent compounds are clear but the mass balance between parent compound attenuation and accumulation of reductive dechlorination daughter products is incomplete. Incomplete mass balance indicates a failure to account for important contaminant attenuation mechanisms, and is consistent with contaminant degradation to non-diagnostic mineralization products. An ongoing technical debate over the potential for mineralization of dichloroethene (DCE) and vinyl chloride (VC) to CO2 in the complete absence of diatomic oxygen has largely obscured the importance of microbial DCE/VC mineralization at dissolved oxygen (DO) concentrations below the current field standard (DO conditions. This study demonstrates that oxygen-based microbial mineralization of DCE and VC can be substantial under field conditions that are frequently characterized as "anoxic." Because mischaracterization of operant contaminant biodegradation processes can lead to expensive and ineffective remedial actions, a modified framework for assessing the potential importance of oxygen during chloroethene biodegradation was developed.

Radiolytic decomposition of dioxins in liquid wastes

International Nuclear Information System (INIS)

Zhao Changli; Taguchi, M.; Hirota, K.; Takigami, M.; Kojima, T.

2006-01-01

The dioxins including polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are some of the most toxic persistent organic pollutants. These chemicals have widely contaminated the air, water, and soil. They would accumulate in the living body through the food chains, leading to a serious public health hazard. In the present study, radiolytic decomposition of dioxins has been investigated in liquid wastes, including organic waste and waste-water. Dioxin-containing organic wastes are commonly generated in nonane or toluene. However, it was found that high radiation doses are required to completely decompose dioxins in the two solvents. The decomposition was more efficient in ethanol than in nonane or toluene. The addition of ethanol to toluene or nonane could achieve >90% decomposition of dioxins at the dose of 100 kGy. Thus, dioxin-containing organic wastes can be treated as regular organic wastes after addition of ethanol and subsequent γ-ray irradiation. On the other hand, radiolytic decomposition of dioxins easily occurred in pure-water than in waste-water, because the reaction species is largely scavenged by the dominant organic materials in waste-water. Dechlorination was not a major reaction pathway for the radiolysis of dioxin in water. In addition, radiolytic mechanism and dechlorinated pathways in liquid wastes were also discussed. (authors)

Compounded effects of chlorinated ethene inhibition on ecological interactions and population abundance in a Dehalococcoides - Dehalobacter coculture.

Science.gov (United States)

Lai, Yenjung; Becker, Jennifer G

2013-02-05

The development of rational and effective engineered bioremediation approaches for sites contaminated with chlorinated solvents requires a fundamental understanding of the factors limiting the in situ activity of dehalorespiring bacteria. Frequently, multiple dehalorespiring bacteria are present at contaminated sites, particularly when bioaugmentation is applied. The ecological interactions between different dehalorespiring populations can-along with hydrodynamic and other environmental factors-affect their activity and thus the rates and extent of dehalorespiration. An integrated experimental and modeling approach was used to evaluate the ecological interactions between two hydrogenotrophic, dehalorespiring strains. A dual Monod model of dehalorespiration provided a good fit to the chlorinated ethene concentrations measured in a coculture of Dehalococcoides mccartyi 195 and Dehalobacter restrictus growing on tetrachloroethene (PCE) and excess H(2) in a continuous-flow reactor. Inhibition of dehalorespiration by chlorinated ethenes was previously observed in cultures containing Dehalococcoides or Dehalobacter strains. Therefore, inhibition coefficients were estimated for Dhc. mccartyi 195 and Dhb. restrictus. The inhibition effects of PCE and TCE on VC dechlorination by Dhc. mccartyi 195, and of VC on PCE and TCE dechlorination by Dhb. restrictus, were compounded when these strains were grown in coculture, and dehalorespiring population abundance and survival could be accurately predicted only by incorporating these complex interactions into the dual Monod model.

Photodegradation of Dechlorane Plus in n-nonane under the irradiation of xenon lamp

Energy Technology Data Exchange (ETDEWEB)

Wang, Siwen; Huang, Jun; Yang, Yang; Yu, Gang, E-mail: yg-den@tsinghua.edu.cn; Deng, Shubo; Wang, Bin

2013-09-15

Highlights: • Photodegradation of isomers of Dechlorane Plus (DP) as a potential persistent organic pollutant were studied. • UV-C was found to be the main contributor to DP photodegradation. • DP degradation followed the pseudo first-order kinetics. • Sequential dechlorination was found as the degradation mechanism. -- Abstract: Photodegradation has been regarded as the main mechanism for the removal of many halogenated organic pollutants in the environment. The photodegradation of Dechlorane Plus (DP), an emerging contaminant taken worldwide concerns in recent years, was investigated under the irradiation of a xenon lamp. Rapid photodegradation was found under the irradiation of 200–750 nm light, while the degradation became much slower when the range of light wavelength changed to 280–750 nm. DP degradation followed the pseudo first-order kinetics. The quantum yields of 200–280 nm (UV-C) were about 2–3 orders of magnitude higher than 280–320 nm, and no yields can be detected in 320–750 nm range, in an agreement with the changing photodegradation rates with wavelength. The photodegradation products were identified as lower chlorinated DPs, implicating a mechanism of reductive dechlorination. No photoisomerization or solvent adducts were observed, and the difference of photodegradation rate between syn- and anti-DP isomers was negligible.

Birnessite-induced mechanochemical degradation of 2,4-dichlorophenol.

Science.gov (United States)

Nasser, A; Mingelgrin, U

2014-07-01

DCP (2,4-dichlorophenol) is the key-intermediate in the synthesis of some widely used pesticides and is an EPA priority pollutant. The mechanochemical breakdown of DCP loaded on birnessite (δ-MnO2), montmorillonite saturated with Na(+) or Cu(2+) and hematite was investigated. Mechanical force was applied by grinding of mixtures of DCP and the minerals, using mortar and pestle. Grinding of DCP for 5 min with the montmorillonites or with hematite resulted in negligible degradation during grinding, while grinding with birnessite induced the immediate degradation of 90% of the loaded DCP. Incubation for 24h after grinding did result in up to 30% degradation of the DCP loaded on the other minerals tested. HPLC and LC-MS analysis revealed that the transformation of DCP yielded oligomerization products as well as partial dechlorination. DCP degradation on birnessite was accompanied with a substantial increase in the extractability of manganese from the mineral into an acidic aqueous solution, indicating that Mn(IV) in the mineral transformed into Mn(II) and that birnessite served as an electron acceptor in the transformation. The oligomerization and partial dechlorination brought about by grinding, suggest a reduction in bioavailability and toxicity. Copyright © 2013 Elsevier Ltd. All rights reserved.

Enantiospecific tritium labeling of 28-homocastasterone.

Science.gov (United States)

Elbert, Tomáš; Patil, Mahadeo R; Marek, Aleš

2017-03-01

A regiospecific and enantiospecific synthesis of tritium-labeled 28-homocastasterone is reported. Appropriate chlorocarbonate, efficiently synthesized from the starting 28-homocastasterone in an overall yield of 46%, undergoes catalytic tritium dechlorination by the T 2 /Pd[0]/Et 3 N system, providing 28-[3β- 3 H]homocastasterone, in a good yield, radiochemical purity (>97%), and with a high specific activity (5.8 Ci/mmol). Copyright © 2016 John Wiley & Sons, Ltd.

USE OF GRANULAR GRAPHITE FOR ELECTROLYTIC DECHLORINATION OF TRICHLOROETHYLENE

Science.gov (United States)

Granular graphite is a potential electrode material for the electrochemical remediation of refractory chlorinated organic compounds such as trichloroethylene (TCE). However, the use of granular graphite can complicate the experimental results. On one hand, up to 99% of TCE was re...

Dechlorination of 1,2– dichloroethane by Pseudomonas aeruginosa ...

African Journals Online (AJOL)

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Transformation of halogenated aliphatic compounds. Environ. Sci. Technol. 21: 722-. 736. Wilson K (1987). Preparation of genomic DNA from bacteria. In: Current Protocols in Molecular Biology. Ausubel FM, Brent R.,. Kingston RE, Moore DD, Seidman J G, Smith AJ, Struhl K (editors),. Wiley publishers, New York, USA, pp.

Biochars made from agro-industrial by-products remove chlorine and lower water toxicity

Science.gov (United States)

Tzachristas, Andreas; Xirou, Maria; Manariotis, Ioannis D.; Dailianis, Stefanos; Karapanagioti, Hrissi K.

2016-04-01

Chlorination is the most common disinfection process for water and treated wastewater. For the industrial use of water in food production, chlorine can add undesired taste and odor to the final product. For this reason, dechlorination is desired for food industries that use municipal tap water. For treated wastewater discharge or reuse, chlorine can be toxic to the receiving aqueous systems and to the irrigated plants. In both the above cases, dechlorination is also required. Traditionally activated carbon has been used as the ideal material for the removal of chlorine. The main mechanisms that describe the interaction between activated carbon and HOCl or OCl- are described by the following equations (AWWA, 1990): HOCl + C* → C*O + H+ + Cl- (1), OCl- + C* → C*O + Cl- (2) Where C* and C*O represent the activated carbon surface and a surface oxide, respectively. The present study proposes the use of agro-industrial by-products for the production of biochars that will be used for dechlorination of tap-water used for food-industry production. Different raw materials such as malt spent rootlets, coffee residue, olive and grape seeds, etc. are used for the production of biochar. Various temperatures and air-to-solid ratios are tested for optimizing biochar production. Batch tests as well as a column test are employed to study the dechlorination efficiency and kinetics of the different raw and biochar materials as well as those of commercial activated carbons. As chlorine concentration increases the removal also increases linearily. After 1 and 24 hours of contact the chlorine relative removal efficiencies for the biochar made from olive seeds are 50 and 77 ± 4%, respectively. It seems that the removal kinetics are faster during the first hour; then, removal continues but with a slower rate. Most of the biochars tested (with 3 mg of solid in 20 mL of chlorine solution at initial concentration Co=1.5 mg/L) demonstrated removal efficiencies with an average of 9.4 ± 0

Mass Transfer Limited Enhanced Bioremediation at Dnapl Source Zones: a Numerical Study

Science.gov (United States)

Kokkinaki, A.; Sleep, B. E.

2011-12-01

The success of enhanced bioremediation of dense non-aqueous phase liquids (DNAPLs) relies on accelerating contaminant mass transfer from the organic to the aqueous phase, thus enhancing the depletion of DNAPL source zones compared to natural dissolution. This is achieved by promoting biological activity that reduces the contaminant's aqueous phase concentration. Although laboratory studies have demonstrated that high reaction rates are attainable by specialized microbial cultures in DNAPL source zones, field applications of the technology report lower reaction rates and prolonged remediation times. One possible explanation for this phenomenon is that the reaction rates are limited by the rate at which the contaminant partitions from the DNAPL to the aqueous phase. In such cases, slow mass transfer to the aqueous phase reduces the bioavailability of the contaminant and consequently decreases the potential source zone depletion enhancement. In this work, the effect of rate limited mass transfer on bio-enhanced dissolution of DNAPL chlorinated ethenes is investigated through a numerical study. A multi-phase, multi-component groundwater transport model is employed to simulate DNAPL mass depletion for a range of source zone scenarios. Rate limited mass transfer is modeled by a linear driving force model, employing a thermodynamic approach for the calculation of the DNAPL - water interfacial area. Metabolic reductive dechlorination is modeled by Monod kinetics, considering microbial growth and self-inhibition. The model was utilized to identify conditions in which mass transfer, rather than reaction, is the limiting process, as indicated by the bioavailability number. In such cases, reaction is slower than expected, and further increase in the reaction rate does not enhance mass depletion. Mass transfer rate limitations were shown to affect both dechlorination and microbial growth kinetics. The complex dynamics between mass transfer, DNAPL transport and distribution, and

Sister Dehalobacter Genomes Reveal Specialization in Organohalide Respiration and Recent Strain Differentiation Likely Driven by Chlorinated Substrates

Directory of Open Access Journals (Sweden)

Shuiquan eTang

2016-02-01

Full Text Available The genomes of two closely related Dehalobacter strains (strain CF and strain DCA were assembled from the metagenome of an anaerobic enrichment culture that reductively dechlorinates chloroform (CF, 1,1,1-trichloroethane (1,1,1-TCA and 1,1-dichloroethane (1,1-DCA. The 3.1 Mbp genomes of strain CF (that dechlorinates CF and 1,1,1-TCA and strain DCA (that dechlorinates 1,1-DCA each contain 17 putative reductive dehalogenase homologous (rdh genes. These two genomes were systematically compared to three other available organohalide-respiring Dehalobacter genomes (Dehalobacter restrictus strain PER-K23, Dehalobacter sp. strain E1 and Dehalobacter sp. strain UNSWDHB, and to the genomes of Dehalococcoides mccartyi strain 195 and Desulfitobacterium hafniense strain Y51. This analysis compared 42 different metabolic and physiological categories. The genomes of strains CF and DCA share 90% overall average nucleotide identity and greater than 99.8% identity over a 2.9 Mbp alignment that excludes large insertions, indicating that these genomes differentiated from a close common ancestor. This differentiation was likely driven by selection pressures around two orthologous reductive dehalogenase genes, cfrA and dcrA, that code for the enzymes that reduce CF or 1,1,1-TCA and 1,1-DCA. The many reductive dehalogenase genes found in the five Dehalobacter genomes cluster into two small conserved regions and were often associated with Crp/Fnr transcriptional regulators. Specialization is on-going on a strain-specific basis, as some strains but not others have lost essential genes in the Wood-Ljungdahl (strain E1 and corrinoid biosynthesis pathways (strains E1 and PER-K23. The gene encoding phosphoserine phosphatase, which catalyzes the last step of serine biosynthesis, is missing from all five Dehalobacter genomes, yet D. restrictus can grow without serine, suggesting an alternative or unrecognized biosynthesis route exists. In contrast to Dehalococcoides mccartyi

Natural transformation of chlordecone into 5b-hydrochlordecone in French West Indies soils : statistical evidence for investigating long-term persistence of organic pollutants

OpenAIRE

Devault, D. A.; Laplanche, C.; Pascaline, H.; Bristeau, S.; Mouvet, C.; Macarie, Hervé

2016-01-01

Chlordecone (CLD) was an organochlorine insecticide whose previous use resulted in an extensive pollution of the environment with severe health effects and social consequences. A closely related compound, 5b-hydrochlordecone (5b-hydroCLD), has been searched for and often detected in environmental matrices from the geographical area where CLD was applied. The current consensus considered that its presence was not the result of a biotic or abiotic dechlorination of CLD in these matrices but rat...

Isolation and Partial Characterization of Bacteria in an Anaerobic Consortium That Mineralizes 3-Chlorobenzoic Acid †

OpenAIRE

Shelton, Daniel R.; Tiedje, James M.

1984-01-01

A methanogenic consortium able to use 3-chlorobenzoic acid as its sole energy and carbon source was enriched from anaerobic sewage sludge. Seven bacteria were isolated from the consortium in mono- or coculture. They included: one dechlorinating bacterium (strain DCB-1), one benzoate-oxidizing bacterium (strain BZ-2), two butyrate-oxidizing bacteria (strains SF-1 and NSF-2), two H2-consuming methanogens (Methanospirillum hungatei PM-1 and Methanobacterium sp. strain PM-2), and a sulfate-reduci...

Effects of particle composition and environmental parameters on catalytic hydrodechlorination of trichloroethylene by nanoscale bimetallic Ni-Fe.

Science.gov (United States)

Wei, Jianjun; Qian, Yajing; Liu, Wenjuan; Wang, Lutao; Ge, Yijie; Zhang, Jianghao; Yu, Jiang; Ma, Xingmao

2014-05-01

Catalytic nickel was successfully incorporated into nanoscale iron to enhance its dechlorination efficiency for trichloroethylene (TCE), one of the most commonly detected chlorinated organic compounds in groundwater. Ethane was the predominant product. The greatest dechlorination efficiency was achieved at 22 molar percent of nickel. This nanoscale Ni-Fe is poorly ordered and inhomogeneous; iron dissolution occurred whereas nickel was relatively stable during the 24-hr reaction. The morphological characterization provided significant new insights on the mechanism of catalytic hydrodechlorination by bimetallic nanoparticles. TCE degradation and ethane production rates were greatly affected by environmental parameters such as solution pH, temperature and common groundwater ions. Both rate constants decreased and then increased over the pH range of 6.5 to 8.0, with the minimum value occurring at pH 7.5. TCE degradation rate constant showed an increasing trend over the temperature range of 10 to 25°C. However, ethane production rate constant increased and then decreased over the range, with the maximum value occurring at 20°C. Most salts in the solution appeared to enhance the reaction in the first half hour but overall they displayed an inhibitory effect. Combined ions showed a similar effect as individual salts. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

FY 1999 report on the result for research and development of instantaneously effective and innovative energy and environment technology. Development of technology to use combustible wastes as resources and fuels; 1999 nendo sokkoteki kakushinteki energy kankyo gijutsu kenkyu kaihatsu kanengomi saishigen nenryoka gijutsu kaihatsu

Energy Technology Data Exchange (ETDEWEB)

NONE

2000-03-01

Manufacturing compressed fuel, or refuse paper and plastic fuel (RPF) from combustible wastes such as used papers and waste plastics to utilize them effectively as a fuel to substitute fossil fuels is regarded as a promising engagement. However, this process indispensably requires removal of chlorine contained in used papers and waste plastics to a degree that they do not impede the combustion. The present research and development is intended to develop a PRF pretreatment technology and a dechlorination technology, and establish a technology to utilize the materials as resources and fuels as thermal recycling of combustible wastes. The current fiscal year has performed research and development on the following themes: development of a sorting system and a crushing system in developing the pretreatment technology, whereas for the former system, sorting tests were carried out by using a vibration type wind power sorting machine and an inertia force wind power sorting machine, and for the latter system, data were obtained on the crushing characteristics; dechlorination tests, in which it was discovered that the mixing ratio of used paper in the material affects the chlorine concentration; research on combustion characteristics, in which fundamental combustion tests using a small fluidized bed, combustion tests using a bench scale fluidized bed, and stoker fired furnace combustion tests were performed; and demonstrative operation researches. (NEDO)

Optimal scheduling of biocide dosing for seawater-cooled power and desalination plants

KAUST Repository

Mahfouz, Abdullah Bin

2011-02-13

Thermal desalination systems are typically integrated with power plants to exploit the excess heat resulting from the power-generation units. Using seawater in cooling the power plant and the desalination system is a common practice in many parts of the world where there is a shortage of freshwater. Biofouling is one of the major problems associated with the usage of seawater in cooling systems. Because of the dynamic variation in the power and water demands as well as the changes in the characteristics of seawater and the process, there is a need to develop an optimal policy for scheduling biocide usage and cleaning maintenance of the heat exchangers. The objective of this article is to introduce a systematic procedure for the optimization of scheduling the dosing of biocide and dechlorination chemicals as well as cleaning maintenance for a power production/thermal desalination plant. A multi-period optimization formulation is developed and solved to determine: the optimal levels of dosing and dechlorination chemicals; the timing of maintenance to clean the heat-exchange surfaces; and the dynamic dependence of the biofilm growth on the applied doses, the seawater-biocide chemistry, the process conditions, and seawater characteristics for each time period. The technical, economic, and environmental considerations of the system are accounted for. A case study is solved to elucidate the applicability of the developed optimization approach. © 2011 Springer-Verlag.

Reinterpreting the importance of oxygen-based biodegradation in chloroethene-contaminated groundwater

Science.gov (United States)

Bradley, Paul M.

