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Palladium-facilitated electrolytic dechlorination of 2-chlorobiphenyl using a granular-graphite electrode.

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 electro-deposited from the K2PdCl6 in the solution and at a Pd-deposited granular-graphite electrode. Using the Pd-deposited graphite cathode in the membrane reactor for a sequence of experiments, each was conducted under a lower current than in the previous one, and the rate of dechlorination became slower in each consecutive experiment. At the end of this sequence, a duplicate experiment showed a loss of activity of the Pd-deposited granular-graphite cathode. In the experiments of dechlorination while Pd was deposited at the granular-graphite electrode, the rate of dechlorination increased with increases of the initial K2PdCl6 concentration and of the applied cathode potential. In each experiment, the dechlorination of 2-Cl BP was relatively fast at the beginning, as demonstrated in an experiment in which 66.4% of 2-Cl BP was dechlorinated within 4h, but the rate of dechlorination decreased over the time. This decrease can be described with two stages of exponential decrease. The values of the rate constant in the first stage varies with the applied potential and the initial K2PdCl6 concentration, but the values of the rate constant in the second stage do not show any dependence on the potential and the K2PdCl6 concentration. The current efficiency of dechlorination was improved by applying part-time current to the electrodes.

Biphenyl Compounds↗

Determination of chlorine dioxide in water by gas chromatography-mass spectrometry.

A sensitive gas chromatographic method has been established for the determination of chlorine dioxide in water. With weak basic conditions (pH 9.0), chlorine dioxide reacts with iodide to form iodine, which reacts with 2,6-dialkylphenol to form 4-iodo-2,6-dialkylphenol. The volatile organic derivative was extracted with ethyl acetate, and then measured by gas chromatography-mass spectrometry (GC-MS). The reaction of the active proton of 2,6-dialkylphenols (2,6-dimethylphenol, 2,6-di-isopropylphenol and 2,6-di-tert-butylphenol) with iodine was tested, and compared to each other in terms of reactivity and stability of the derivatives. 2,6-dimethylphenol showed rapid reaction with iodine, and its derivative was stable for 2 weeks. The detection limit of chlorine dioxide in water was about 1.0 ng/mL, and the calibration curve showed good linearity with r2 = 0.998. The existent concentration of chlorine dioxide in water was calculated from multiplying the concentration calculated from the calibration curve of 4-iodo-2,6-dimethylphenol by 0.544. The method was sensitive, reproducible and simple enough to permit the reliable analysis of chlorine dioxide at the low ng/mL level in water.

Calibration↗

Rapid semi-continuous calibration and field test of membrane-enclosed silicone collector as passive water sampler.

The new membrane-enclosed silicone collector (MESCO) was, in two different configurations with respect to the thickness of low-density polyethylene membrane used, subject to serial batch extraction tests to obtain (preliminary) sampling rates for estimating water concentrations of selected chlorinated organic compounds and polycyclic aromatic hydrocarbons. This rapid calibration procedure is simple to implement compared to experiments in a flow-through apparatus and yielded reasonable sampling rates in the range of 50 microL-2 mL per hour for the compounds tested. The new MESCO formats were also exposed for 28 days in the polluted creek to test their field performance. For priority contaminants of special interest, alpha-hexachlorocyclohexane and hexachlorobenzene, the time-weighted average concentrations derived from the freshly calibrated sampling devices agree well with those obtained by conventional water analysis of spot samples.

Calibration↗

Retention behaviour of volatile C(1)-C(3) fluoroalkanes upon selected preconcentration adsorbents I. Carbon molecular sieves and activated charcoals.

The retention behaviour of several gaseous fluorinated greenhouse gases on carbon-based adsorbents is presented. Retention, calculated on the basis of compound breakthrough volume (BTV), is dependent on the molecular composition of the adsorbate, with compounds possessing chlorine or polarizable hydrogens being better retained than those possessing higher fluorine content. Of the adsorbents tested the carbon molecular sieves (CMSs) of highest surface area show greater retention than those with lower area. Retention of fluorocarbons is generally higher on activated charcoals but this adsorbent type can cause irreversible retention, possible degradation and is more difficult to use practically due to its heterogeneous composition. These breakthrough volume results can be used to determine the best combination and quantities of each adsorbent that can be used within a preconcentration device with a view to developing an analytical system for the determination of fluorocarbon gases in low concentration air samples.