2011-01-01

Chlororespiration is common in shallow aquifer systems under conditions nominally identified as anoxic. Consequently, chlororespiration is a key component of remediation at many chloroethene-contaminated sites. In some instances, limited accumulation of reductive dechlorination daughter products is interpreted as evidence that natural attenuation is not adequate for site remediation. This conclusion is justified when evidence for parent compound (tetrachloroethene, PCE, or trichloroethene, TCE) degradation is lacking. For many chloroethene-contaminated shallow aquifer systems, however, nonconservative losses of the parent compounds are clear but the mass balance between parent compound attenuation and accumulation of reductive dechlorination daughter products is incomplete. Incomplete mass balance indicates a failure to account for important contaminant attenuation mechanisms and is consistent with contaminant degradation to nondiagnostic mineralization products like CO2. While anoxic mineralization of chloroethene compounds has been proposed previously, recent results suggest that oxygen-based mineralization of chloroethenes also can be significant at dissolved oxygen concentrations below the currently accepted field standard for nominally anoxic conditions. Thus, reassessment of the role and potential importance of low concentrations of oxygen in chloroethene biodegradation are needed, because mischaracterization of operant biodegradation processes can lead to expensive and ineffective remedial actions. A modified interpretive framework is provided for assessing the potential for chloroethene biodegradation under different redox conditions and the probable role of oxygen in chloroethene biodegradation.

Continuous-flow column study of reductive dehalogenation of PCE upon bioaugmentation with the Evanite enrichment culture

Science.gov (United States)

Azizian, Mohammad F.; Behrens, Sebastian; Sabalowsky, Andrew; Dolan, Mark E.; Spormann, Alfred M.; Semprini, Lewis

2008-08-01

A continuous-flow anaerobic column experiment was conducted to evaluate the reductive dechlorination of tetrachloroethene (PCE) in Hanford aquifer material after bioaugmentation with the Evanite (EV) culture. An influent PCE concentration of 0.09 mM was transformed to vinyl chloride (VC) and ethene (ETH) within a hydraulic residence time of 1.3 days. The experimental breakthrough curves were described by the one-dimensional two-site-nonequilibrium transport model. PCE dechlorination was observed after bioaugmentation and after the lactate concentration was increased from 0.35 to 0.67 mM. At the onset of reductive dehalogenation, cis-dichloroethene (c-DCE) concentrations in the column effluent exceeded the influent PCE concentration indicating enhanced PCE desorption and transformation. When the lactate concentration was increased to 1.34 mM, c-DCE reduction to vinyl chloride (VC) and ethene (ETH) occurred. Spatial rates of PCE and VC transformation were determined in batch-incubated microcosms constructed with aquifer samples obtained from the column. PCE transformation rates were highest in the first 5 cm from the column inlet and decreased towards the column effluent. Dehalococcoides cell numbers dropped from ˜ 73.5% of the total Bacterial population in the original inocula, to about 0.5% to 4% throughout the column. The results were consistent with estimates of electron donor utilization, with 4% going towards dehalogenation reactions.

Magnetite nanoparticles enhance the performance of a combined bioelectrode-UASB reactor for reductive transformation of 2,4-dichloronitrobenzene.

Science.gov (United States)

Wang, Caiqin; Ye, Lu; Jin, Jie; Chen, Hui; Xu, Xiangyang; Zhu, Liang

2017-09-04

Direct interspecies electron transfer (DIET) among the cometabolism microbes plays a key role in the anaerobic degradation of persistent organic pollutants and stability of anaerobic bioreactor. In this study, the COD removal efficiency increased to 99.0% during the start-up stage in the combined bioelectrode-UASB system (R1) with magnetite nanoparticles addition, which was higher than those in the coupled bioelectrode-UASB (R2; 83.2%) and regular UASB (R3; 71.0%). During the stable stage, the increase of 2,4-dichloronitrobenzene (2,4-DClNB) concentration from 25 mg L -1 to 200 mg L -1 did not affect the COD removal efficiencies in R1 and R2, whereas the performance of R3 was deteriorated obviously. Further intermediates analysis indicated that magnetite nanoparticles enhanced the reductive dechlorination of 2,4-DClNB. High-throughput sequencing results showed that the functional microbes like Syntrophobacter and Syntrophomonas which have been reported to favor the DIET, were predominant on the cathode surface of R1 reactor. It is speculated that the addition of magnetite nanoparticles favors the cooperative metabolism of dechlorinating microbes and electricigens during 2,4-DClNB degradation process in the combined bioelectrode-UASB reactor. This study may provide a new strategy to improve the performance of microbial electrolysis cells and enhance the pollutant removal efficiency.

Changing redox potential by controlling soil moisture and addition of inorganic oxidants to dissipate pentachlorophenol in different soils

International Nuclear Information System (INIS)

Lin Jiajiang; He Yan; Xu Jianming

2012-01-01

The potential for dissipation of pentachlorophenol (PCP) was investigated in soils from four different sites in China. These were an umbraqualf (Soil 1), a Plinthudult (Soil 2), a Haplustalf (Soil 3) and an Argiustoll (Soil 4) which were either flooded, to produce anaerobic conditions, or incubated aerobically at 60% water-holding capacity (WHC). The dissipation of PCP in Soil 1 at 60% WHC was higher than under flooded condition, while the opposite occurred in the other three soils. Under flooded conditions, the redox potential decreased significantly in Soil 1 and Soil 4, where sulphate reduction was occurred and the dissipation of PCP was statistically significant (about 96% and 98%, respectively) at the end of incubation. After addition of inorganic oxidants, dissipation of PCP was significantly inhibited by FeCl 3 , while Na 2 SO 4 and NaNO 3 had different effects, depending upon the soil type. - Highlights: ► The extent of the aerobic/anaerobic interface depends upon the soil properties. ► The dissipation of PCP was accelerated in some soils due to the soil-water interface. ► The addition of oxidants inhibited the decrease in soil redox potential. ► Most external oxidants added under flooded condition inhibited PCP dechlorination. - The addition of inorganic oxidants limited the decrease in redox potential and inhibited the reductive dechlorination of pentachlorophenol.

Synthesis of poly(dimethylsilylene-co-diphenylsilylene) polymers as precursors for SiC ceramics

International Nuclear Information System (INIS)

Bushnell-Watson, S.M.; Emsley, R.J.P.; Morris, M.J.; Sharp, J.H.

1993-01-01

Silicon carbide ceramics, especially fibres, are being fabricated via polymeric precursors. Although such fibres are commercially available, there is a demand for improved performance particularly at elevated temperatures. A range of copolymers has been synthesized from the monomers, dimethyldichlorosilane and diphenyldichlorosilane, by a Wurtz reaction involving dechlorination using sodium metal in xylene. The products of reaction were characterised by a range of techniques, including gel permeation chromatography (GPC), infra-red spectroscopy (IR), X-ray powder diffraction (XRD) and thermogravimetry (TG). (orig.)

Dehalogenation of Chlorinated Hydroxybiphenyls by Fungal Laccase

Science.gov (United States)

Schultz, Asgard; Jonas, Ulrike; Hammer, Elke; Schauer, Frieder

2001-01-01

We have investigated the transformation of chlorinated hydroxybiphenyls by laccase produced by Pycnoporus cinnabarinus. The compounds used were transformed to sparingly water-soluble colored precipitates which were identified by gas chromatography-mass spectrometry as oligomerization products of the chlorinated hydroxybiphenyls. During oligomerization of 2-hydroxy-5-chlorobiphenyl and 3-chloro-4-hydroxybiphenyl, dechlorinated C—C-linked dimers were formed, demonstrating the dehalogenation ability of laccase. In addition to these nonhalogenated dimers, both monohalogenated and dihalogenated dimers were identified. PMID:11526052

Copper-mediated reductive dechlorination by green rust intercalated with dodecanoate

DEFF Research Database (Denmark)

Huang, Lizhi; Yin, Zhou; Cooper, Nicola G.A.

2018-01-01

A layered FeII-FeIII hydroxide (green rust, GR) was intercalated with dodecanoate (known as GRC12) and then amended with CuII (GRC12(Cu)) before reaction with chloroform (CF), carbon tetrachloride (CT), trichloroethylene (TCE) or tetrachloroethylene (PCE). Reduction of CT by GRC12(Cu) was 37 times...

Intrinsic dechlorination of 1,2-dichloroethane at an industrial site

NARCIS (Netherlands)

Bosma, T.N.P.; Aalst-van Leeuwen, M.A. van; Gerritse, J.; Heiningen, E. van; Taat, J.; Pruijn, M.

1998-01-01

Bioremediation strategies for an industrial site located in the Rotterdam Harbor Area, the Netherlands and contaminated with 1,2-dichloroethane (1,2-DCA), are under investigation. The contamination is present in a confined anaerobic aquifer. The objective of the research is to assess the potential

Enhanced reductive dechlorination in clay till contaminated with chlorinated solvents

DEFF Research Database (Denmark)

Damgaard, Ida

Chlorinated solvents are among the most frequently found contaminants in groundwater. In fractured media, chlorinated ethenes and ethanes are transported downwards through preferential pathways with subsequent diffusion into the sediment matrix. Due to slow back diffusion it can serve as a long...... (direct push delivery, Gl. Kongevej). Degradation of chlorinated ethenes (and ethanes) in the clay till matrix and in embedded high permeability features was investigated by high resolution sampling of intact cores combined with groundwater sampling. An integrated approach using chemical analysis...... (hydraulic fracturing with gravitational injection and direct push delivery) were therefore tested in clay till by injection of amendment-comparable tracers to investigate the possibility to overcome diffusion limitations in the low permeability matrix. The study of hydraulic fracturing demonstrated...

Dehalogenimonas lykanthroporepellens BL-DC-9T simultaneously transcribes many rdhA genes during organohalide respiration with 1,2-DCA, 1,2-DCP, and 1,2,3-TCP as electron acceptors.

Science.gov (United States)

Mukherjee, Kalpataru; Bowman, Kimberly S; Rainey, Fred A; Siddaramappa, Shivakumara; Challacombe, Jean F; Moe, William M

2014-05-01

The genome sequence of the organohalide-respiring bacterium Dehalogenimonas lykanthroporepellensBL-DC-9(T) contains numerous loci annotated as reductive dehalogenase homologous (rdh) genes based on inferred protein sequence identity with functional dehalogenases of other bacterial species. Many of these genes are truncated, lack adjacent regulatory elements, or lack cognate genes coding for membrane-anchoring proteins typical of the functionally characterized active reductive dehalogenases of organohalide-respiring bacteria. To investigate the expression patterns of the rdh genes in D. lykanthroporepellensBL-DC-9(T), oligonucleotide primers were designed to uniquely target 25 rdh genes present in the genome as well as four putative regulatory genes. RNA extracts from cultures of strain BL-DC-9(T) actively dechlorinating three different electron acceptors, 1,2-dichloroethane, 1,2-dichloropropane, and 1,2,3-trichloropropane were reverse-transcribed and subjected to PCR amplification using rdh-specific primers. Nineteen rdh gene transcripts, including 13 full-length rdhA genes, six truncated rdhA genes, and five rdhA genes having cognate rdhB genes were consistently detected during the dechlorination of all three of the polychlorinated alkanes tested. Transcripts from all four of the putative regulatory genes were also consistently detected. Results reported here expand the diversity of bacteria known to simultaneously transcribe multiple rdh genes and provide insights into the transcription factors associated with rdh gene expression. © 2014 Federation of European Microbiological Societies. Published by John Wiley & Sons Ltd. All rights reserved.

The use of mechanical alloying for the preparation of palladized magnesium bimetallic particles for the remediation of PCBs.

Science.gov (United States)

Coutts, Janelle L; Devor, Robert W; Aitken, Brian; Hampton, Michael D; Quinn, Jacqueline W; Clausen, Christian A; Geiger, Cherie L

2011-09-15

The kinetic rate of dechlorination of a polychlorinated biphenyl (PCB-151) by mechanically alloyed Mg/Pd was studied for optimization of the bimetallic system. Bimetal production was first carried out in a small-scale environment using a SPEX 8000M high-energy ball mill with 4-μm-magnesium and palladium impregnated on graphite, with optimized parameters including milling time and Pd-loading. A 5.57-g sample of bimetal containing 0.1257% Pd and ball milled for 3 min resulted in a degradation rate of 0.00176 min(-1)g(-1) catalyst as the most reactive bimetal. The process was then scaled-up, using a Red Devil 5400 Twin-Arm Paint Shaker, fitted with custom plates to hold milling canisters. Optimization parameters tested included milling time, number of ball bearings used, Pd-loading, and total bimetal mass milled. An 85-g sample of bimetal containing 0.1059% Pd and ball-milled for 23 min with 16 ball bearings yielded the most reactive bimetal with a degradation rate of 0.00122 min(-1)g(-1) catalyst. Further testing showed adsorption did not hinder extraction efficiency and that dechlorination products were only seen when using the bimetallic system, as opposed to any of its single components. The bimetallic system was also tested for its ability to degrade a second PCB congener, PCB-45, and a PCB mixture (Arochlor 1254); both contaminants were seen to degrade successfully. Copyright © 2011 Elsevier B.V. All rights reserved.

Irradiation as an alternative for disinfection of domestic waste in the Canadian Arctic

International Nuclear Information System (INIS)

1981-01-01

This study evaluated the technical and economic feasibility of various methods for disinfecting wastewater in the Canadian Arctic with specific reference to gamma radiation. More conventional disinfection practices, such as chlorination, chlorination-dechlorination, and ozonation were compared to gamma radiation along with ultraviolet irradiation and lime disinfection. The quality of lagoon effluent, highly diluted (weak) sewage, holding tank wastes and honey-bag wastes, which are the typical waste types found in northern communities, was established from data available in the literature. Further literature reviews were undertaken to establish a data base for design and effectiveness of disinfection systems operated in cold climates. Capital and operating costs for all technically feasible disinfection process alternates were estimated based on historical cost data adjusted to 1977 for the construction and instalation of similar systems in the north. The costs of equipment, chemicals, fuel and electrical power were obtained from suppliers. The environmental impact of each of the disinfection processes was reviewed with emphasis on gamma irradiation. Safety and health aspects were also considered. The study concluded that gamma irradiation was capable of providing safe, reliable disinfection for concentrated honey-bag and holding wastes. Pilot-scale testing was recommended prior to construction of full-scale disinfection facilities. For lagoon effluents and weak sewage, gamma irradiation was not cost competitive with other alternates; rather chlorination-dechlorination was found to be the most cost-effective and environmentally acceptable alternative

A CuNi bimetallic cathode with nanostructured copper array for enhanced hydrodechlorination of trichloroethylene (TCE).

Science.gov (United States)

Liu, Bo; Zhang, Hao; Lu, Qi; Li, Guanghe; Zhang, Fang

2018-09-01

To address the challenges of low hydrodechlorination efficiency by non-noble metals, a CuNi bimetallic cathode with nanostructured copper array film was fabricated for effective electrochemical dechlorination of trichloroethylene (TCE) in aqueous solution. The CuNi bimetallic cathodes were prepared by a simple one-step electrodeposition of copper onto the Ni foam substrate, with various electrodeposition time of 5/10/15/20 min. The optimum electrodeposition time was 10 min when copper was coated as a uniform nanosheet array on the nickel foam substrate surface. This cathode exhibited the highest TCE removal, which was twice higher compared to that of the nickel foam cathode. At the same passed charge of 1080C, TCE removal increased from 33.9 ± 3.3% to 99.7 ± 0.1% with the increasing operation current from 5 to 20 mA cm -2 , while the normalized energy consumption decreased from 15.1 ± 1.0 to 2.6 ± 0.01 kWh log -1  m -3 . The decreased normalized energy consumption at a higher current density was due to the much higher removal efficiency at a higher current. These results suggest that CuNi cathodes prepared by simple electrodeposition method represent a promising and cost-effective approach for enhanced electrochemical dechlorination. Copyright © 2018 Elsevier B.V. All rights reserved.

Tribology of carbide derived carbon films synthesized on tungsten carbide

Science.gov (United States)

Tlustochowicz, Marcin

Tribologically advantageous films of carbide derived carbon (CDC) have been successfully synthesized on binderless tungsten carbide manufactured using the plasma pressure compaction (P2CRTM) technology. In order to produce the CDC films, tungsten carbide samples were reacted with chlorine containing gas mixtures at temperatures ranging from 800°C to 1000°C in a sealed tube furnace. Some of the treated samples were later dechlorinated by an 800°C hydrogenation treatment. Detailed mechanical and structural characterizations of the CDC films and sliding contact surfaces were done using a series of analytical techniques and their results were correlated with the friction and wear behavior of the CDC films in various tribosystems, including CDC-steel, CDC-WC, CDC-Si3N4 and CDC-CDC. Optimum synthesis and treatment conditions were determined for use in two specific environments: moderately humid air and dry nitrogen. It was found that CDC films first synthesized at 1000°C and then hydrogen post-treated at 800°C performed best in air with friction coefficient values as low as 0.11. However, for dry nitrogen applications, no dechlorination was necessary and both hydrogenated and as-synthesized CDC films exhibited friction coefficients of approximately 0.03. A model of tribological behavior of CDC has been proposed that takes into consideration the tribo-oxidation of counterface material, the capillary forces from adsorbed water vapor, the carbon-based tribofilm formation, and the lubrication effect of both chlorine and hydrogen.

Microbial reductive dehalogenation of trihalomethanes by a Dehalobacter-containing co-culture.

Science.gov (United States)

Zhao, Siyan; Rogers, Matthew J; He, Jianzhong

2017-07-01

Trihalomethanes such as chloroform and bromoform, although well-known as a prominent class of disinfection by-products, are ubiquitously distributed in the environment due to widespread industrial usage in the past decades. Chloroform and bromoform are particularly concerning, of high concentrations detected and with long half-lives up to several hundred days in soils and groundwater. In this study, we report a Dehalobacter- and Desulfovibrio-containing co-culture that exhibits dehalogenation of chloroform (~0.61 mM) to dichloromethane and bromoform (~0.67 mM) to dibromomethane within 10-15 days. This co-culture was further found to dechlorinate 1,1,1-trichloroethane (1,1,1-TCA) (~0.65 mM) to 1,1-dichloroethane within 12 days. The Dehalobacter species present in this co-culture, designated Dehalobacter sp. THM1, was found to couple growth with dehalogenation of chloroform, bromoform, and 1,1,1-TCA. Strain THM1 harbors a newly identified reductive dehalogenase (RDase), ThmA, which catalyzes chloroform, bromoform, and 1,1,1-TCA dehalogenation. Additionally, based on the sequences of thmA and other identified chloroform RDase genes, ctrA, cfrA, and tmrA, a pair of chloroform RDase gene-specific primers were designed and successfully applied to investigate the chloroform dechlorinating potential of microbial communities. The comparative analysis of chloroform RDases with tetrachloroethene RDases suggests a possible approach in predicting the substrate specificity of uncharacterized RDases in the future.

Nanoscale zerovalent iron alters soil bacterial community structure and inhibits chloroaromatic biodegradation potential in Aroclor 1242-contaminated soil

International Nuclear Information System (INIS)

Tilston, Emma L.; Collins, Chris D.; Mitchell, Geoffrey R.; Princivalle, Jessica; Shaw, Liz J.

2013-01-01

Nanoscale zerovalent iron (nZVI) has potential for the remediation of organochlorine-contaminated environments. Environmental safety concerns associated with in situ deployment of nZVI include potential negative impacts on indigenous microbes whose biodegradative functions could contribute to contaminant remediation. With respect to a two-step polychlorinated biphenyl remediation scenario comprising nZVI dechlorination followed by aerobic biodegradation, we examined the effect of polyacrylic acid (PAA)-coated nZVI (mean diameter = 12.5 nm) applied at 10 g nZVI kg −1 to Aroclor-1242 contaminated and uncontaminated soil over 28 days. nZVI had a limited effect on Aroclor congener profiles, but, either directly or indirectly via changes to soil physico-chemical conditions (pH, Eh), nZVI addition caused perturbation to soil bacterial community composition, and reduced the activity of chloroaromatic mineralizing microorganisms. We conclude that nZVI addition has the potential to inhibit microbial functions that could be important for PCB remediation strategies combining nZVI treatment and biodegradation. Highlights: ► Impact of nano-sized zerovalent iron on microbes was investigated in soil microcosms. ► Zerovalent iron had short-lived effects on redox potential and Aroclor dechlorination. ► Microbial populations also showed short-lived perturbations in their size. ► The activity of chloroaromatic degrading microbes did not recover within 28 days. ► Zerovalent iron application inhibits ensuing PCB bioremediative microbial functions. - nZVI inhibits microbial functions of potential importance for remediation strategies combining nZVI treatment and biodegradation.

Determinação de ascarel em óleo isolante de transformadores Ascarel determination in insulating oil of transformers

Directory of Open Access Journals (Sweden)

Izoldir Antonello

2007-06-01

Full Text Available The contamination level of silicon oil used as insulation liquid in high-voltage transformers by ascarel (PCBs is above those permitted by the Brazilian law. Thus new techniques able to detect ascarel, with low operational costs, are very attractive. The present work proposes an analysis of the contamination levels of silicon oil using the following techniques: naphthalene anion radical reaction for ascarel dechlorination; and potentiometry with an ion-selective electrode for chloride ion determination. The data obtained with the proposed methodology agree well with those from the official methodology, (method IEC 61619.

Development and Optimization of Targeted Nanoscale Iron Delivery Methods for Treatment of NAPL Source Zones

Science.gov (United States)

2011-04-01

k3 ), kobs is the modeled reaction rate constant with headspace, KH is the dimensionless Henry’s law constant for the reactant (here, the value of...2 Lhr-1g-1, and k3 = 1.9 × 10-2 Lhr-1g-1. Expressed as surface area normalized rate coefficients the values of k1, k2 and k3 are 1.1 × 10-4 Lhr-1m-2...tetrachloroethylene-reductive dechlorination catalyzed by vitamin B. Environmental Toxicology and Chemistry, 17(9), 1681-1688. Chiao, F.F., Currie, R.C

Compound-Specific Isotope Analyses to Assess TCE Biodegradation in a Fractured Dolomitic Aquifer.

Science.gov (United States)

Clark, Justin A; Stotler, Randy L; Frape, Shaun K; Illman, Walter A

2017-01-01

The potential for trichloroethene (TCE) biodegradation in a fractured dolomite aquifer at a former chemical disposal site in Smithville, Ontario, Canada, is assessed using chemical analysis and TCE and cis-DCE compound-specific isotope analysis of carbon and chlorine collected over a 16-month period. Groundwater redox conditions change from suboxic to much more reducing environments within and around the plume, indicating that oxidation of organic contaminants and degradation products is occurring at the study site. TCE and cis-DCE were observed in 13 of 14 wells sampled. VC, ethene, and/or ethane were also observed in ten wells, indicating that partial/full dechlorination has occurred. Chlorine isotopic values (δ 37 Cl) range between 1.39 to 4.69‰ SMOC for TCE, and 3.57 to 13.86‰ SMOC for cis-DCE. Carbon isotopic values range between -28.9 and -20.7‰ VPDB for TCE, and -26.5 and -11.8‰ VPDB for cis-DCE. In most wells, isotopic values remained steady over the 15-month study. Isotopic enrichment from TCE to cis-DCE varied between 0 and 13‰ for carbon and 1 and 4‰ for chlorine. Calculated chlorine-carbon isotopic enrichment ratios (ϵ Cl /ϵ C ) were 0.18 for TCE and 0.69 for cis-DCE. Combined, isotopic and chemical data indicate very little dechlorination is occurring near the source zone, but suggest bacterially mediated degradation is occurring closer to the edges of the plume. © 2016, National Ground Water Association.

Degradation of Trichloroethene with a Novel Ball Milled Fe–C Nanocomposite

Energy Technology Data Exchange (ETDEWEB)

Gao, Jie; Wang, Wei [Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Rondinone, Adam J. [Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); He, Feng, E-mail: fenghe@zjut.edu.cn [College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou, Zhejiang 310032 (China); Liang, Liyuan [Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States)

2015-12-30

Highlights: • Novel, inexpensive iron–carbon (Fe–C) nanocomposite was obtained by milling. • Fe–C instantaneously sorbed >90% of trichloroethene and continuously degraded them. • The carbon reduced the generation of C{sub 3}−C{sub 6} intermediates and mainly produced C{sub 2}H{sub 4}. • Fe–C can attach to the DNAPL phase thus enhancing degradation efficiency. - Abstract: Nanoscale zero-valent iron (NZVI) is effective in reductively degrading dense non-aqueous phase liquids (DNAPLs), such as trichloroethene (TCE), in groundwater (i.e., dechlorination) although the NZVI technology itself still suffers from high material costs and inability to target hydrophobic contaminants in source zones. To address these problems, we developed a novel, inexpensive iron–carbon (Fe–C) nanocomposite material by simultaneously milling micron-size iron and activated carbon powder. Microscopic and X-ray diffraction (XRD) characterization of the composite material revealed that nanoparticles of Fe were dispersed in activated carbon and a new iron carbide phase was formed. Bench-scale studies showed that this material instantaneously sorbed >90% of TCE from aqueous solutions and subsequently decomposed TCE into non-chlorinated products. Compared to milled Fe, Fe–C nanocomposite dechlorinated TCE at a slightly slower rate and favored the production of ethene over other TCE degradation products such as C{sub 3}−C{sub 6} compounds. When placed in hexane-water mixture, the Fe–C nanocomposite materials are preferentially partitioned into the organic phase, indicating the ability of the composite materials to target DNAPL during remediation.

Isotope fractionation associated with the direct photolysis of 4-chloroaniline.

Science.gov (United States)

Ratti, Marco; Canonica, Silvio; McNeill, Kristopher; Erickson, Paul R; Bolotin, Jakov; Hofstetter, Thomas B

2015-04-07

Compound-specific isotope analysis is a useful approach to track transformations of many organic soil and water pollutants. Applications of CSIA to characterize photochemical processes, however, have hardly been explored. In this work, we systematically studied C and N isotope fractionation associated with the direct photolysis of 4-Cl-aniline used as a model compound for organic micropollutants that are known to degrade via photochemical processes. Laboratory experiments were carried out at an irradiation wavelength of 254 nm over the pH range 2.0 to 9.0 as well as in the presence of Cs(+) as a quencher of excited singlet 4-Cl-aniline at pH 7.0 and 9.0. We observed considerable variation of C and N isotope enrichment factors, ϵC and ϵN, between -1.2 ± 0.2‰ to -2.7 ± 0.2‰ for C and -0.6 ± 0.2‰ to -9.1 ± 1.6‰ for N, respectively, which could not be explained by the speciation of 4-Cl-aniline alone. In the presence of 1 M Cs(+), we found a marked increase of apparent (13)C-kinetic isotope effects ((13)C-AKIE) and decrease of 4-Cl-aniline fluorescence lifetimes. Our data suggest that variations of C and N isotope fractionation originate from heterolytic dechlorination of excited triplet and singlet states of 4-Cl-aniline. Linear correlations of (13)C-AKIE vs (15)N-AKIE were distinctly different for these two reaction pathways and may be explored further for the identification of photolytic aromatic dechlorination reactions.

Dechlorane Plus (DP) in air and plants at an electronic waste (e-waste) site in South China

Energy Technology Data Exchange (ETDEWEB)

Chen Shejun [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Tian Mi; Wang Jing; Shi Tian [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Graduate School, Chinese Academy of Sciences, Beijing 100049 (China); Luo Yong [Guangdong Forestry Survey and Planning Institute, Guangzhou 510520 (China); Luo Xiaojun [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Mai Bixian, E-mail: nancymai@gig.ac.cn [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China)

2011-05-15

Air and foliage samples (Eucalyptus spp. and Pinus massoniana Lamb.) were collected from e-waste and reference sites in South China and analyzed for Dechlorane Plus (DP) and two dechlorinated DPs. DP concentrations in the air were 13.1-1794 pg/m{sup 3} for the e-waste site and 0.47-35.7 pg/m{sup 3} for the reference site, suggesting the recycling of e-waste is an important source of DP to the environment. Plant DP, with concentrations of 0.45-51.9 ng/g dry weight at the e-waste site and 0.09-2.46 ng/g at the reference site, exhibited temporal patterns similar to the air DP except for pine needle at the reference site. The air-plant exchange of DP could be described with the two-compartment model. Anti-Cl{sub 11} DP was measured in most air and plant samples from the e-waste site. The ratios of anti-Cl{sub 11} DP to anti-DP in the air and plants may indicate the preferential uptake of dechlorinated DP by plant compared with DP. - Highlights: > Dechlorane Plus was widely present in the air and plants in South China. > Temporal patterns of the plant DP could be described with the two-compartment model. > Plant uptake can efficiently reduce air DP concentration at the reference site. > Anti-Cl{sub 11} DP was measured in most air and plant samples from the e-waste site. - E-waste recycling in South China results in wide occurrence of DP in the air and plant.

Single turnover studies of oxidative halophenol dehalogenation by horseradish peroxidase reveal a mechanism involving two consecutive one electron steps: toward a functional halophenol bioremediation catalyst.

Science.gov (United States)

Sumithran, Suganya; Sono, Masanori; Raner, Gregory M; Dawson, John H

2012-12-01

Horseradish peroxidase (HRP) catalyzes the oxidative para-dechlorination of the environmental pollutant/carcinogen 2,4,6-trichlorophenol (2,4,6-TCP). A possible mechanism for this reaction is a direct oxygen atom transfer from HRP compound I (HRP I) to trichlorophenol to generate 2,6-dichloro 1,4-benzoquinone, a two-electron transfer process. An alternative mechanism involves two consecutive one-electron transfer steps in which HRP I is reduced to compound II (HRP II) and then to the ferric enzyme as first proposed by Wiese et al. [F.W. Wiese, H.C. Chang, R.V. Lloyd, J.P. Freeman, V.M. Samokyszyn, Arch. Environ. Contam. Toxicol. 34 (1998) 217-222]. To probe the mechanism of oxidative halophenol dehalogenation, the reactions between 2,4,6-TCP and HRP compounds I or II have been investigated under single turnover conditions (i.e., without excess H(2)O(2)) using rapid scan stopped-flow spectroscopy. Addition of 2,4,6-TCP to HRP I leads rapidly to HRP II and then more slowly to the ferric resting state, consistent with a mechanism involving two consecutive one-electron oxidations of the substrate via a phenoxy radical intermediate. HRP II can also directly dechlorinate 2,4,6-TCP as judged by rapid scan stopped-flow and mass spectrometry. This observation is particularly significant since HRP II can only carry out one-electron oxidations. A more detailed understanding of the mechanism of oxidative halophenol dehalogenation will facilitate the use of HRP as a halophenol bioremediation catalyst. Copyright © 2012 Elsevier Inc. All rights reserved.

Compendium of Technical Papers on the Reductive Dechlorination of Chlorinated Solvents.

Science.gov (United States)

1997-08-01

30), was added to cultures atarate of 20 pL (for in Thauer et al. (22) with temperature = 25 °C; pH = 7; HC0 3- = 70 supplement (E0),twas)added0to...34Biotransformation of chlorinated organic solvents in static niicrocosrrs." Environmental Toxicology and Chemistry 4: 739-742. Tandoi, V., T D. DiStefano, R A

Dechlorination Ability of Municipal Waste Incineration Fly Ash for Polychlorinated Phenols

Czech Academy of Sciences Publication Activity Database

Vlková, Leona; Pekárek, Vladimír; Pacáková, V.; Karban, Jindřich; Bureš, M.; Štulík, K.

2004-01-01

Roč. 56, č. 10 (2004), s. 935-942 ISSN 0045-6535 R&D Projects: GA AV ČR IAA4072206; GA MŠk 1P04OE156 Institutional research plan: CEZ:AV0Z4072921 Keywords : chlorophenols * de novo synthesis * fly ash Subject RIV: CC - Organic Chemistry Impact factor: 2.359, year: 2004

Biodegradation of Trichloroethylene by an Endophyte of Hybrid Poplar

Science.gov (United States)

Kang, Jun Won; Khan, Zareen

2012-01-01

We isolated and characterized a novel endophyte from hybrid poplar. This unique endophyte, identified as Enterobacter sp. strain PDN3, showed high tolerance to trichloroethylene (TCE). Without the addition of inducers, such as toluene or phenol, PDN3 rapidly reduced TCE levels in medium from 72.4 μM to 30.1 μM in 24 h with a concurrent release of 127 μM chloride ion, and nearly 80% of TCE (55.3 μM) was dechlorinated by PDN3 in 5 days with 166 μM chloride ion production, suggesting TCE degradation. PMID:22367087

Purification and characterization of the 3-chloro-4-hydroxy-phenylacetate reductive dehalogenase of Desulfitobacterium hafniense

DEFF Research Database (Denmark)

Christensen, Nina; Ahring, Birgitte Kiær; Wohlfarth, Gert

1998-01-01

The membrane-bound 3-chloro-4-hydroxyphenylacetate (Cl-OHPA) reductive dehalogenase from the chlorophenol- educing anaerobe Desulfitobacterium hafniense was purified 11.3-fold to apparent homogeneity in the presence of the detergent CHAPS. The purified dehalogenase catalyzed the reductive...... dechlorination of Cl-OHPA to 4-hydroxyphenylacetate with reduced methyl viologen as the electron donor at a specific activity of 103.2 nkat/mg protein. SDS-PAGErevealed a single protein band with an apparent molecular mass of 46.5 kDa. The enzyme contained 0.68±0.2 mol corrinoid, 12.0±0.7 mol iron, and 13...

Destruction of TCE Using Oxidative and Reductive Pathways as Potential In-Situ Treatments for the Contaminated Paducah Groundwater

Energy Technology Data Exchange (ETDEWEB)

Lewis, S; Li, Y; Xu, J; Tee, Y; Lynch, Andrew

2007-05-01

When considering reductive technologies for ground water remediation, it is important to understand the underlying principles that govern kinetics of zero-valent metal dechlorination. Studies involving the use of nanoscale metals (characteristic length <100nm) for chloro-organic degradation have increased reaction rates by 1-2 orders of magnitude with minimal intermediate formation. Typically, these metals are synthesized using modifications of the aqueous phase reduction of metal ions using sodium borohydride presented by Glavee and coworkers. The use of a bimetallic system increases the reactivity of the particle surface by incorporating a second metal that can typically act as a hydrogenation promotor.

Catalytic Hydrodechlorination of Trichlorobenzenes with Pd(PhenCl2 as Catalyst Precursor

Directory of Open Access Journals (Sweden)

Guanlin Zhang

2015-01-01

Full Text Available We reported the catalytic hydrodechlorination (HDC of trichlorobenzenes by an organometallic compound Pd(PhenCl2 as a catalyst precursor. The catalyst precursor was prepared by chemical coordination reaction and characterized by FTIR and 1H NMR techniques. The HDC performance of Pd(PhenCl2 as catalyst precursor was evaluated on 1,2,3-, 1,2,4-, and 1,3,5-trichlorobenzenes (TCBs. All TCBs could be converted to dechlorination products with high conversion. Products distribution was closely related with the substrate structures and C-Cl bond energies. A reasonable reaction mechanism was also proposed.

Global Transcriptomic and Proteomic Responses of Dehalococcoides ethenogenes Strain 195 to Fixed Nitrogen Limitation

Energy Technology Data Exchange (ETDEWEB)

Lee, Patrick K. H. [University of California, Berkeley; Dill, Brian [ORNL; Louie, Tiffany S. [University of California, Berkeley; Shah, Manesh B [ORNL; Verberkmoes, Nathan C [ORNL; Andersen, Gary L. [Lawrence Berkeley National Laboratory (LBNL); Zinder, Stephen H. [Cornell University; Alvarez-Cohen, Lisa [Lawrence Berkeley National Laboratory (LBNL)

2012-01-01

Bacteria of the genus Dehalococcoides play an important role in the reductive dechlorination of chlorinated ethenes. A systems level approach was taken in this study to examine the global transcriptomic and proteomic responses of exponentially growing D. ethenogenes strain 195 to fixed nitrogen limitation (FNL) as dechlorination activity and cell yield both decrease during FNL. As expected, the nitrogen-fixing (nif) genes were differentially up-regulated in the transcriptome and proteome of strain 195 during FNL. Aside from the nif operon, a putative methylglyoxal synthase-encoding gene (DET1576), the product of which is predicted to catalyze the formation of the toxic electrophile methylglyoxal and implicated in the uncoupling of anabolism from catabolism in bacteria, was strongly up-regulated in the transcriptome and could potentially play a role in the observed growth inhibition during FNL. Carbon catabolism genes were generally down regulated in response to FNL and a number of transporters were differentially regulated in response to nitrogen limitation, with some playing apparent roles in nitrogen acquisition while others were associated with general stress responses. A number of genes related to the functions of nucleotide synthesis, replication, transcription, translation, and post-translational modifications were also differentially expressed. One gene coding for a putative reductive dehalogenase (DET1545) and a number coding for oxidoreductases, which have implications in energy generation and redox reactions, were also differentially regulated. Interestingly, most of the genes within the multiple integrated elements were not differentially expressed. Overall, this study elucidates the molecular responses of strain 195 to FNL and identifies differentially expressed genes that are potential biomarkers to evaluate environmental cellular nitrogen status.

Electroremediation of PCB contaminated soil combined with iron nanoparticles: Effect of the soil type.

Science.gov (United States)

Gomes, Helena I; Dias-Ferreira, Celia; Ottosen, Lisbeth M; Ribeiro, Alexandra B

2015-07-01

Polychlorinated biphenyls (PCB) are carcinogenic and persistent organic pollutants that accumulate in soils and sediments. Currently, there is no cost-effective and sustainable remediation technology for these contaminants. In this work, a new combination of electrodialytic remediation and zero valent iron particles in a two-compartment cell is tested and compared to a more conventional combination of electrokinetic remediation and nZVI in a three-compartment cell. In the new two-compartment cell, the soil is suspended and stirred simultaneously with the addition of zero valent iron nanoparticles. Remediation experiments are made with two different historically PCB contaminated soils, which differ in both soil composition and contamination source. Soil 1 is a mix of soils with spills of transformer oils, while Soil 2 is a superficial soil from a decommissioned school where PCB were used as windows sealants. Saponin, a natural surfactant, was also tested to increase the PCB desorption from soils and enhance dechlorination. Remediation of Soil 1 (with highest pH, carbonate content, organic matter and PCB concentrations) obtained the maximum 83% and 60% PCB removal with the two-compartment and the three-compartment cell, respectively. The highest removal with Soil 2 were 58% and 45%, in the two-compartment and the three-compartment cell, respectively, in the experiments without direct current. The pH of the soil suspension in the two-compartment treatment appears to be a determining factor for the PCB dechlorination, and this cell allowed a uniform distribution of the nanoparticles in the soil, while there was iron accumulation in the injection reservoir in the three-compartment cell. Copyright © 2015 Elsevier Ltd. All rights reserved.

Development of an integrated, in-situ remediation technology. Draft topical report for task No. 9. Part II. Entitled: TCE degradation using non-biological methods, September 26, 1994--May 25, 1996

Energy Technology Data Exchange (ETDEWEB)

Orth, R.G.; McKenzie, D.E.