Adsorption↗

Screening ecological risk assessment for the benthic community in the Venice lagoon (Italy).

According to the risk hypothesis: the sediment as source of potential risk for the benthic community, an Ecological Risk Assessment (ERA) based on the quotient method was undertaken. The exposure of the benthic community to different classes of pollutants (metals, chlorinated organic compounds and polynuclear aromatic hydrocarbons) was inferred by estimating the pollutant stocks in the top 15-cm sediment of the whole Venice lagoon, after application of geostatistic techniques. The risk was calculated by comparing the sediment exposure profiles with the ecotoxicological benchmarks for benthic organisms. Kriging based maps of the spatial distribution of the estimated risk for the benthic community over the whole lagoon were obtained. The highest risk, found in the areas nearest to the sources of contamination (e.g., the industrial district of Porto Marghera and the river mouths), was posed by mercury (40% of the sampling stations showed exposure levels higher than the Probable Effect Level), arsenic and nickel (75% of the sampling stations exceeded the Threshold Effect Level).

Animals↗

Atmospheric concentrations of the Cl atom, ClO radical, and HO radical in the coastal marine boundary layer.

Atmospheric concentrations of chlorine atom (Cl*), chlorine monoxide radical (ClO*), and hydroxyl radical (HO*) in the coastal marine boundary layer are estimated in this study. A steady-state approach to their concentrations in equilibrium with other atmospheric chemical species is used. Measurements of atmospheric trace species, HCl, Cl2, HCHO, H2O2, CH3OOH, CH4, CO, SO2, NO, NO2, and O3, were performed at four sites in Taiwan during the spring of 1999. The results indicate that the concentrations of the Cl* atom and the ClO* and HO* radicals decrease significantly with cloud cover. The calculated average daytime concentrations of Cl*, ClO*, and HO* are 3 x 10(5), 1 x 10(7), and 6 x 10(5) molecules/cm3, respectively. Due to the high reactivity of Cl* with hydrocarbons and its concentration level competitive to that of HO*, Cl* should be a significant sink for hydrocarbons in these cases.

Air Pollutants↗

A novel pesticide-induced conformational state of the oestrogen receptor ligand-binding domain, detected by conformation-specific peptide binding.

The diverse effects of different natural and synthetic oestrogen receptor ligands depend on induction of different receptor conformations, allowing differential interactions with other transcription factors. Different conformations of the oestrogen receptor ligand binding domains can be monitored by conformation-specific binding to peptides selected from phage-displayed peptide libraries. We now report that a group of chlorinated pesticides, including 2,4-dichlorodiphenyl-dichloroethylene, induces a peptide recognition pattern different from those induced by any one of the classical oestrogen receptor ligands. The pesticide-complexed oestrogen receptors recognized peptides reacting with the receptors complexed both with the natural oestrogen 17beta-oestradiol and with the synthetic partial antagonist 4-hydroxy-tamoxifen, respectively, indicating that the pesticide-induced conformation shares features with both the 17beta-oestradiol- and the 4-hydroxy-tamoxifen-induced conformations. The substitution H524A in the ligand binding domain conferred the pesticide-specific peptide recognition pattern and transactivation activity to the oestradiol- and the 4-hydroxy-tamoxifen-complexed receptors, indicating that one important determinant of the pesticide-induced conformation is a lack of stabilisation of any one particular receptor conformation by ligand interaction with H524, which is known to interact with both oestradiol and 4-hydroxy-tamoxifen. Thus, peptide binding analyses of oestrogen receptor conformations induced by environmental endocrine disruptors can give novel information about molecular mechanisms of oestrogen action in general.

Amino Acid Substitution↗

The use of chlorine dioxide to control Alicyclobacillus acidoterrestris spores in aqueous suspension and on apples.