1997-04-01

Contamination in low permeability soils poses a significant technical challenge to in-situ remediation efforts. Poor accessibility to the contaminants and difficulty in delivery of treatment reagents have rendered existing in-situ treatments such as bioremediation, vapor extraction, pump and treat rather ineffective when applied to low permeability soils present at many contaminated sites. The technology is an integrated in-situ treatment in which established geotechnical methods are used to install degradation zones directly in the contaminated soil and electro-osmosis is utilized to move the contaminants back and forth through those zones until the treatment is completed. The use of zero valence iron for reductive dechlorination of aliphatic chlorinated hydrocarbons is currently under investigation by a number of research groups as a potential method of in-situ treatment of contaminated ground water. The reaction appears to involve the transfer of electrons to chloro-aliphatic compounds by the oxidation of zero valence iron to ferrous iron (Fe{sup +2}). Our studies have indicated that this reaction is consistent with those of corrosion, and as such, can be influenced or increased by the presence of small amounts of metals (5% by weight) such as copper, tin, silver, gold and palladium coated on the iron surface. Incomplete coverage of the iron surface with a more electropositive metal results in an open galvanic cell, which increases the oxidation of iron and facilitates and increases the concurrent reduction of trichloroethylene and other chlorinated aliphatic compounds to the corresponding alkenes and alkanes. Our results show that plating more electropositive metals onto certain iron surfaces results in approximately a factor of ten increase in the dechlorination rate of small organochlorine compounds such as TCE.

Chelate-Modified Fenton Reaction for the Degradation of Trichloroethylene in Aqueous and Two-Phase Systems

Energy Technology Data Exchange (ETDEWEB)

Lewis, Scott [Univ of KY, dept of chemical and materials engineering; lynch, Andrew [Univ of KY, dept of chemical and materials engineering; Bachas, Leonidas [Univ of KY, Dept of Chemistry; hampson, Steve [Univ of KY Center for Applied Energy Research - KY Research Consortium of Energy and Environment; Ormsbee, Lindelle [Univ of KY Center for Applied Energy Research - KY Research Consortium of Energy and Environment; Bhattacharyya, Dibakar [Univ of KY, dept of chemical and materials engineering

2008-06-01

The Standard Fenton reaction has been used for In-Situ Chemical Oxidation (ISCO) of toxic organics in groundwater. However, it requires low pH operating conditions, and thus has limitations for in situ applications. In addition, hydroxyl radicals are rapidly consumed by hydroxyl scavengers found in the subsurface. These problems are alleviated through the chelate-modified Fenton (hydroxyl radical) reaction, which includes the addition of nontoxic chelate (L) such as citrate or gluconic acid. This chelate allows the reaction to take place at bear neutral pH and control hydrogen peroxide consumption by binding to Fe(II), forming an FeL complex. The chelate also binds to Fe(III), preventing its precipitation as ferric hydroxide and thus prevents problems associated with injection well plugging. The rate of TCE dechlorination in chelate-modified Fenton systems is a function of pH, H2O2 concentration, and FE:L ratio. The primary objective of this research is to model and apply this process to the destruction of trichloroethylene (TCE) present in both the aqueous and organic (in the form of droplets) phases. Experimentation proved the chelate-modified Fenton reaction effectively dechlorinates TCE in both the aqueous and organic phases at near-neutral pH. Other focuses of this work include determining the effect of [L]:[Fe] ratios on H2O2 and TCE degradation as well as reusability of the FE citrate solution under repeated H2O2 injections. Generalized models were developed to predict the concentration of TCE in the aqueous phase and TCE droplet radius as a function of time using established hydroxyl radial kinetics and mass transfer relationships.

Development of an integrated, in-situ remediation technology. Draft topical report for task No. 9. Part II. Entitled: TCE degradation using non-biological methods, September 26, 1994--May 25, 1996

International Nuclear Information System (INIS)

Orth, R.G.; McKenzie, D.E.

1997-01-01

Contamination in low permeability soils poses a significant technical challenge to in-situ remediation efforts. Poor accessibility to the contaminants and difficulty in delivery of treatment reagents have rendered existing in-situ treatments such as bioremediation, vapor extraction, pump and treat rather ineffective when applied to low permeability soils present at many contaminated sites. The technology is an integrated in-situ treatment in which established geotechnical methods are used to install degradation zones directly in the contaminated soil and electro-osmosis is utilized to move the contaminants back and forth through those zones until the treatment is completed. The use of zero valence iron for reductive dechlorination of aliphatic chlorinated hydrocarbons is currently under investigation by a number of research groups as a potential method of in-situ treatment of contaminated ground water. The reaction appears to involve the transfer of electrons to chloro-aliphatic compounds by the oxidation of zero valence iron to ferrous iron (Fe +2 ). Our studies have indicated that this reaction is consistent with those of corrosion, and as such, can be influenced or increased by the presence of small amounts of metals (5% by weight) such as copper, tin, silver, gold and palladium coated on the iron surface. Incomplete coverage of the iron surface with a more electropositive metal results in an open galvanic cell, which increases the oxidation of iron and facilitates and increases the concurrent reduction of trichloroethylene and other chlorinated aliphatic compounds to the corresponding alkenes and alkanes. Our results show that plating more electropositive metals onto certain iron surfaces results in approximately a factor of ten increase in the dechlorination rate of small organochlorine compounds such as TCE

Complete Detoxification of Short Chain Chlorinated Aliphatic Compounds: Isolation of Halorespiring Organisms and Biochemical Studies of the Dehalogenating Enzyme Systems - Final Report; FINAL

International Nuclear Information System (INIS)

Tiedje, J.M.

1999-01-01

Work focused on the isolation and characterization of halorespiring populations, and the initial investigation of the dechlorinating enzyme systems. In addition, tools to evaluate the presence/activity to halorespiring populations in the environment were developed. The tools developed in this work (measurements of hydrogen consumption thresholds, molecular probes) are relevant for regulatory agencies in order to facilitate decisions on which bioremediation technology (biostimulation or bioaugmentation) is most promising at a particular site. In addition, a better understanding of the physiology of the halorespiring organisms as well as the biochemistry of the dehalogenating enzyme systems enhances our knowledge of how these organisms can successfully be employed in the bioremediation of contaminated sites

Electrodialytic remediation of polychlorinated biphenyls contaminated soil with iron nanoparticles and two different surfactants

DEFF Research Database (Denmark)

Gomes, Helena I.; Dias-Ferreira, Celia; Ottosen, Lisbeth M.

2014-01-01

Polychlorinated biphenyls (PCB) are persistent organic pollutants (POP) that strongly adsorb in soils and sediments. There is a need to develop new and cost-effective solutions for the remediation of PCB contaminated soils. The suspended electrodialytic remediation combined with zero valent iron......ZVI showed encouraging tendencies and a base is thus formed for further optimization towards a new method for remediation of PCB polluted soils....... nanoparticles (nZVI) could be a competitive alternative to the commonly adapted solutions of incineration or landfilling. Surfactants can enhance the PCB desorption, dechlorination, and the contaminated soil cleanup. In this work, two different surfactants (saponin and Tween 80) were tested to enhance PCB...

The potential for reductive dechlorination after thermal treatment of TCE-contaminated aquifers

DEFF Research Database (Denmark)

Friis, Anne Kirketerp

Klorerede opløsningsmidler som fx triklorethen (TCE) er en alvorlig kilde til jord- og grundvandsforurening. Der er kun ganske få afværgeteknikker, der er effektive i området tæt på kilden til forureningen, og en af de mest anvendelige er termisk oprensning, hvor undergrunden opvarmes, så...... elektrisk opvarmning (ERH) i felten, var der bakterier som overlevede i eller blev transporteret til det opvarmede område med grundvandet. Disse bakterier kunne delvist nedbryde TCE (til cDCE) og bibeholdt redoxforhold efter opvarmningen, der kun var lidt mindre favorable for dechlorering i forhold til...... bioaugmenteret ved tilførsel af organisk stof og en mikrobiel blandingskultur med deklorerende bakterier. Bioaugmentationen førte til deklorering af TCE til ethen både i laboratorieopvarmede samt in-situ-opvarmede sedimenter. Dette faktum har påvist et potentiale og behov for bioaugmentation efter ERH...

Particle Surface Hydrophobicity and the Dechlorination of Chloro-Compounds by Iron Sulfides

Energy Technology Data Exchange (ETDEWEB)

Park, Sang-Won, E-mail: spark3@uncc.edu; Kim, Sung-Kuk; Kim, Jeong-Bae; Choi, Sung-Woo [Keimyung University, Department of Environmental Science and Engineering (Korea, Republic of); Inyang, Hilary I. [University of North Carolina at Charlotte, Global Institute for Energy and Environmental Systems (United States); Tokunaga, Shuzo [National Institute of Advanced Industrial Science and Technology (Japan)

2006-02-15

Halogenated aliphatic compounds (HACs) can be reduced by iron sulfides in aqueous systems. Generally, the thermodynamics and kinetics of dehalogenation reactions are controlled by the mineralogical and particle surface characteristics of the iron sulfide, the composition of the HAC and reaction conditions such as component concentrations, pH and Eh. In this theoretical and experimental investigation of CCl{sub 4} and C{sub 2}Cl{sub 6} reduction by FeS and FeS{sub 2}, the roles of hydrophobic and hydrophilic sites on the iron sulfides were analyzed. Experimental data obtained through zeta potential measurements, were used along with the Gouy-Chapman model and the simple two-layer surface complexation model to relate iron sulfide surface hydroxyl densities to the degree of HAC dehalogenation. The surface hydroxyl site densities of FeS and FeS{sub 2} were found to be 0.11 sites/nm{sup 2} and 0.21 sites/nm{sup 2}, respectively. During the dehalogenation reaction process, CCl{sub 4} was found to decrease to its first intermediate product CHCl{sub 3} within the first 20 hours followed by a slower process of conversion to CH{sub 2}Cl{sub 2}. The results also show that FeS is less hydrated (more hydrophobic) than FeS{sub 2}. For CCl{sub 4} and C{sub 2}Cl{sub 6}, FeS is a better dehalogenator than FeS{sub 2}. These results imply that particle surface hydrophobicity is a critical factor in surface-mediated dehalogenation of chlorinated compounds.

Organometallic copper I, II or III species in an intramolecular dechlorination reaction

KAUST Repository

Poater, Albert; Cavallo, Luigi

2013-01-01

these species are less stable than other isomers. Thus this study constitutes an additional piece towards the full understanding of a class of reaction of biological relevance. Further, the lack of high energy barriers and deep energy wells along the reaction

Biological treatment processes for PCB contaminated soil at a site in Newfoundland

International Nuclear Information System (INIS)

Punt, M.; Cooper, D.; Velicogna, D.; Mohn, W.; Reimer, K.; Parsons, D.; Patel, T.; Daugulis, A.

2002-01-01

SAIC Canada is conducting a study under the direction of a joint research and development contract between Public Works and Government Services Canada and Environment Canada to examine the biological options for treating PCB contaminated soil found at a containment cell at a former U.S. Military Base near Stephenville, Newfoundland. In particular, the study examines the feasibility of using indigenous microbes for the degradation of PCBs. The first phase of the study involved the testing of the microbes in a bioreactor. The second phase, currently underway, involves a complete evaluation of possible microbes for PCB degradation. It also involves further study into the biological process options for the site. Suitable indigenous and non-indigenous microbes for PCB dechlorination and biphenyl degradation are being identified and evaluated. In addition, the effectiveness and economics of microbial treatment in a conventional bioreactor is being evaluated. The conventional bioreactor used in this study is the two-phase partitioning bioreactor (TPPB) using a biopile process. Results thus far will be used to help Public Works and Government Services Canada to choose the most appropriate remedial technology. Preliminary results suggest that the use of soil classification could reduce the volume of soil requiring treatment. The soil in the containment cell contains microorganisms that could grow in isolation on biphenyl, naphthalene and potentially Aroclor 1254. Isolated native microbes were inoculated in the TPPB for growth. The TPPB was also run successfully under anaerobic conditions. Future work will involve lab-scale evaluation of microbes for PCB dechlorination and biphenyl degradation using both indigenous and non-indigenous microbes. The next phase of study may also involve field-scale demonstration of treatment methods. 2 refs., 3 tabs., 5 figs

Complete Reductive Dehalogenation of Brominated Biphenyls by Anaerobic Microorganisms in Sediment

Science.gov (United States)

Bedard, Donna L.; Van Dort, Heidi M.

1998-01-01

We sought to determine whether microorganisms from the polychlorinated biphenyl (PCB)-contaminated sediment in Woods Pond (Lenox, Mass.) could dehalogenate brominated biphenyls. The PCB dechlorination specificities for the microorganisms in this sediment have been well characterized. This allowed us to compare the dehalogenation specificities for brominated biphenyls and chlorinated biphenyls within a single sediment. Anaerobic sediment microcosms were incubated separately at 25°C with 16 different mono- to tetrabrominated biphenyls (350 μM) and disodium malate (10 mM). Samples were extracted and analyzed by gas chromatography with an electron capture detector and a mass spectrometer detector at various times for up to 54 weeks. All of the tested brominated biphenyls were dehalogenated. For most congeners, including 2,6-dibromobiphenyl (26-BB) and 24-25-BB, the dehalogenation began within 1 to 2 weeks. However, for 246-BB and 2-2-BB, debromination was first observed at 7 and 14 weeks, respectively. Most intermediate products did not persist, but when 2-2-BB was produced as a dehalogenation product, it persisted for at least 15 weeks before it was dehalogenated to 2-BB and then to biphenyl. The dehalogenation specificities for brominated and chlorinated biphenyls were similar: meta and para substituents were generally removed first, and ortho substituents were more recalcitrant. However, the brominated biphenyls were better dehalogenation substrates than the chlorinated biphenyls. All of the tested bromobiphenyls, including those with ortho and unflanked meta and para substituents, were ultimately dehalogenated to biphenyl, whereas their chlorinated counterparts either were not dehalogenation substrates or were only partially dehalogenated. Our data suggest that PCB-dechlorinating microorganisms may be able to dehalogenate brominated biphenyls and may exhibit a relaxed specificity for these substrates. PMID:16349530

Successive self-propagating sintering process using carbonaceous materials: A novel low-cost remediation approach for dioxin-contaminated solids

Energy Technology Data Exchange (ETDEWEB)

Zhao, Long, E-mail: zhaolong@craes.org.cn [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Dayangfang 8, Beijing 100012 (China); Hou, Hong, E-mail: houhong@craes.org.cn [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Dayangfang 8, Beijing 100012 (China); Zhu, Tengfei; Li, Fasheng [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Dayangfang 8, Beijing 100012 (China); Terada, Akihiko; Hosomi, Masaaki [Department of Chemical Engineering, Faculty of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588 (Japan)

2015-12-15

Highlights: • A SSPSP using carbonaceous materials for removing dioxin pollutants was developed. • Removal and degradation efficiencies of DL-PCBs were higher than those of PCDD/Fs. • Compositions of PCDD/Fs were dependent on the available precursors in raw materials. • Dechlorination of O{sub 8}CDD and formation pathways of PCDFs were deduced. • Dioxin levels in the effluent gas complied with the International emission limit. - Abstract: The disposal of dioxin-contaminated solids was studied using a novel successive self-propagating sintering process (SSPSP) incorporating a carbonaceous material. Among the five types of carbonaceous materials investigated, Charcoal B displayed optimum adsorbent properties and was selected as the best thermal source in the current remediation approach based on economical efficiency aspects. The feasibility of this proposed approach, removal efficiencies, and congener compositions of dioxins were examined using two types of dioxin-contaminated solids (Fugan sediment and Toyo soil) that displayed different characteristics including the initial concentrations of dioxins. The removal efficiencies of DL-PCBs (“dioxin-like” polychlorinated biphenyls) were higher than those of PCDD/Fs (polychlorinated dibenzo-p-dioxins/dibenzofurans), achieving 99.9 and 92% removal in the Fugan sediment and Toyo soil, respectively. In contrast, the degradation efficiencies of DL-PCBs were lower (i.e., 89.3 and 88.8%, respectively). The initial concentrations of dioxins, available precursors, and properties of the solids strongly influenced the congener compositions and removal efficiencies of dioxins. Furthermore, the dechlorination reaction pathways of high-chlorinated PCDDs and potential regeneration pathways of PCDFs from PCBs were deduced using isotope labeling. The proposed novel low-cost remediation approach for the removal of dioxins from solids is a highly efficient and environmentally sound treatment technology.

Successive self-propagating sintering process using carbonaceous materials: A novel low-cost remediation approach for dioxin-contaminated solids

International Nuclear Information System (INIS)

Zhao, Long; Hou, Hong; Zhu, Tengfei; Li, Fasheng; Terada, Akihiko; Hosomi, Masaaki

2015-01-01

Highlights: • A SSPSP using carbonaceous materials for removing dioxin pollutants was developed. • Removal and degradation efficiencies of DL-PCBs were higher than those of PCDD/Fs. • Compositions of PCDD/Fs were dependent on the available precursors in raw materials. • Dechlorination of O_8CDD and formation pathways of PCDFs were deduced. • Dioxin levels in the effluent gas complied with the International emission limit. - Abstract: The disposal of dioxin-contaminated solids was studied using a novel successive self-propagating sintering process (SSPSP) incorporating a carbonaceous material. Among the five types of carbonaceous materials investigated, Charcoal B displayed optimum adsorbent properties and was selected as the best thermal source in the current remediation approach based on economical efficiency aspects. The feasibility of this proposed approach, removal efficiencies, and congener compositions of dioxins were examined using two types of dioxin-contaminated solids (Fugan sediment and Toyo soil) that displayed different characteristics including the initial concentrations of dioxins. The removal efficiencies of DL-PCBs (“dioxin-like” polychlorinated biphenyls) were higher than those of PCDD/Fs (polychlorinated dibenzo-p-dioxins/dibenzofurans), achieving 99.9 and 92% removal in the Fugan sediment and Toyo soil, respectively. In contrast, the degradation efficiencies of DL-PCBs were lower (i.e., 89.3 and 88.8%, respectively). The initial concentrations of dioxins, available precursors, and properties of the solids strongly influenced the congener compositions and removal efficiencies of dioxins. Furthermore, the dechlorination reaction pathways of high-chlorinated PCDDs and potential regeneration pathways of PCDFs from PCBs were deduced using isotope labeling. The proposed novel low-cost remediation approach for the removal of dioxins from solids is a highly efficient and environmentally sound treatment technology.

Anaerobic biological treatment

International Nuclear Information System (INIS)

Speece, R.E.

1990-01-01

The Enso-Fenox process has been very successfully used to remove chlorinated phenolic compounds from pulp bleaching effluents. It is a two-stage anaerobic/aerobic process consisting of a nonmethanogenic anaerobic fluidized bed followed by a trickling filter. Studies have been conducted on reductive dechlorination of chlorinated aromatic compounds under anaerobic conditions with chlorinated phenols as the sole carbon and energy source. Approximately 40% of the added chlorophenols was converted to CH 4 and CO 2 . Substrate loading rates were 20 mg/L/d at hydraulic detention times of 2-4 days with 90% substrate conversion efficiency. Reductive dechlorination of mono, di-, tri-, and pentachlorophenols has been demonstrated in anaerobic sewage sludge. The following constituents were tested in the laboratory at their approximate concentrations in coal conversion wastewater (CCWW) and were anaerobically degraded in serum bottles: 1,000 mg/L phenol; 500 mg/L resorcinol; 1,000 mg/L benzoic acid; 500 mg/L p-cresol; 200 mg/L pyridine; 2,000 mg/L benzoic acid; 250 mg/L 40 methylcatechol; 500 mg/L 4-ethylpyridine; and 2,000 mg/L hexanoic acid. A petrochemical may initially exhibit toxicity to an unacclimated population of methane-fermenting bacteria, but with acclimation the toxicity may be greatly reduced or disappear. In addition, the microorganisms may develop the capacity to actually degrade compounds which showed initial toxicity. Since biomass digestion requires a complete consortium of bacteria, it is relevant to study the effect of a given process as well as to individual steps within the process. A toxicant can inhibit the rate-limiting step and/or change the step that is rate-limiting. Both manifestations of toxicity can severely affect the overall process

Development of an integrated, in-situ remediation technology. Topical report for task No. 6: lab-scale development of microbial degradation process, September 26, 1994--May 25, 1996

International Nuclear Information System (INIS)

Odom, J.M.

1997-01-01

Contamination in low permeability soils poses a significant technical challenge to in situ remediation efforts. Poor accessibility to the contaminants and difficulty in delivery of treatment reagents have rendered existing in situ treatments such as bioremediation, vapor extraction, and pump and treat rather ineffective when applied to low permeability soils present at many contaminated sites. The technology is an integrated in situ treatment in which established geotechnical methods are used to install degradation zones directly in the contaminated soil, and electro-osmosis is utilized to move the contaminants back and forth through those zones until the treatment is completed. The present Topical Report for Task No. 6 summarizes the results of a study of the potential for stimulating microbial reductive dehalogenation as part of the integrated in situ treatment process at the field experiment test site at DOE's Gaseous Diffusion Plant in Paducah, Kentucky. A series of open-quotes microcosm bottle testsclose quotes were performed on samples of contaminated soil and groundwater taken from the Paducah site and spiked with trichloroethene (TCE). A number of bottles were set up, each spiked with a different carbon source in order to enhance the growth of different microbial subpopulations already present within the indigenous population in the soil. In addition, a series of bottle tests were completed with samples of the granular activated carbon (GAC) treatment zone material retrieved from the test site during the Paducah field experiment. In these tests, the GAC samples were used in place of the soil. Results of the soil-groundwater microcosms yielded a negative indication of the presence of dechlorinating bacteria at the site. However, charcoal (GAC) samples from one location in the test plot exhibited marked dechlorination with conversion of TCE to dichloroethene

Photodegradation of lambda-cyhalothrin and cypermethrin in aqueous solution as affected by humic acid and/or copper: intermediates and degradation pathways.

Science.gov (United States)

Xie, Jimin; Wang, Pingli; Liu, Jun; Lv, Xiaomeng; Jiang, Deli; Sun, Cheng

2011-11-01

The influence of coexisting humic acids (HA) or Cu²⁺ on the photodegradation of pesticides lambda-cyhalothrin (λ-CHT) and cypermethrin (CPM) in aqueous solution was studied under xenon lamp irradiation. The removal efficiency of pesticides λ-CHT and CPM were enhanced in the presence of either Cu²⁺ or HA but restrained in the presence of both Cu²⁺ and HA. The photodegradation of λ-CHT and CPM followed first-order reaction kinetics. The photodegradation intermediates of λ-CHT and CPM were determined using gas chromatography/mass spectrometry. Possible photodegradation pathways included decarboxylation, ester bond cleavage, dechlorination, and phenyl group removal. Copyright © 2011 SETAC.

Electrokinetically Enhanced Delivery for ERD Remediation of Chlorinated Ethenes in a Fractured Limestone Aquifer

DEFF Research Database (Denmark)

Broholm, Mette Martina; Hyldegaard, Bente Højlund; With Nedergaard, Lærke

causing very long remediation timeframes. Electrokinetics (EK) offers some unique transport processes, which can potentially overcome the diffusion limitations in the matrix. A novel technology combines ERD and EK for enhanced delivery. The combined technology (EK-BIO) has shown promising results in clay....... Experimental work on EK-BIO in limestone was conducted in a laboratory setup with limestone cores. EK was demonstrated to be promising in establishing enhanced contact between the donor lactate, bacteria, and cis-DCE within the limestone matrix. Complete dechlorination is expected to take place in the matrix......, since back diffusion limitations in the limestone matrix are overcome. This is essential for the overall time perspective of a remediation in limestone aquifers....

[Preparation of Coated CMC-Fe0 Using Rheological Phase Reaction Method and Research on Degradation of TCE in Water].

Science.gov (United States)

Fan, Wen-jing; Cheng, Yue; Yu, Shu-zhen; Fan, Xiao-feng

2015-06-01

The coated nanoscale zero-valent iron (coated CMC-Fe0) was synthesized with cheap and environment friendly CMC as the coating agent using rheological phase reaction. The sample was characterized by means of XRD, SEM, TEM and N2 adsorption-stripping and used to study reductive dechlorination of TCE. The experimental results indicated that the removal rate of TCE was about 100% when the CMC-Fe0 dosage was 6 g x L(-1), the initial TCE concentration was 5 mg x L(-1) and the reaction time was 40 h. The TCE degradation reaction of coated CMC-Fe0 followed a pseudo-first-order kinetic model. Finally, the product could be simply recovered.

Application of activated carbons from coal and coconut shell for removing free residual chlorine.

Science.gov (United States)

Ogata, Fumihiko; Tominaga, Hisato; Ueda, Ayaka; Tanaka, Yuko; Iwata, Yuka; Kawasaki, Naohito

2013-01-01

This study investigated the removal of free residual chlorine by activated carbon (AC). ACs were prepared from coal (AC1) and coconut shell (AC2). The specific surface area of AC1 was larger than that of AC2. The removal of free residual chlorine increased with elapsed time and amount of adsorbent. The removal mechanism of free residual chlorine was the dechlorination reaction between hypochlorous acid or hypochlorite ion and AC. Moreover, AC1 was useful in the removal of free residual chlorine in tap water. The optimum condition for the removal of free residual chlorine using a column is space velocity 306 1/h; liner velocity 6.1 m/h.

Inhibition of Ps Formation in Benzene and Cyclohexane by CH3CI and CH3Br

DEFF Research Database (Denmark)

Wikander, G.; Mogensen, O. E.; Pedersen, Niels Jørgen

1983-01-01

Positron-annihilation lifetime spectra have been measured for mixtures of CH3Cl and CH3Br in cyclohexane and of CH3Cl in benzene. The ortho-positronium (Ps) yield decreased monotonically from 38% and 43% in cyclohexane and benzene respectively to 11% in pure CH3Cl and 6% in pure CH3Br. The strength......− anions to form Ps. while it forms a bound state with the halides. X−. CH3Cl was a roughly three times weaker Ps inhibitor in benzene than in cyclohexane, which shows that CH3Cl− does not dechlorinate in times comparable to or shorter than 400–500 ps in benzene. An improved model for the explanation of Ps...

Effects of Pseudomonas species on the release of bound 14C residues from soil treated with [14C]atrazine

International Nuclear Information System (INIS)

Khan, S.U.; Behki, R.M.

1990-01-01

The release of bound (nonextractable) 14 C residues from soil previously treated with [ 14 C]atrazine was investigated by incubation of the solvent-extracted soil with two species of Pseudomonas capable of metabolizing atrazine. The two species, 192 and 194, released bound 14 C residues from the soil. Addition of glucose, known to increase microbiological activities, to the incubated soil appeared to enhance the release of soil-bound 14 C residues, in particular in the presence of Pseudomonas species 192. The 14 C bound residues in soil, mainly present as the parent compound and its hydroxy and monodealkylated analogues, were released into the incubation mixture and were subsequently metabolized by the two species involving dechlorination and dealkylation

Immobilization of fission products arising from pyrometallurgical reprocessing in chloride media

Science.gov (United States)

Leturcq, G.; Grandjean, A.; Rigaud, D.; Perouty, P.; Charlot, M.

2005-12-01

Spent nuclear fuel reprocessing to recover energy-producing elements such as uranium or plutonium can be performed by a pyrochemical process. In such method, the actinides and fission products are extracted by electrodeposition in a molten chloride medium. These processes generate chlorinated alkali salt flows contaminated by fission products, mainly Cs, Ba, Sr and rare earth elements constituting high-level waste. Two possible alternatives are investigated for managing this wasteform; a protocol is described for dechlorinating the fission products to allow vitrification, and mineral phases capable of immobilizing chlorides are listed to allow specification of a dedicated ceramic matrix suitable for containment of these chlorinated waste streams. The results of tests to synthesize chlorosilicate phases are also discussed.

Reductive dechlorination of trichloroethylene and tetrachloroethylene under aerobic conditions in a sediment column

International Nuclear Information System (INIS)

Enzien, M.V.; Picardal, F.; Hazen, T.

1994-01-01

This study investigated the bioremediation of chlorinated solvents in a sediment column. Biodegradation potentials of trichloroethylene and tetrachloroethylene during aerobic methanotrophic biostimulation were studied at the Savannah River Site. 30 refs., 3 figs., 3 tabs

Reductive Dechlorination of Trichloroethylene and Tetrachloroethylene under Aerobic Conditions in a Sediment Column

OpenAIRE

1994-01-01

Biodegradation of trichloroethylene and tetrachloroethylene under aerobic conditions was studied in a sediment column. Cumulative mass balances indicated 87 and 90% removal for trichloroethylene and tetrachloroethylene, respectively. These studies suggest the potential for simultaneous aerobic and anaerobic biotransformation processes under bulk aerobic conditions.

ELECTROLYTIC DECHLORINATION OF 2-CHLOROBIPHENYL AT A PALLADIUM MODIFIED GRANULAR-GRAPHITE-PACKED ELECTRODE

Science.gov (United States)

Polychlorinated biphenyls (PCBs) and other chlorinated aromatic compounds are distributed in soils and sediments at over 400 sites in the USA. A national need exists for both in situ and ex situ methods to destroy these persistent organic pollutants in soils and sediments at ambi...

Study of chlordecone desorption from activated carbons and subsequent dechlorination by reduced cobalamin.

Science.gov (United States)

Ranguin, Ronald; Durimel, Axelle; Karioua, Reeka; Gaspard, Sarra

2017-11-01

Since 1972, the French departments of Guadeloupe and Martinique have intensively used organochlorinated pesticides such as chlordecone (CLD) and hexachlorocyclohexane (HCH) isomers to prevent the proliferation of banana weevil (Cosmopolite sordidus). These molecules are stable in the environment, leading to a continuous contamination of soils, water, and food chain in the banana-producing areas. In these polluted areas, water treatment plants are equipped with activated carbon (AC) filters. In order to improve treatment of CLD-contaminated waters by AC, CLD adsorption and desorption kinetic studies are carried out using different ACs produced from sugar cane bagasse as adsorbents and subsequent CLD degradation is performed using reduced vitamin B12 (VB12). A GC-MS method for CLD quantification is as well optimized. This study shows that bagasse ACs are able to capture the pollutant, leading to a CLD concentration decrease from 1 to 73 μg L -1 , with an adsorption capacity of 162 μg mg -1 . Adsorption capacity increase with the temperature indicates an endothermic process. Polar solvents favor CLD desorption from ACs, suggesting hydrogen bonding between CLD and surface groups of ACs, the best solvent for chemical desorption being ethanol. Subsequent degradation of CLD in ethanol is performed using vitamin B12 reduced by either 1,4-dithiotreitol (DTT) or zerovalent zinc, leading to 90% of CLD removal and to the molecule cage structure opening for formation of a pentachloroindene intermediate product, characterized by GC MS/MS. A pathway for pentachloroindene formation from CLD is proposed.

Catalytic decomposition of trichloroethylene over Pt-/Ni-catalyst under microwave heating

Energy Technology Data Exchange (ETDEWEB)

Takashima, Hideaki; Karches, Martin [Chemiace Laboratory, 36-13 Hon-cho, Hachioji 192-0066 (Japan); Kanno, Yoshinori [Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi, 4-3-11 Takeda, Kofu 400-8511 (Japan)], E-mail: kanno@yamanashi.ac.jp

2008-01-30

Microwave (MW)-activated catalytic reactor system was studied and the results were compared with that of a conventional system based on the thermal activation method. Trichloroethylene (TCE) was decomposed under various MW-powers supply. Results showed that there is an optimum film thickness that was loaded on supports in MW heating system. The threshold may be within 1-3 {mu}m. Lower temperature cannot activate the catalyst, while higher temperature results in carbon deposition and catalyst deactivation. This means that the dechlorination reaction needs to fix an optimum film MW-power supply in order to avoid the deposition of carbon on the surface of the active phase. MW-activated system is also worth compensating the conventional system in VOCs decomposition reaction.

Remediation of TCE-contaminated groundwater using nanocatalyst and bacteria.

Science.gov (United States)

Kang, Ser Ku; Seo, Hyunhee; Sun, Eunyoung; Kim, Inseon; Roh, Yul

2011-08-01

The objective of this study was to develop and evaluate the remediation of trichloroethene (TCE)-contaminated groundwater using both a nanocatalyst (bio-Zn-magnetite) and bacterium (similar to Clostridium quinii) in anoxic environments. Of the 7 nanocatalysts tested, bio-Zn-magnetite showed the highest TCE dechlorination efficiency, with an average of ca. 90% within 8 days in a batch experiment. The column tests confirmed that the application of bio-Zn-magnetite in combination with the bacterium achieved high degradation efficiency (ca. 90%) of TCE within 5 days compared to the nanocatalyst only, which degraded only 30% of the TCE. These results suggest that the application of a nanocatalyst and the bacterium have potential for the remediation of TCE-contaminated groundwater in subsurface environments.

The influence of chlorine on the fate and activity of alkali metals during the gasification of wood

Energy Technology Data Exchange (ETDEWEB)

Struis, R; Scala, C von; Schuler, A; Stucki, S [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1999-08-01

Chlorine clearly inhibits the CO{sub 2}-gasification reaction of charcoal at 800{sup o}C. From this and other observations the picture emerges that the reduction in the gasification reactivity of the charcoal is intimately related to the deactivation of the catalytically active alkali metals residing in the wood due to the formation of the chloride salt. It is argued that the heavy metal chlorides will likely transfer the chlorine to the indigenous alkali metals during the pyrolysis stage of the wood. The fate of the thus formed alkali metal chlorides can then be either their removal from the sample (evaporation), or, when present at the gasification stage, re-activation (i.e., de-chlorination) under our gasification conditions. (author) 3 figs., 4 refs.

Simultaneous biodegradation of carbon tetrachloride and trichloroethylene in a coupled anaerobic/aerobic biobarrier

Energy Technology Data Exchange (ETDEWEB)

Kwon, Kiwook [Department of Civil and Environmental Engineering, Hanyang University, 55 Hanyangdaehak-ro, Sangnok-gu, Ansan, Gyeonggi-do 15588 (Korea, Republic of); Shim, Hojae [Department of Civil and Environmental Engineering, Faculty of Science and Technology, University of Macau, Macau SAR, 999078 (China); Bae, Wookeun, E-mail: wkbae@hanyang.ac.kr [Department of Civil and Environmental Engineering, Hanyang University, 55 Hanyangdaehak-ro, Sangnok-gu, Ansan, Gyeonggi-do 15588 (Korea, Republic of); Oh, Juhyun; Bae, Jisu [Department of Civil and Environmental Engineering, Hanyang University, 55 Hanyangdaehak-ro, Sangnok-gu, Ansan, Gyeonggi-do 15588 (Korea, Republic of)

2016-08-05

Highlights: • Coupled biodegradation of carbon tetrachloride (CT) and trichloroethylene (TCE) in biobarrier with polyethylene glycol carriers. • TCE aerobically cometabolized and CT anaerobically dechlorinated. • Removal efficiencies of over 98%, leaving residuals below or near the regulatory standards. • Coupled aerobic/anaerobic environments established by H{sub 2}O{sub 2} injected at 50% of electron donor. • Longer retention time (from 3.6 to 7.2 days) achieved satisfactory removal at lower temperature (18 °C). - Abstract: Simultaneous biodegradation of carbon tetrachloride (CT) and trichloroethylene (TCE) in a biobarrier with polyethylene glycol (PEG) carriers was studied. Toluene/methanol and hydrogen peroxide (H{sub 2}O{sub 2}) were used as electron donors and an electron acceptor source, respectively, in order to develop a biologically active zone. The average removal efficiencies for TCE and toluene were over 99.3%, leaving the respective residual concentrations of ∼12 and ∼57 μg/L, which are below or close to the groundwater quality standards. The removal efficiency for CT was ∼98.1%, with its residual concentration (65.8 μg/L) slightly over the standards. TCE was aerobically cometabolized with toluene as substrate while CT was anaerobically dechlorinated in the presence of electron donors, with the respective stoichiometric amount of chloride released. The oxygen supply at equivalent to 50% chemical oxygen demand of the injected electron donors supported successful toluene oxidation and also allowed local anaerobic environments for CT reduction. The originally augmented (immobilized in PEG carriers) aerobic microbes were gradually outcompeted in obtaining substrate and oxygen. Instead, newly developed biofilms originated from indigenous microbes in soil adapted to the coupled anaerobic/aerobic environment in the carrier for the simultaneous and almost complete removal of CT, TCE, and toluene. The declined removal rates when temperature

Diffusion Study on Dissolved Hydrogen toward Effective Bioremediation of Chlorinated Ethenes in Aquitards

Science.gov (United States)

Yoshikawa, M.; Zhang, M.; Takeuchi, M.; Komai, T.

2010-12-01

In Japan, the demand for in-situ remediation of contaminated sediments is expected to increase in the future due to the recent amendment of Soil Contamination Countermeasures Act. The Japanese law requires remediating not only contaminated groundwater but also contaminated sediments including those in aquitards. In-situ remediation of contaminated aquitards has been a challenging issue and bioremediation is considered to be one of the effective techniques. In microbial degradation of chrolinated ethenes such as tetrachloroethene and trichloroethene under anaerobic environments, dissolved hydrogen plays an important role. The dechlorinating microbes utilize hydrogen and chlorinated ethenes as an electron donor and an electron accepter, respectively. The size of hydrogen molecule is extremely small and the diffusion rate of dissolved hydrogen in an aquitard would be the key factor that controls the process of microbial dechlorination. However, the diffusion behavior of dissolved hydrogen in subsurface sediments remains unclear. The purposes of this study are to develop a practically utilizable test apparatus, carry out a series of dissolved hydrogen diffusion tests on representative samples, and illustrate the applicability of bioremediation in aquitards. A completely leak-free apparatus was developed by using aluminum alloy and gas tight rubber. This apparatus is capable of testing specimens with a diameter as large as 100 mm by a length from 5 mm to 10 mm, depending on the maximum grain size within a test specimen. Preliminary tests have been performed with glass beads as an ideal material, commercially available kaolin clay, and core samples taken from a polluted site containing clay minerals. The effective diffusion coefficients of these samples were all on the order of 10E-10 m2/s, though their coefficients of permeability varied between the orders of 10E-2 and 10E-7 cm/s. These results showed that there was no obvious relationship between the effective

Electroremediation of PCB contaminated soil combined with iron nanoparticles: Effect of the soil type

DEFF Research Database (Denmark)

Gomes, Helena I.; Dias-Ferreira, Celia; Ottosen, Lisbeth M.

2015-01-01

Polychlorinated biphenyls (PCB) are carcinogenic and persistent organic pollutants that accumulate in soils and sediments. Currently, there is no cost-effective and sustainable remediation technology for these contaminants. In this work, a new combination of electrodialytic remediation and zero...... nanoparticles. Remediation experiments are made with two different historically PCB contaminated soils, which differ in both soil composition and contamination source. Soil 1 is a mix of soils with spills of transformer oils, while Soil 2 is a superficial soil from a decommissioned school where PCB were used...... as windows sealants. Saponin, a natural surfactant, was also tested to increase the PCB desorption from soils and enhance dechlorination. Remediation of Soil 1 (with highest pH, carbonate content, organic matter and PCB concentrations) obtained the maximum 83% and 60% PCB removal with the two...