Alicyclobacillus acidoterrestris, a thermoacidophilic, spore-forming bacterium, has been identified as a spoilage organism in commercial, pasteurized fruit juices. This study was undertaken to evaluate chlorine dioxide for reducing numbers of A. acidoterrestris spores on laboratory media and on apples. A. acidoterrestris spores in aqueous suspension and on apple surfaces of four different cultivars were treated with several concentrations of chlorine dioxide. Spores in aqueous suspension treated with 40 ppm for 5 min were reduced by more than 4 log. Treatment with 80 ppm for 1 min and 120 ppm for 30 s resulted in about 1.8 log and 4.8 log reductions of spore viability, respectively, and treatment at 80 and 120 ppm for 5 min reduced spore viability to undetectable levels (<0.7 log CFU/ml). When applied to the surfaces of four different apple cultivars ('Red Delicious', 'Golden Delicious', 'Gala', and 'Fuji'), 40 ppm free chlorine dioxide reduced A. acidoterrestris spore numbers by 1.5, 3.2, 4.5, >4.8 log after 1-, 2-, 3-, and 4-min treatments, respectively. Spore numbers were reduced by >4.8 log with 120 ppm free chlorine dioxide after only 1-min treatment. However, there was no significant difference between apple cultivars (P>0.05) on spore reduction. These results show the great effectiveness of chlorine dioxide in controlling A. acidoterrestris spores both in aqueous suspension and on apple surfaces. There was no synergistic effect on spore reduction when chlorine dioxide treatment of aqueous suspension was followed by heat.

Beverages↗

Efficacy of chlorine dioxide gas against Alicyclobacillus acidoterrestris spores on apple surfaces.

Alicyclobacillus acidoterrestris is a thermophilic spore-forming bacterium that spoils acidic juices. In the orchard, apples may be contaminated with spores which can potentially grow in the resulting juice and cause spoilage. This study was undertaken to evaluate the efficacy of gaseous chlorine dioxide against A. acidoterrestris spores on apple surfaces. A. acidoterrestris spores were inoculated onto apple surfaces and were placed at room temperature, in a tightly sealed chamber containing a chlorine dioxide generating sachet, low, medium, or high release, for 30 min, 1, 2, and 3 h. After exposure, surviving spores were enumerated on K agar. Chlorine dioxide treated apples were stored at 4 degrees C for 7 days to assess the effect on visual quality. Inoculated, untreated apples served as the visual quality control. After exposure to high and medium release sachets for 1 h, spores were reduced to an undetectable level, a 5 log10 reduction; however, visual quality was compromised. After 1, 2, and 3 h of exposure to low release sachets, spore reductions were 2.7, 3.7, and 4.5 log10, respectively. And, after 7 days of storage, there were no significant visual quality differences between the apples exposed to low release sachet for all treatment times when compared to the control. Gaseous chlorine dioxide can effectively reduce viable A. acidoterrestris spores on apple surfaces. Due to the efficacy and easy of use, chlorine dioxide gas sachets may be useful to maintain apple quality during storage and shipping.

Anti-Bacterial Agents↗

Survival of Enterobacter sakazakii on fresh produce as affected by temperature, and effectiveness of sanitizers for its elimination.

A study was done to determine the survival characteristics of Enterobacter sakazakii on the surface of apples, cantaloupes, strawberries, lettuce, and tomatoes stored at 4, 12, and 25 degrees C for 8-28 days. Populations significantly decreased (p or=50 microg/ml, were equivalent in killing E. sakazakii on apples. Populations of E. sakazakii on apples treated with 10 microg/ml chlorine dioxide for 1 or 5 min were significantly reduced (p or=4.00 log CFU/apple. Reductions of >or=3.70 log CFU/tomato were achieved by treatment with 10 microg/ml chlorine or chlorine dioxide or 40 microg/ml Tsunami 200 for 5 min. Reductions in populations of E. sakazakii on lettuce treated with chlorine at 10, 50, and 100 microg/ml for 1 min ranged from 1.61 to 2.50 log CFU/sample (26+/-4 g), compared to populations remaining on lettuce washed with water. Chlorine was less effective in killing E. sakazakii on lettuce than on apples or tomatoes. Treatment of lettuce with Tsunami 200 (40 and 80 microg/ml) for 5 min caused a reduction of >or=5.31 log CFU/sample. Results provide insights to predicting survival characteristics of E. sakazakii on produce and the efficacy of sanitizers in killing the bacterium.

Chlorine↗

Chlorinated river and lake water extract caused oxidative damage, DNA migration and cytotoxicity in human cells.