PCB management at Manitoba Hydro's Waverley Service Centre

International Nuclear Information System (INIS)

Rempel, R.G.; Engstrom, T.

1996-01-01

Manitoba Hydro was the first Canadian utility to initiate a program to decontaminate insulating oil contaminated with polychlorinated biphenyls (PCBs). This paper describes Manitoba Hydro's recovery, reuse and recycling program, operated out of the utility's Waverley Service Centre (WSC). The WSC is a central facility serving to phase out and and destroy PCBs which remain in Manitoba Hydro's electrical system. Several hundred thousand litres of PCB-contaminated insulating oil are decontaminated annually at the WSC. The decontaminated oil is then reconditioned for reuse within the system operations. A PCBX unit was purchased from Sun Ohio for the decontamination of insulating oils containing PCBs. PCB decontamination is achieved through a chemical dechlorination treatment process. The PCBX treatment unit and the PCB storage building were described. 18 refs., 8 figs

Evaluation of remediation of coal mining wastewater by chitosan microspheres using biomarkers

Energy Technology Data Exchange (ETDEWEB)

Benassi, J.C.; Laus, R.; Geremias, R.; Lima, P.L.; Menezes, C.T.B.; Laranjeira, M.C.M.; Wilhelm, D.; Favere, V.T.; Pedrosa, R.C. [Universidade Federal de Santa Catarina, Florianopolis (Brazil)

2006-11-15

The aim of this work was to evaluate the remediation of mining wastewater effluents by chitosan microspheres using biomarkers of exposure and effect. DNA damage (Comet assay) and several biomarkers of oxidative stress, such as lipoperoxidation levels (TBARS), superoxide dismutase (SOD), catalase (CAT), and glutathione S-transferase (GST) activities, and contents of reduced glutathione (GSH), were measured in blood and liver of tilapia (Oreochromis niloticus) exposed for 7, 15, and 30 days to dechlorinated tap water, 10% coal mining wastewater (CMW), and coal mining wastewater treated with chitosan microspheres (RCM). The results obtained indicated that the use of oxidative stress biomarkers were useful tools for the toxicity evaluation of coal mining effluents and also suggest that chitosan microspheres may be used as an alternative approach for remediation of coal mining wastewaters.

Analysis of dechlorination kinetics of chlorinated aliphatic hydrocarbons by Fe(II) in cement slurries

Energy Technology Data Exchange (ETDEWEB)

Jung, Bahngmi [Department of Earth and Environmental Sciences, Wright State University, Dayton, OH 45435-0001 (United States)], E-mail: jung.bahngmi@gmail.com; Batchelor, Bill [Department of Civil Engineering, Texas A and M University, College Station, TX 77843-3136 (United States)

2008-03-21

Degradative solidification/stabilization with ferrous iron (DS/S-Fe(II)) has been found to be effective in degrading a number of chlorinated aliphatic hydrocarbons including 1,1,1-trichloroethane (1,1,1-TCA), 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA), tetrachloroethylene (PCE), trichloroethylene (TCE), 1,1-dichloroethylene (1,1-DCE), vinyl chloride (VC), carbon tetrachloride (CT) and chloroform (CF). Previous studies have characterized degradation kinetics in DS/S-Fe(II) systems as affected by Fe(II) dose, pH and initial target organic concentration. The goal of this study is to investigate the importance of various chemical properties on degradation kinetics of DS/S-Fe(II). This was accomplished by first measuring rate constants for degradation of 1,1,1-TCA, 1,1,2,2-TeCA and 1,2-dichloroethane (1,2-DCA) in individual batch experiments. Rate constants developed in these experiments and those obtained from the literature were related to thermodynamic parameters including one-electron reduction potential, two-electron reduction potential, bond dissociation energy and lowest unoccupied molecular orbital energies. Degradation kinetics by Fe(II) in cement slurries were generally represented by a pseudo-first-order rate law. The results showed that the rate constants for chlorinated methanes (e.g. CT, CF) and chlorinated ethanes (e.g. 1,1,1-TCA) were higher than those for chlorinated ethylenes (e.g. PCE, TCE, 1,1-DCE and VC) under similar experimental conditions. The log of the pseudo-first-order rate constant (k) was found to correlate better with lowest unoccupied molecular orbital energies (E{sub LUMO}) (R{sup 2} = 0.874) than with other thermodynamic parameter descriptors.

Technical Protocol for Using Soluble Carbohydrates to Enhance Reductive Dechlorination of Chlorinated Aliphatic Hydrocarbons

Science.gov (United States)

2002-12-19

lead, arsenic, nickel, mercury and cadmium) is also widespread at the same military facilities due to the use of these metals in ordnance...Eds.), Bioremediation and phytoremediation of chlorinated and recalcitrant compounds. Battelle Second International Conference on Remediation of...Electron Donors, in Wickramanayake, G., Gavashkar, A., Alleman, B., Magar, V., eds. Bioremediation and Phytoremediation of Chlorinated and Recalcitrant

Retention and transport of an anaerobic trichloroethene dechlorinating microbial culture in anaerobic porous media.

Science.gov (United States)

Zhang, Huixin; Ulrich, Ania C; Liu, Yang

2015-06-01

The influence of solution chemistry on microbial transport was examined using the strictly anaerobic trichloroethene (TCE) bioaugmentation culture KB-1(®). A column was employed to determine transport behaviors and deposition kinetics of three distinct functional species in KB-1(®), Dehalococcoides, Geobacter, and Methanomethylovorans, over a range of ionic strengths under a well-controlled anaerobic condition. A quantitative polymerase chain reaction (qPCR) was utilized to enumerate cell concentration and complementary techniques were implemented to evaluate cell surface electrokinetic potentials. Solution chemistry was found to positively affect the deposition rates, which was consistent with calculated Derjaguin-Landau-Verwey-Overbeek (DLVO) interaction energies. Retained microbial profiles showed spatially constant colloid deposition rate coefficients, in agreement with classical colloid filtration theory (CFT). It was interesting to note that the three KB-1(®) species displayed similar transport and retention behaviors under the defined experimental conditions despite their different cell electrokinetic properties. A deeper analysis of cell characteristics showed that factors, such as cell size and shape, concentration, and motility were involved in determining adhesion behavior. Copyright © 2015 Elsevier B.V. All rights reserved.

BioReD: Biomarkers and Tools for Reductive Dechlorination Site Assessment, Monitoring and Management

Science.gov (United States)

2013-11-01

as amino acid and lipid metabolism and transport were over-represented in the transcripts as compared to the average Dhc gene (Figure 2.7...genes involved in corrinoid transport were transcribed, supporting the salvaging of corrinoids from the environment. Moreover, transcription of...soil and sediment samples. Appl. Environ. Microbiol. 65:4715-4724. 107. Miller, N. J., and S. M. Mudge. 1997. The effect of biodiesel on the rate of

Reactions of clofibric acid with oxidative and reductive radicals-Products, mechanisms, efficiency and toxic effects

Science.gov (United States)

Csay, Tamás; Rácz, Gergely; Salik, Ádám; Takács, Erzsébet; Wojnárovits, László

2014-09-01

The degradation of clofibric acid induced by hydroxyl radical, hydrated electron and O2-•/HO2• reactive species was studied in aqueous solutions. Clofibric acid was decomposed more effectively by hydroxyl radical than by hydrated electron or O2-•/HO2•. Various hydroxylated, dechlorinated and fragmentation products have been identified and quantified. A new LC-MS method was developed based on 18O isotope labeling to follow the formation of hydroxylated derivatives of clofibric acid. Possible degradation pathways have been proposed. The overall degradation was monitored by determination of sum parameters like COD, TOC and AOX. It was found that the organic chlorine degrades very effectively prior to complete mineralization. After the treatment no toxic effect was found according to Vibrio fischeri tests. However, at early stages some of the reaction products were more harmful than clofibric acid.

Assessment of pollutant biodegradation at the Yangtze three gorges dam, China

Energy Technology Data Exchange (ETDEWEB)

Kranzioch, Irene; Tiehm, Andreas [DVGW Technologiezentrum Wasser (TZW), Karlsruhe (Germany)

2012-07-01

The microbiological degradation of pollutants in the aquatic environment is affected by several key factors such as (1) the composition of the microbial community, (2) the oxidation-reduction-conditions, i.e. the availability of electron acceptors and electron donors, and (3) the mass transfer processes (e.g. biovailability of pollutants). As part of the joint Sino-German Yangtze project (www.yangtze-project.de), the Water Technology Centre (TZW) studies the microbial transformation processes with samples taken at the three gorges dam (TGD) area. In particular molecular microbiological methods such as the Polymerase Chain Reaction (PCR) are adapted and applied for a specific monitoring. The first studies focussed on the presence of dechlorinating bacteria and the degradation of halogenated substances. The experiments provide more insight into biodegradation processes and thus contribute to a better understanding of pollutant conversion in the Yangtze area. (org.)

Permeable reactive barrier of surface hydrophobic granular activated carbon coupled with elemental iron for the removal of 2,4-dichlorophenol in water

Energy Technology Data Exchange (ETDEWEB)

Yang Ji, E-mail: yangji@ecust.edu.cn [School of Resources and Environmental Engineering, State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, East China University of Science and Technology, Shanghai 200237 (China); Cao Limei; Guo Rui; Jia Jinping [School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China)

2010-12-15

Granular activated carbon was modified with dimethyl dichlorosilane to improve its surface hydrophobicity, and therefore to improve the performance of permeable reactive barrier constructed with the modified granular activated carbon and elemental iron. X-ray photoelectron spectroscopy shows that the surface silicon concentration of the modified granular activated carbon is higher than that of the original one, leading to the increased surface hydrophobicity. Although the specific surface area decreased from 895 to 835 m{sup 2} g{sup -1}, the modified granular activated carbon could adsorb 20% more 2,4-dichlorophenol than the original one did in water. It is also proven that the permeable reactive barrier with the modified granular activated carbon is more efficient at 2,4-dichlorophenol dechlorination, in which process 2,4-dichlorophenol is transformed to 2-chlorophenol or 4-chlorophenol then to phenol, or to phenol directly.

Life cycle assessment (LCA) as a decision-suppport tool for the evaluation of environmental impacts of site remediation on the global, regional and local scale

DEFF Research Database (Denmark)

Lemming, Gitte; Bulle, C.; Margni, Manuele

2010-01-01

Life cycle assessment (LCA) was used to compare the environment al impacts of three alternatives for remediating a TCE-contaminated site: (i) enhanced reductive dechlorination (ERD); (ii) in situ thermal desorption (ISTD) and (iii) excavation with off-site soil treatment. In addition......, the remediation alternatives were compared to a no action scenario, where only monitoring and natural attenuation takes place. A numerical reactive fracture model was used to predict the timeframes for the ERD and the no action scenarios. Moreover, the model was used to estimate the mass discharge of TCE...... of the LCA showed that of the three remediation methods compared, the ERD had the lowest total environmental impacts, even though it had significant primary impacts due to its long timeframe. The environmental impacts of ERD were comparable or only slightly higher than those of the no action scenario. ISTD...

Permeable reactive barrier of surface hydrophobic granular activated carbon coupled with elemental iron for the removal of 2,4-dichlorophenol in water

International Nuclear Information System (INIS)

Yang Ji; Cao Limei; Guo Rui; Jia Jinping

2010-01-01

Granular activated carbon was modified with dimethyl dichlorosilane to improve its surface hydrophobicity, and therefore to improve the performance of permeable reactive barrier constructed with the modified granular activated carbon and elemental iron. X-ray photoelectron spectroscopy shows that the surface silicon concentration of the modified granular activated carbon is higher than that of the original one, leading to the increased surface hydrophobicity. Although the specific surface area decreased from 895 to 835 m 2 g -1 , the modified granular activated carbon could adsorb 20% more 2,4-dichlorophenol than the original one did in water. It is also proven that the permeable reactive barrier with the modified granular activated carbon is more efficient at 2,4-dichlorophenol dechlorination, in which process 2,4-dichlorophenol is transformed to 2-chlorophenol or 4-chlorophenol then to phenol, or to phenol directly.

Anaerobic transformation of chlorinated dioxins by microorganisms

Energy Technology Data Exchange (ETDEWEB)

Adrian, L. [Fachgebiet Technische Biochemie, Technische Univ. Berlin (Germany); Lechner, U. [Inst. fuer Mikrobiologie, Martin-Luther-Univ. Halle-Wittenberg (Germany)

2004-09-15

Mixed bacterial cultures catalyze diverse chlorodioxin-dehalogenation pathways. Some of these pathways lead to relatively harmless end products, which can undergo further biological degradation e.g. by aerobic bacteria. However, the possible formation of highly toxic products is a critical problem for a bioremediation approach but also for untreated sites where such dechlorination reactions can occur. Bioaugmentation with suitable pure or mixed cultures is promising. This has recently been demonstrated in a tetrachloroethene-contaminated groundwater using a Dehalococcoidescontaining inoculum that almost completely converted tetrachloroethene to ethene without accumulation of the toxic intermediate vinyl chloride. With Dehalococcoides sp. strain CBDB1 the first bacterium is now known, that grows by dehalorespiration with dioxins. Learning from the physiology and biochemistry of this bacterium will help us to understand the role of these bacteria in the environment and to predict the fate of dioxin pollution.

Hydrometallurgical treatment of plutonium. Bearing salt baths waste

International Nuclear Information System (INIS)

Bros, P.; Gozlan, J.P.; Lecomte, M.; Bourges, J.

1993-01-01

The salt flux issuing from the electrorefining of plutonium metal alloy in salt baths (KCI + NaCI) poses a difficult problem of the back-end alpha waste management. An alternative to the salt process promoted by Los Alamos Laboratory is to develop a hydrometallurgical treatment. A new process based on the electrochemistry technique in aqueous solution has been defined and tested successfully in the CEA. The diagram of the process exhibits two principal steps: in the head-end, a dissolution in HNO 3 medium accompanied with an electrolytic dechlorination leading to a quantitative elimination of chloride as CI 2 gas followed by its trapping one soda lime cartridge, a complete oxidative dissolution of the refractory Pu residues by electrogenerated Ag(II), in the back-end: the Pu and Am recoveries by chromatographic extractions. (authors). 10 figs., 9 refs

Simultaneous electrodialytic removal of PAH, PCB, TBT and heavy metals from sediments

DEFF Research Database (Denmark)

Pedersen, Kristine B.; Lejon, Tore; Jensen, Pernille Erland

2017-01-01

with the need of different remedial actions for each pollutant. In this study, electrodialytic remediation (EDR) of sediments was found effective for simultaneous removal of heavy metals and organic pollutants for sediments from Arctic regions - Sisimiut in Greenland and Hammerfest in Norway. The influence...... was found to be important for the removal of heavy metals and TBT, while photolysis was significant for removal of PAH, PCB and TBT. In addition, dechlorination was found to be important for the removal of PCB. The highest removal efficiencies were found for heavy metals, TBT and PCB (>40%) and lower......Contaminated sediments are remediated in order to protect human health and the environment, with the additional benefit of using the treated sediments for other activities. Common for many polluted sediments is the contamination with several different pollutants, making remediation challenging...

Metabolism of the synthetic cannabinoids AMB-CHMICA and 5C-AKB48 in pooled human hepatocytes and rat hepatocytes analyzed by UHPLC-(IMS)-HR-MSE

DEFF Research Database (Denmark)

Mardal, Marie; Dalsgaard, Petur Weihe; Qi, Bing

2018-01-01

metabolites of the synthetic cannabinoids, AMB-CHMICA and 5C-AKB48, using an in silico-assisted workflow with analytical data acquired using ultra-high-performance liquid chromatography–(ion mobility spectroscopy)–high resolution–mass spectrometry in data-independent acquisition mode (UHPLC......-(IMS)-HR-MSE). The metabolites were identified after incubation with rat and pooled human hepatocytes using UHPLC-HR-MSE, followed by UHPLC-IMS-HR-MSE. Metabolites of AMB-CHMICA and 5C-AKB48 were predicted with Meteor (Lhasa Ltd) and imported to the UNIFI software (Waters). The predicted metabolites were assigned to analytical...... components supported by the UNIFI in silico fragmentation tool. The main metabolic pathway of AMB-CHMICA was O-demethylation and hydroxylation of the methylhexyl moiety. For 5C-AKB48, the main metabolic pathways were hydroxylation(s) of the adamantyl moiety and oxidative dechlorination with subsequent...

Influência do magnésio metálico e diferentes sais de magnésio em desovas de Biomphalaria glabrata (Say, 1818 Influence of metallic magnesium and various magnesium salts on egg-masses of Biomphalaria glabrata (Say, 1818

Directory of Open Access Journals (Sweden)

Nelymar Martineli Mendes

1983-12-01

Full Text Available Soluções de magnésio metálico e diferentes sais de magnésio foram testadas em laboratório, a fim de comprovar a ação das mesmas sobre a oviposição de B. glabrata. Usaram-se, para cada solução, dez caramujos adultos originários da Pampulha, Belo Horizonte-MG (Brasil, criados em laboratório. No experimento I foram estudadas soluções em água desclorada de magnésio elementar (Mg, cloreto de magnésio (MgCl2.6H2O, carbonato de magnésio [(MgCO34.Mg(OH2.nH2O], nitrato de magnésio [Mg(NO32. 6H2O] e sulfato de magnésio (MgSO4.7H2O, e no experimento II, Mg, Mg + latossolo, MgCO3, MgCO3 + latossolo, sempre nas concentrações de 500 e 1.000 ppm. Durante duas semanas os planorbídeos permaneceram em água para adaptação; em seguida, por quatro semanas em exposição com as soluções testadas e, posteriormente, em água por mais duas semanas para recuperação. A cada sete dias as desovas eram contadas, eliminadas e as soluções renovadas. Foi observado que as soluções de Mg e MgCO3, isoladamente ou associada ao latossolo, produziram uma diminuição significativa do número de desovas dos caramujos, mas não parada completa de oviposição, quando comparados os períodos de adaptação com os de exposição. As soluções de Mg e MgCO3 não devem ser consideradas como produtos promissores para o controle da população de B. glabrata, em virtude da diminuição das desovas só terem sido observadas quando foram utilizadas concentrações muito altas.Solutions of magnesium metallic and other salts of magnesium were tested in the laboratory to study the action on B. glabrata oviposition. For each solution, 10 adult snails from Pampulha, Belo Horizonte-MG (Brazil, reared in the laboratory, were used. In experiment I solutions, in dechlorinated water, of magnesium (Mg, magnesium chloride (MgCl2. 6H2O, magnesium carbonate [(MgCO34.Mg(OH2.nH2O], magnesium nitrate [Mg(NO32.6H2O] and magnesium sulfate (MgSO4.7H2O were tested; and in

TECHNOLOGY EVALUATION FOR WATERBORNE MERCURY REMOVAL AT THE Y12 NATIONAL SECURITY COMPLEX

Energy Technology Data Exchange (ETDEWEB)

He, Feng [ORNL; Liang, Liyuan [ORNL; Miller, Carrie L [ORNL

2011-01-01

The Hg-contaminated processing water produced at Y-12 facility is discharged through the storm drain system, merged at Outfall 200, and then discharged to EFPC. Most of the baseflow mercury at Outfall 200 arises from a small number of short sections of storm drain. This report discusses the waterborne mercury treatment technologies to decrease mercury loading to the surface water of EFPC at Y-12 NSC. We reviewed current available waterborne Hg treatment technologies based on the specific conditions of Y-12 and identified two possible options: SnCl2 reduction coupled with air stripping (SnCl2/air stripping) and sorption. The ORNL 2008 and 2009 field studies suggested that SnCl2/air stripping has the capability to remove waterborne mercury with efficiency higher than 90% at Outfall 200. To achieve this goal, dechlorination (i.e., removing residual chlorine from water) using dechlorinating agents such as thiosulfate has to be performed before the reduction. It is unclear whether or not SnCl2/air stripping can reduce the mercury concentration from ~1000 ng/L to 51 ng/L at a full-scale operation. Therefore, a pilot test is a logical step before a full-scale design to answer questions such as Hg removal efficiency, selection of dechlorinating agents, and so on. The major advantages of the SnCl2/air stripping system are: (1) expected low cost at high flow (e.g., the flow at Outfall 200); and (2) production of minimum secondary waste. However, there are many environmental uncertainties associated with this technology by introducing tin to EFPC ecosystem, for example tin methylation causing abiotic Hg methylation, which should be addressed before a full-scale implementation. Mercury adsorption by granular activated carbon (GAC) is a proven technology for treating Hg at Y-12. The ONRL 2010 lab sorption studies suggest that thiol-based resins hold the promise to combine with GAC to form a more cost-effective treatment system. To achieve a treatment goal of 51 ng/L at Outfall

Development and Sensitivity Analysis of a Fully Kinetic Model of Sequential Reductive Dechlorination in Groundwater

DEFF Research Database (Denmark)

Malaguerra, Flavio; Chambon, Julie Claire Claudia; Bjerg, Poul Løgstrup

2011-01-01

experiments of complete trichloroethene (TCE) degradation in natural sediments. Global sensitivity analysis was performed using the Morris method and Sobol sensitivity indices to identify the most influential model parameters. Results show that the sulfate concentration and fermentation kinetics are the most...

Catabolic thiosulfate disproportionation and carbon dioxide reduction in strain DCB-1, a reductively dechlorinating anaerobe

Energy Technology Data Exchange (ETDEWEB)

Mohn, W.W.; Tiedje, J.M. (Michigan State Univ., East Lansing (USA))

1990-04-01

Strain DCB-1 is a strict anaerobe capable of reductive dehalogenation. We elucidated metabolic processes in DCB-1 which may be related to dehalogenation and which further characterize the organism physiologically. Sulfoxy anions and CO2 were used by DCB-1 as catabolic electron acceptors. With suitable electron donors, sulfate and thiosulfate were reduced to sulfide. Sulfate and thiosulfate supported growth with formate or hydrogen as the electron donor and thus are probably respiratory electron acceptors. Other electron donors supporting growth with sulfate were CO, lactate, pyruvate, butyrate, and 3-methoxybenzoate. Thiosulfate also supported growth without an additional electron donor, being disproportionated to sulfide and sulfate. In the absence of other electron acceptors, CO2 reduction to acetate plus cell material was coupled to pyruvate oxidation to acetate plus CO2. Pyruvate could not be fermented without an electron acceptor. Carbon monoxide dehydrogenase activity was found in whole cells, indicating that CO2 reduction probably occurred via the acetyl coenzyme A pathway. Autotrophic growth occurred on H2 plus thiosulfate or sulfate. Diazotrophic growth occurred, and whole cells had nitrogenase activity. On the basis of these physiological characteristics, DCB-1 is a thiosulfate-disproportionating bacterium unlike those previously described.

Biomarkers’ Responses to Reductive Dechlorination Rates and Oxygen Stress in Bioaugmentation Culture KB-1TM

Directory of Open Access Journals (Sweden)

Gretchen L. W. Heavner

2018-02-01

Full Text Available Using mRNA transcript levels for key functional enzymes as proxies for the organohalide respiration (OHR rate, is a promising approach for monitoring bioremediation populations in situ at chlorinated solvent-contaminated field sites. However, to date, no correlations have been empirically derived for chlorinated solvent respiring, Dehalococcoides mccartyi (DMC containing, bioaugmentation cultures. In the current study, genome-wide transcriptome and proteome data were first used to confirm the most highly expressed OHR-related enzymes in the bioaugmentation culture, KB-1TM, including several reductive dehalogenases (RDases and a Ni-Fe hydrogenase, Hup. Different KB-1™ DMC strains could be resolved at the RNA and protein level through differences in the sequence of a common RDase (DET1545-like homologs and differences in expression of their vinyl chloride-respiring RDases. The dominant strain expresses VcrA, whereas the minor strain utilizes BvcA. We then used quantitative reverse-transcriptase PCR (qRT-PCR as a targeted approach for quantifying transcript copies in the KB-1TM consortium operated under a range of TCE respiration rates in continuously-fed, pseudo-steady-state reactors. These candidate biomarkers from KB-1TM demonstrated a variety of trends in terms of transcript abundance as a function of respiration rate over the range: 7.7 × 10−12 to 5.9 × 10−10 microelectron equivalents per cell per hour (μeeq/cell∙h. Power law trends were observed between the respiration rate and transcript abundance for the main DMC RDase (VcrA and the hydrogenase HupL (R2 = 0.83 and 0.88, respectively, but not transcripts for 16S rRNA or three other RDases examined: TceA, BvcA or the RDase DET1545 homologs in KB1TM. Overall, HupL transcripts appear to be the most robust activity biomarker across multiple DMC strains and in mixed communities including DMC co-cultures such as KB1TM. The addition of oxygen induced cell stress that caused respiration rates to decline immediately (>95% decline within one hour. Although transcript levels did decline, they did so more slowly than the respiration rate observed (transcript decay rates between 0.02 and 0.03 per hour. Data from strain-specific probes on the pangenome array strains suggest that a minor DMC strain in KB-1™ that harbors a bvcA homolog preferentially recovered following oxygen stress relative to the dominant, vcrA-containing strain.

Origin of VC-only plumes from naturally enhanced dechlorination in a peat-rich hydrogeologic setting

Science.gov (United States)

Filippini, Maria; Amorosi, Alessandro; Campo, Bruno; Herrero-Martìn, Sara; Nijenhuis, Ivonne; Parker, Beth L.; Gargini, Alessandro

2016-09-01

The occurrence of vinyl chloride (VC) is often a main concern at sites contaminated with chlorinated solvents due to its high degree of toxicity and carcinogenicity. VC occurrence in aquifers is most often related to the degradation of higher chlorinated ethenes or ethanes and it is generally detected in plumes along with parent contaminants. However, specific combination of stratigraphic, hydrogeologic and geochemical conditions can enhance the degradation of parents and lead to the formation of plumes almost entirely composed of VC (i.e. VC-only plumes). This paper investigates the causes of VC-only plumes in the aquifers below the city of Ferrara (northern Italy) by combining multiple lines of evidence. The City of Ferrara is located on an alluvial lowland, built by the River Po, and is made up of alternating unconsolidated sandy aquifer and silt-clay aquitard deposits of fluvial origin. This region has been strongly impacted by prior industrial activities, with the occurrence of chlorinated compounds at several sites. VC-only plumes with uncertain source location were found at two contaminated sites. The source zone of a third plume composed of chloroethenes from PCE to VC was investigated for high resolution depositional facies architecture and contaminant distribution (contaminant concentration and Compound Specific Isotope Analysis - CSIA). The investigation suggested that degradation of PCE and TCE takes place during contaminant migration through peat-rich (swamp) layers related to the Holocene transgression, which locally act as a ;reactor; for stimulating degradation with the accumulation of VC in the strongly reducing environment of the peat. Regional-scale stratigraphic architecture showed the ubiquitous occurrence of swamp layers at distinct stratigraphic levels in the investigated system and their apparent linkage to the in situ creation of the VC-only plumes.

Photochemical organic oxidations and dechlorinations with a mu-oxo bridged heme/non-heme diiron complex.

Science.gov (United States)

Wasser, Ian M; Fry, H Christopher; Hoertz, Paul G; Meyer, Gerald J; Karlin, Kenneth D

2004-12-27

Steady state and laser flash photolysis studies of the heme/non-heme mu-oxo diiron complex [((6)L)Fe(III)-O-Fe(III)-Cl](+) (1) have been undertaken. The anaerobic photolysis of benzene solutions of 1 did not result in the buildup of any photoproduct. However, the addition of excess triphenylphosphine resulted in the quantitative photoreduction of 1 to [((6)L)Fe(II)...Fe(II)-Cl](+) (2), with concomitant production by oxo-transfer of 1 equiv of triphenylphosphine oxide. Under aerobic conditions and excess triphenylphosphine, the reaction produces multiple turnovers (approximately 28) before the diiron complex is degraded. The anaerobic photolysis of tetrahydrofuran (THF) or toluene solutions of 1 likewise results in the buildup of 2. The oxidation products from these reactions included gamma-butyrolactone (approximately 15%) for the reaction in THF and benzaldehyde (approximately 23%) from the reaction in toluene. In either case, the O-atom which is incorporated into the carbonyl product is derived from dioxygen present under workup or under aerobic photolysis conditions. Transient absorption measurements of low-temperature THF solutions of 1 revealed the presence of an (P)Fe(II)-like [P = tetraaryl porphyrinate dianion] species suggesting that the reactive species is a formal (heme)Fe(II)/Fe(IV)=O(non-heme) pair. The non-heme Fe(IV)=O is thus most likely responsible for C-H bond cleavage and subsequent radical chemistry. The photolysis of 1 in chlorobenzene or 1,2-dichlorobenzene resulted in C-Cl cleavage reactions and the formation of [[((6)L)Fe(III)-Cl...Fe(III)-Cl](2)O](2+) (3), with chloride ligands that are derived from solvent dehalogenation chemistry. The resulting organic products are biphenyl trichlorides or biphenyl monochlorides, derived from dichlorobenzene and chlorobenzene, respectively. Similarly, product 3 is obtained by the photolysis of benzene-benzyl chloride solutions of 1; the organic product is benzaldehyde (approximately 70%). A brief discussion of the dehalogenation chemistry, along with relevant environmental perspectives, is included.

Biomarkers' Responses to Reductive Dechlorination Rates and Oxygen Stress in Bioaugmentation Culture KB-1TM.

Science.gov (United States)

Heavner, Gretchen L W; Mansfeldt, Cresten B; Debs, Garrett E; Hellerstedt, Sage T; Rowe, Annette R; Richardson, Ruth E

2018-02-08

Using mRNA transcript levels for key functional enzymes as proxies for the organohalide respiration (OHR) rate, is a promising approach for monitoring bioremediation populations in situ at chlorinated solvent-contaminated field sites. However, to date, no correlations have been empirically derived for chlorinated solvent respiring, Dehalococcoides mccartyi (DMC) containing, bioaugmentation cultures. In the current study, genome-wide transcriptome and proteome data were first used to confirm the most highly expressed OHR-related enzymes in the bioaugmentation culture, KB-1 TM , including several reductive dehalogenases (RDases) and a Ni-Fe hydrogenase, Hup. Different KB-1™ DMC strains could be resolved at the RNA and protein level through differences in the sequence of a common RDase (DET1545-like homologs) and differences in expression of their vinyl chloride-respiring RDases. The dominant strain expresses VcrA, whereas the minor strain utilizes BvcA. We then used quantitative reverse-transcriptase PCR (qRT-PCR) as a targeted approach for quantifying transcript copies in the KB-1 TM consortium operated under a range of TCE respiration rates in continuously-fed, pseudo-steady-state reactors. These candidate biomarkers from KB-1 TM demonstrated a variety of trends in terms of transcript abundance as a function of respiration rate over the range: 7.7 × 10 -12 to 5.9 × 10 -10 microelectron equivalents per cell per hour (μeeq/cell∙h). Power law trends were observed between the respiration rate and transcript abundance for the main DMC RDase (VcrA) and the hydrogenase HupL (R² = 0.83 and 0.88, respectively), but not transcripts for 16S rRNA or three other RDases examined: TceA, BvcA or the RDase DET1545 homologs in KB1 TM . Overall, HupL transcripts appear to be the most robust activity biomarker across multiple DMC strains and in mixed communities including DMC co-cultures such as KB1 TM . The addition of oxygen induced cell stress that caused respiration rates to decline immediately (>95% decline within one hour). Although transcript levels did decline, they did so more slowly than the respiration rate observed (transcript decay rates between 0.02 and 0.03 per hour). Data from strain-specific probes on the pangenome array strains suggest that a minor DMC strain in KB-1™ that harbors a bvcA homolog preferentially recovered following oxygen stress relative to the dominant, vcrA -containing strain.

Functionalized membranes for environmental remediation and selective separation

Science.gov (United States)

Xiao, Li

Membrane process including microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) have provided numerous successful applications ranging from drinking water purification, wastewater treatment, to material recovery. The addition of functional moiety in the membranes pores allows such membranes to be used in challenging areas including tunable separations, toxic metal capture, and catalysis. In this work, polyvinylidene fluoride (PVDF) MF membrane was functionalized with temperature responsive (poly(N-isopropylacrylamide), PNIPAAm) and pH responsive (polyacrylic acid, PAA) polymers. It's revealed that the permeation of various molecules (water, salt and dextran) through the membrane can be thermally or pH controlled. The introduction of PAA as a polyelectrolyte offers an excellent platform for the immobilization of metal nanoparticles (NPs) applied for degradation of toxic chlorinated organics with significantly increased longevity and stability. The advantage of using temperature and pH responsive polymers/hydrogels also includes the high reactivity and effectiveness in dechlorination. Further advancement on the PVDF functionalization involved the alkaline treatment to create partially defluorinated membrane (Def-PVDF) with conjugated double bounds allowing for the covalent attachment of different polymers. The PAA-Def-PVDF membrane shows pH responsive behavior on both the hydraulic permeability and solute retention. The sponge-like PVDF (SPVDF) membranes by phase inversion were developed through casting PVDF solution on polyester backing. The SPVDF membrane was demonstrated to have 4 times more surface area than commercial PVDF MF membrane, allowing for enhanced nanoparticles loading for chloro-organics degradation. The advanced functionalization method and process were also validated to be able to be scaled-up through the evaluation of full-scale functionalized membrane provided by Ultura Inc. California, USA. Nanofiltration (NF

Enhanced selection of micro-aerobic pentachlorophenol degrading granular sludge

Energy Technology Data Exchange (ETDEWEB)

Lv, Yuancai, E-mail: donkey1204@hotmail.com [State Key Laboratory of Pulp and Paper Engineering, College of Light Industry and Food Science, South China University of Technology, Guangzhou 510640 (China); Chen, Yuancai, E-mail: chenyc@scut.edu.cn [State Key Laboratory of Pulp and Paper Engineering, College of Light Industry and Food Science, South China University of Technology, Guangzhou 510640 (China); Ministry of Education Key Laboratory of Pollution Control and Ecological Remediation for Industrial Agglomeration Area, College of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); Song, Wenzhe, E-mail: songwenzhe007@126.com [Ministry of Education Key Laboratory of Pollution Control and Ecological Remediation for Industrial Agglomeration Area, College of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); Hu, Yongyou, E-mail: ppyyhu@scut.edu.cn [State Key Laboratory of Pulp and Paper Engineering, College of Light Industry and Food Science, South China University of Technology, Guangzhou 510640 (China); Ministry of Education Key Laboratory of Pollution Control and Ecological Remediation for Industrial Agglomeration Area, College of Environment and Energy, South China University of Technology, Guangzhou 510006 (China)

2014-09-15

Graphical abstract: In this work, an aerobic column reactor was placed before the USB to maintain micro-oxygen condition in the reactor and the micro-aerobic pentachlorophenol (PCP) degrading granular sludge under oxygen-limited conditions (0.1–0.2 mg L{sup −1}) was successfully obtained. PCP degradation by the micro-aerobic system was studied and the variance of microbial community was also discussed by using PCR-DGGE analysis. - Highlights: • Micro-aerobic granular sludge was cultivated in column-type combined reactors. • PCP biodegradation, VFA accumulation and biogas production were studied. • The function of Methanogenic archaeon in the system was investigated. • Fluctuation and diversity of microbial community were discussed by DGGE analysis. • The dominated microorganisms were identified by 16S rDNA sequences. - Abstract: Column-type combined reactors were designed to cultivate micro-aerobic pentachlorophenol (PCP) degrading granular sludge under oxygen-limited conditions (0.1–0.2 mg L{sup −1}) over 39-day experimental period. Micro-aerobic granular had both anaerobic activity (SMA: 2.34 mMCH{sub 4}/h g VSS) and aerobic activity (SOUR: 2.21 mMO{sub 2}/h g VSS). Metabolite analysis results revealed that PCP was sequentially dechlorinated to TCP, DCP, and eventually to MCP. Methanogens were not directly involved in the dechlorination of PCP, but might played a vital role in stabilizing the overall structure of the granule sludge. For Eubacteria, the Shannon Index (2.09 in inoculated granular sludge) increased both in micro-aerobic granular sludge (2.61) and PCP-degradation granular sludge (2.55). However, for Archaea, it decreased from 2.53 to 1.85 and 1.84, respectively. Although the Shannon Index demonstrated slight difference between micro-aerobic granular sludge and PCP-degradation granular sludge, the Principal Component Analysis (PCA) indicated obvious variance of the microbial composition, revealing significant effect of micro

The role of cow urine in the oviposition site preference of culicine and Anopheles mosquitoes

Directory of Open Access Journals (Sweden)

Kweka Eliningaya J

2011-09-01

Full Text Available Abstract Background Chemical and behavioural ecology of mosquitoes plays an important role in the development of chemical cue based vector control. To date, studies available have focused on evaluating mosquito attractants and repellents of synthetic and human origins. This study, however, was aimed at seasonal evaluation of the efficiency of cow urine in producing oviposition cues to Anopheles gambiae s.l. and Culex quinquefasciatus in both laboratory and field conditions. Methods Oviposition response evaluation in laboratory conditions was carried out in mosquito rearing cages. The oviposition substrates were located in parallel or in diagonal positions inside the cage. Urine evaluation against gravid females of An. arabiensis and Cx. quinquefasciatus was carried out at Day 1, Day 3 and Day 7. Five millilitres (mls of cow urine was added to oviposition substrate while de-chlorinated water was used as a control. In field experiments, 500 mls of cow urine was added in artificial habitats with 2500 mls of de-chlorinated water and 2 kgs of soil. The experiment was monitored for thirty consecutive days, eggs were collected daily from the habitats at 7.00 hrs. Data analysis was performed using parametric and non-parametric tests for treatments and controls while attraction of the oviposition substrate in each species was presented using Oviposition Activity Index (OAI. Results The OAI was positive with ageing of cattle urine in culicine species in both laboratory and field experiments. The OAI for anopheline species was positive with fresh urine. The OAI during the rainy season was positive for all species tested while in the dry season the OAI for culicine spp and Anopheles gambiae s.l., changed with time from positive to negative values. Based on linear model analysis, seasons and treatments had a significant effect on the number of eggs laid in habitats, even though the number of days had no effect. Conclusion Oviposition substrates treated with

Spatial and temporal dynamics of organohalide-respiring bacteria in a heterogeneous PCE-DNAPL source zone.

Science.gov (United States)

Cápiro, Natalie L; Löffler, Frank E; Pennell, Kurt D

2015-11-01

Effective treatment of sites contaminated with dense non-aqueous phase liquids (DNAPLs) requires detailed understanding of the microbial community responses to changes in source zone strength and architecture. Changes in the spatial and temporal distributions of the organohalide-respiring Dehalococcoides mccartyi (Dhc) strains and Geobacter lovleyi strain SZ (GeoSZ) were examined in a heterogeneous tetrachloroethene- (PCE-) DNAPL source zone within a two-dimensional laboratory-scale aquifer flow cell. As part of a combined remedy approach, flushing with 2.3 pore volumes (PVs) of 4% (w/w) solution of the nonionic, biodegradable surfactant Tween® 80 removed 55% of the initial contaminant mass, and resulted in a PCE-DNAPL distribution that contained 51% discrete ganglia and 49% pools (ganglia-to-pool ratio of 1.06). Subsequent bioaugmentation with the PCE-to-ethene-dechlorinating consortium BDI-SZ resulted in cis-1,2-dichloroethene (cis-DCE) formation after 1 PV (ca. 7 days), while vinyl chloride (VC) and ethene were detected 10 PVs after bioaugmentation. Maximum ethene yields (ca. 90 μM) within DNAPL pool and ganglia regions coincided with the detection of the vcrA reductive dehalogenase (RDase) gene that exceeded the Dhc 16S rRNA genes by 2.0±1.3 and 4.0±1.7 fold in the pool and ganglia regions, respectively. Dhc and GeoSZ cell abundance increased by up to 4 orders-of-magnitude after 28 PVs of steady-state operation, with 1 to 2 orders-of-magnitude increases observed in close proximity to residual PCE-DNAPL. These observations suggest the involvement of these dechlorinators the in observed PCE dissolution enhancements of up to 2.3 and 6.0-fold within pool and ganglia regions, respectively. Analysis of the solid and aqueous samples at the conclusion of the experiment revealed that the highest VC (≥155 μM) and ethene (≥65 μM) concentrations were measured in zones where Dhc and GeoSZ were predominately attached to the solids. These findings demonstrate

Enhanced selection of micro-aerobic pentachlorophenol degrading granular sludge

International Nuclear Information System (INIS)

Lv, Yuancai; Chen, Yuancai; Song, Wenzhe; Hu, Yongyou

2014-01-01

Graphical abstract: In this work, an aerobic column reactor was placed before the USB to maintain micro-oxygen condition in the reactor and the micro-aerobic pentachlorophenol (PCP) degrading granular sludge under oxygen-limited conditions (0.1–0.2 mg L −1 ) was successfully obtained. PCP degradation by the micro-aerobic system was studied and the variance of microbial community was also discussed by using PCR-DGGE analysis. - Highlights: • Micro-aerobic granular sludge was cultivated in column-type combined reactors. • PCP biodegradation, VFA accumulation and biogas production were studied. • The function of Methanogenic archaeon in the system was investigated. • Fluctuation and diversity of microbial community were discussed by DGGE analysis. • The dominated microorganisms were identified by 16S rDNA sequences. - Abstract: Column-type combined reactors were designed to cultivate micro-aerobic pentachlorophenol (PCP) degrading granular sludge under oxygen-limited conditions (0.1–0.2 mg L −1 ) over 39-day experimental period. Micro-aerobic granular had both anaerobic activity (SMA: 2.34 mMCH 4 /h g VSS) and aerobic activity (SOUR: 2.21 mMO 2 /h g VSS). Metabolite analysis results revealed that PCP was sequentially dechlorinated to TCP, DCP, and eventually to MCP. Methanogens were not directly involved in the dechlorination of PCP, but might played a vital role in stabilizing the overall structure of the granule sludge. For Eubacteria, the Shannon Index (2.09 in inoculated granular sludge) increased both in micro-aerobic granular sludge (2.61) and PCP-degradation granular sludge (2.55). However, for Archaea, it decreased from 2.53 to 1.85 and 1.84, respectively. Although the Shannon Index demonstrated slight difference between micro-aerobic granular sludge and PCP-degradation granular sludge, the Principal Component Analysis (PCA) indicated obvious variance of the microbial composition, revealing significant effect of micro-aerobic condition and

Photochemical degradation of PCBs in snow.

Science.gov (United States)

Matykiewiczová, Nina; Klánová, Jana; Klán, Petr

2007-12-15

exclusively to the photoreductive dechlorination process, is 1-2 orders of magnitude longer than that in surface waters when subjected to the equivalent solar radiation. However, in case that the concentration of the hydrogen peroxide in natural snow is sufficient, the photoinduced oxidation process could succeed the photoreductive dechlorination and evaporative fluxes as the major sink.

Synergistic degradation of chlorinated hydrocarbons with microorganisms and zero valent iron

Science.gov (United States)

Schöftner, Philipp; Summer, Dorothea; Leitner, Simon; Watzinger, Andrea; Wimmer, Bernhard; Reichenauer, Thomas

2016-04-01

Sites contaminated with chlorinated hydrocarbons (CHC) are located mainly within build-up regions. Therefore in most cases only in-situ technologies without excavation of soil material can be used for remediation. This project examines a novel in-situ remediation method, in which the biotic degradation via bacteria is combined with abiotic degradation via zero-valent iron particles (ZVI). ZVI particles are injected into the aquifer where CHC-molecules are reductively dechlorinated. However Fe0 is also oxidized by reaction with water leading to generation of H2 without any CHC degradation. To achieve biotic degradation often strictly anaerobic strains of the bacteria Dehalococcoides are used. These bacteria can dechlorinate CHC by utilizing H2. By combining these processes the H2, produced during the anaerobic corrosion of Fe0, could be used by bacteria for further CHC degradation. Therefore the amount of used Fe0 and as a consequence also remediation costs could be reduced. Additionally the continuous supply of H2 could make the bacterial degradation more controllable. Different Fe0 particles (nano- and micro-scale) were tested for their perchloroethene (PCE) degradation rate and H2 production rate in microcosms. PCE-degradation rate by different bacterial cultures was investigated in the same microcosm system. In course of these experiments the 13C enrichment factors of the PCE degradation of the different particles and cultures were determined to enable the differentiation of biotic and abiotic degradation. Preliminary results showed, that the nano-scale particles reacted faster with PCE and water than their micro-scaled counterparts. The PCE degradation via micro-scaled particles lead to 13C enrichment factors in the range of -3,6 ‰ ± 0,6 to -9,5 ‰ ± 0,2. With one of the examined bacterial cultures a fast reduction of PCE to ethene was observed. Although PCE and TCE were completely degraded by this culture the metabolites DCE and VC could still be detected

Cl and C isotope analysis to assess the effectiveness of chlorinated ethene degradation by zero-valent iron: Evidence from dual element and product isotope values

International Nuclear Information System (INIS)

Audí-Miró, Carme; Cretnik, Stefan; Otero, Neus; Palau, Jordi; Shouakar-Stash, Orfan; Soler, Albert

2013-01-01

Highlights: ► TCE and cis-DCE Cl isotope fractionation was investigated for the first time with ZVI. ► A C–Cl bond is broken in the rate-limiting step during ethylene ZVI dechlorination. ► Dual C/Cl isotope plot is a promising tool to discriminate abiotic degradation. ► Product-related carbon isotopic fractionation gives evidence of abiotic degradation. ► Hydrogenolysis and β-dichloroelimination pathways occur simultaneously. - Abstract: This study investigated C and, for the first time, Cl isotope fractionation of trichloroethene (TCE) and cis-dichloroethene (cis-DCE) during reductive dechlorination by cast zero-valent iron (ZVI). Hydrogenolysis and β-dichloroelimination pathways occurred as parallel reactions, with ethene and ethane deriving from the β-dichloroelimination pathway. Carbon isotope fractionation of TCE and cis-DCE was consistent for different batches of Fe studied. Transformation of TCE and cis-DCE showed Cl isotopic enrichment factors (ε Cl ) of −2.6‰ ± 0.1‰ (TCE) and −6.2‰ ± 0.8‰ (cis-DCE), with Apparent Kinetic Isotope Effects (AKIE Cl ) for Cl of 1.008 ± 0.001 (TCE) and 1.013 ± 0.002 (cis-DCE). This indicates that a C–Cl bond breakage is rate-determining in TCE and cis-DCE transformation by ZVI. Two approaches were investigated to evaluate if isotope fractionation analysis can distinguish the effectiveness of transformation by ZVI as opposed to natural biodegradation. (i) Dual isotope plots. This study reports the first dual (C, Cl) element isotope plots for TCE and cis-DCE degradation by ZVI. The pattern for cis-DCE differs markedly from that reported for biodegradation of the same compound by KB-1, a commercially available Dehalococcoides-containing culture. The different trends suggest an expedient approach to distinguish abiotic and biotic transformation, but this needs to be confirmed in future studies. (ii) Product-related isotope fractionation. Carbon isotope ratios of the hydrogenolysis product cis

Degradation of 2,4,5-trichlorophenoxyacetic acid in aqueous solution by 60Co-γ irradiation

International Nuclear Information System (INIS)

Liu Yuanxia; Yu Yuan; Bao Huaying

2010-01-01

2,4,5-trichlorophenoxyacetic acid(2,4,5-T) is one kind of phenoxy-hydroxy-acid herbicides, also is one kind of Endocrine Disrupting Chemicals. The degradation of 2,4,5-T in aqueous solution by 60 Co-γ irradiation was investigated in the paper. The degradation effect of different influencing factors, such as absorbed dose and irradiation aura, was studied respectively. The degradation products were preliminarily analyzed by High Performance Liquid Chromatography, UV-Vis spectrophotometer and Ion Chromatography. The results showed that 2,4,5-T could be effectively degraded in aqueous solutions by 60 Co-γ irradiation. Meanwhile, the Chloride ion was detected in the solution, whose concentration increased with the growth of absorbed dose. It was found that although both e-aq and ·OH originated from water radiolysis could eliminate 2,4,5-T, the dechlorination effect and the degradation products were different. (authors)

Permeable reactive barrier of surface hydrophobic granular activated carbon coupled with elemental iron for the removal of 2,4-dichlorophenol in water.

Science.gov (United States)

Yang, Ji; Cao, Limei; Guo, Rui; Jia, Jinping

2010-12-15

Granular activated carbon was modified with dimethyl dichlorosilane to improve its surface hydrophobicity, and therefore to improve the performance of permeable reactive barrier constructed with the modified granular activated carbon and elemental iron. X-ray photoelectron spectroscopy shows that the surface silicon concentration of the modified granular activated carbon is higher than that of the original one, leading to the increased surface hydrophobicity. Although the specific surface area decreased from 895 to 835 m(2)g(-1), the modified granular activated carbon could adsorb 20% more 2,4-dichlorophenol than the original one did in water. It is also proven that the permeable reactive barrier with the modified granular activated carbon is more efficient at 2,4-dichlorophenol dechlorination, in which process 2,4-dichlorophenol is transformed to 2-chlorophenol or 4-chlorophenol then to phenol, or to phenol directly. Copyright © 2010 Elsevier B.V. All rights reserved.

Inter- and intramolecular deuterium isotope effects on the cytochrome P-450-catalyzed oxidative dehalogenation of 1,1,2,2-tetrachloroethane

International Nuclear Information System (INIS)

Hales, D.B.; Ho, B.; Thompson, J.A.

1987-01-01

The oxidation of 1,1,2,2-tetrachloroethane to dichloroacetic acid was investigated with rat liver microsomes and purified cytochrome P-450. Deuterium substitution had no effect on Km values, but both the inter- and intramolecular isotope effects (kH/kD) on Vmax were in the range 5.7-6.1. The equivalence of the inter- and intramolecular values indicates that 6.0 may be a good estimate of the intrinsic isotope effect. The intermolecular kH/kD value for the conversion of 1,1,2,2-trichloroethane and its 1- 2 H analog to chloroacetic acid was 5.5. These data, and the finding that 1 atom of 18 O was incorporated into the product when TCEA was oxidized in an 18 O 2 atmosphere, support an oxidative dechlorination mechanism that involves hydrogen atom abstraction by the P-450 intermediate oxo complex

Treatability study for removal of leachable mercury in crushed fluorescent lamps

International Nuclear Information System (INIS)

Bostick, W.D.; Beck, D.E.; Bowser, K.T.

1996-02-01

Nonserviceable fluorescent lamps removed from radiological control areas at the Oak Ridge Department of Energy facilities have been crushed and are currently managed as mixed waste (hazardous and radiologically contaminated). We present proposed treatment flowsheets and supporting treatability study data for conditioning this solid waste residue so that it can qualify for disposal in a sanitary landfill. Mercury in spent fluorescent lamps occurs primarily as condensate on high-surface-area phosphor material. It can be solubilized with excess oxidants (e.g., hypochlorite solution) and stabilized by complexation with halide ions. Soluble mercury in dechlorinated saline solution is effectively removed by cementation with zero-valent iron in the form of steel wool. In packed column dynamic flow testing, soluble mercury was reduced to mercury metal and insoluble calomel, loading > 1.2 g of mercury per grain of steel wool before an appreciable breakthrough of soluble mercury in the effluent

Advanced hydraulic fracturing methods to create in situ reactive barriers

International Nuclear Information System (INIS)

Murdoch, L.

1997-01-01

This article describes the use of hydraulic fracturing to increase permeability in geologic formations where in-situ remedial action of contaminant plumes will be performed. Several in-situ treatment strategies are discussed including the use of hydraulic fracturing to create in situ redox zones for treatment of organics and inorganics. Hydraulic fracturing methods offer a mechanism for the in-situ treatment of gently dipping layers of reactive compounds. Specialized methods using real-time monitoring and a high-energy jet during fracturing allow the form of the fracture to be influenced, such as creation of assymmetric fractures beneath potential sources (i.e. tanks, pits, buildings) that should not be penetrated by boring. Some examples of field applications of this technique such as creating fractures filled with zero-valent iron to reductively dechlorinate halogenated hydrocarbons, and the use of granular activated carbon to adsorb compounds are discussed

Assessing chlorinated ethene degradation in a large scale contaminant plume by dual carbon–chlorine isotope analysis and quantitative PCR

DEFF Research Database (Denmark)

Hunkeler, D.; Abe, Y.; Broholm, Mette Martina

2011-01-01

The fate of chlorinated ethenes in a large contaminant plume originating from a tetrachloroethene (PCE) source in a sandy aquifer in Denmark was investigated using novel methods including compound-specific carbon and chlorine isotope analysis and quantitative real-time polymerase chain reaction (q...... reduction by pyrite as indicated by the formation of cDCE and stable carbon isotope data. TCE and cDCE showed carbon isotope trends typical for reductive dechlorination with an initial depletion of 13C in the daughter products followed by an enrichment of 13C as degradation proceeded. At 1000 m downgradient......DCE. The significant enrichment of 13C in VC indicates that VC was transformed further, although the mechanismcould not be determined. The transformation of cDCEwas the rate limiting step as no accumulation of VC occurred. In summary, the study demonstrates that carbon–chlorine isotope analysis and qPCR combinedwith...

Treatment of a suspension of PCB contaminated soil using iron nanoparticles and electric current

DEFF Research Database (Denmark)

Comes, Helena I.; Ottosen, Lisbeth M.; Ribeiro, Alexandra B.

2015-01-01

Contaminated soils and sediments with polychlorinated biphenyls (PCB) are an important environmental problem due to the persistence of these synthetic aromatic compounds and to the lack of a cost-effective and sustainable remediation technology. Recently, a new experimental setup has been proposed...... using electrodialytic remediation and iron nanoparticles. The current work compares the performance of this new setup (A) with conventional electrokinetics (setup B). An historically contaminated soil with an initial PCB concentration of 258 mu g kg-1 was treated during 5, 10, 20 and 45 d using...... different amounts of iron nanoparticles in both setups A and B. A PCB removal of 83% was obtained in setup A compared with 58% of setup B. Setup A also showed additional advantages, such as a higher PCB dechlorination, in a shorter time, with lower nZVI consumption, and with the use of half of the voltage...

Partitioning of K, Cl, S and P during combustion of poplar and brassica energy crops

DEFF Research Database (Denmark)

Díaz-Ramírez, Maryori; Jappe Frandsen, Flemming; Glarborg, Peter

2014-01-01

K-, Cl-, S- and P-release from a herbaceous (brassica) and a short rotation coppice (poplar) cultivated in the Mediterranean region, have been investigated under combustion conditions [500-1100 °C]. Contrary to brassica, Cl- and S-release from poplar were substantial for all temperatures tested....... Low-temperature [500-700 °C] Cl-release from the high-Cl brassica appeared to be primarily limited by the fuel chemical composition and secondarily by interactions of the ash-forming elements with the fuel organic matrix. Below 700 °C, Cl-release was nearly 50%, whereas complete dechlorination...... resulted around 800 °C. S-release from brassica was up to 40% at low temperature. Above 1000 °C, additional S-release was observed presumably by sulfate dissociation. K-release was linked to Cl-release around 700 °C and, gradually increased afterwards. At 1100 °C, nearly 60% of K in poplar was retained...

Degradation of persistent organochlorine pollutants by gamma-radiation and the possible use for waste water treatment

International Nuclear Information System (INIS)

Vollner, L.; Rohleder, H.; Korte, F.

1975-01-01

Some organochlorine pesticides, polychlorinated biphenyls and related chemicals have become ubiquitous pollutants by their persistence and are common contaminants in waste waters. Since gamma-radiation represents a possible treatment for decontamination, radiation yield and degradation chemistry were investigated. The pattern of hexane extractable compounds obtained from acetone-water and from pure water solutions are not very different when compared by GC-analysis. Dechlorination and dehydrochlorination were found to be the most important mechanisms of the first attack. The complete destruction of chlorine pesticides and of other chlorinated hydrocarbons (as PCBs) at the ppm-level demand considerable radiation doses. G-values for dieldrin and its hexane extractable degradation products are 1 x 10 -3 in deionized water and 3.6 x 10 -5 in twice-distilled water. G-values for aldrin, lindane, chlordane and PCBs are in the same order of magnitude. (orig./HK) [de

Metabolic fate of 14-C-fenitrothion in a rice field model ecosystem

International Nuclear Information System (INIS)

Nashriyah binti Mat; Nambu, K.; Miyashita, T.; Sakata, S.; Ohshima, M.

1991-01-01

Pesticide fenitrothion (Sumithion sup R)is widely used to control rice stem borer and other pests. Its metabolic fate and degradation was studied using the sup 14 C-ring labelled fenitrothion in a model ecosystem consisting of Takarazuka paddy field soil, rice plant (Oryza sativa var. nihonbare), carp fish (Cyprinus carpio L.) and dechlorinated water. Radioactive fenitrothion was applied at a normal rate as used by Japanese farmers and samples of rice plant, fish soil and water were analysed after ten days of application. Fenitrothion was readily metabolized in rice plant and fish and also readily degraded to a number of metabolites in water and flooded soil. Most of the radioactivity applied was found in the soil component of the ecosystem. A trace amount of fenitrooxon, the activated metabolite of fenitrothion was detected only in soil and water. A possible metabolic pathway of fenitrothion in the rice model ecosystem was proposed

Treatability study for removal of leachable mercury in crushed fluorescent lamps

Energy Technology Data Exchange (ETDEWEB)

Bostick, W.D.; Beck, D.E.; Bowser, K.T. [and others

1996-02-01

Nonserviceable fluorescent lamps removed from radiological control areas at the Oak Ridge Department of Energy facilities have been crushed and are currently managed as mixed waste (hazardous and radiologically contaminated). We present proposed treatment flowsheets and supporting treatability study data for conditioning this solid waste residue so that it can qualify for disposal in a sanitary landfill. Mercury in spent fluorescent lamps occurs primarily as condensate on high-surface-area phosphor material. It can be solubilized with excess oxidants (e.g., hypochlorite solution) and stabilized by complexation with halide ions. Soluble mercury in dechlorinated saline solution is effectively removed by cementation with zero-valent iron in the form of steel wool. In packed column dynamic flow testing, soluble mercury was reduced to mercury metal and insoluble calomel, loading > 1.2 g of mercury per grain of steel wool before an appreciable breakthrough of soluble mercury in the effluent.