Consumption of chlorinated drinking water is suspected to be associated with adverse health effects, including mutations and cancer. In the present study, the genotoxic potential of water from Donghu lake, Yangtze river and Hanjiang river in Wuhan, an 8-million metropolis in China, was investigated using HepG2 cells and the alkaline version of the comet assay. It could be shown that all water extracts caused dose-dependent DNA migration in concentrations corresponding to dried extracts of 0.167-167 ml chlorinated drinking water per ml medium. To explore whether the intracellular redox status is regulated by chlorinated drinking water, we determined lipid peroxidation (LPO) and depletion of reduced glutathione (GSH). The malondialdehyde (thiobarbituric acid (TBA)-reactive aldehydes) concentration increased after chlorinated drinking water treatment of HepG2 cells in a dose-dependent manner, the GSH content decreased. The activity of lactate dehydrogenase (LDH) increased in chlorinated drinking water treated HepG2 cells indicating cytotoxicity. In accordance with former studies which dealt with in vivo and in vitro micronucleus induction the present study shows that chlorinated drinking water from polluted raw water may entail genetic risks.

China↗

Batch-test study on the dechlorination of 1,1,1-trichloroethane in contaminated aquifer material by zero-valent iron.

Chlorinated aliphatic hydrocarbons are common groundwater contaminants. One possible remediation option is in-situ reductive dechlorination by zero-valent iron, either by direct injection or as reactive barriers. Chlorinated ethenes (tetrachloroethene: PCE; trichloroethene: TCE) have received extensive attention in this context. However, another common groundwater pollutant, 1,1,1-trichlorethane (TCA), has attracted much less attention. We studied TCA reduction by three types of granular zero-valent irons in a series of batch experiments using polluted groundwater, with and without added aquifer material. Two types of iron were able to reduce TCA completely with no daughter product concentration increases (1,1-dichloroethane: DCA; chloroethane: CA). One type of iron showed slower reduction, with intermediate rise of DCA and CA concentrations. When evaluating the formation of daughter products, the tests on the groundwater alone showed different results than the groundwater plus aquifer batches: DCA did not temporarily accumulate in the batches with added aquifer material, contrary to the batches without added aquifer material. 1,1-dichloroethene (DCE, also present in the groundwater as an abiotic degradation product of TCA) was also reduced slower in the batches without added aquifer material than in the batches with aquifer material. Redox potentials gradually decreased to low values in batches with aquifer material without iron, while the batches with groundwater alone maintained a constant higher redox potential. Either adsorption processes or microbiological activity in the samples could explain these phenomena. Polymerase Chain Reaction (PCR: a targeted gene probe technique) for chlorinated aliphatic compound (CAH)-degrading bacteria confirmed the presence of Dehalococcoides sp. (chloroethene-degraders) but was negative for Desulfobacterium autotrophicum (a known co-metabolic TCA degrader). DCA reduction was rate determining: first-order half-lives of 300-350 h were observed. TCA was fully removed within hours. CA is resistant to reduction by zero-valent iron but it is known to hydrolyze easily. Since CA did not accumulate in our batches, it may have disappeared by the latter mechanism or it may not have formed as a major daughter product.

Acetates↗

Mass removal of chlorinated ethenes from rough-walled fractures using permanganate.

In situ chemical oxidation (ISCO) employing permanganate is an emerging technology that has been successful at enhancing mass removal from DNAPL source zones in unconsolidated media at the pilot-scale. The focus of this study was to evaluate the applicability of flushing a permanganate solution across two single vertical fractures in a laboratory environment to remove free phase DNAPL. The fracture experiments were designed to represent a portion of a larger fractured aquifer system impacted by a near-surface DNAPL spill over a shallow fractured rock aquifer. Each fracture was characterized by hydraulic and tracer tests, and the aperture field for one of the fractures was mapped using a co-ordinate measurement machine. Following DNAPL emplacement, a series of water and permanganate flushes were performed. To support observations from the fracture experiments, a set of batch experiments was conducted. The data from both fracture experiments showed that the post-oxidation effluent concentration was not impacted by the oxidant flush; however, changes in the aperture distribution, flow field, and flow rate were observed. These changes resulted in a significant decrease to the mass loading from the fractures, and were attributed to the build-up of oxidation by-products (manganese oxides and carbon dioxide) within the fracture which was corroborated by the batch experiment data and visual examination of the walls of one fracture. These results provide insight into the potential impact that a permanganate solution and oxidation by-products can have on the aperture distribution within a fracture and on DNAPL mass transfer rates. A permanganate flush or injection completed within a fractured rock aquifer may lead to the development of an insoluble product adjacent to the DNAPL which results in the reduction or complete elimination of advective regions near the DNAPL and reduces mass transfer rates. This outcome would have significant implications on the plume generating potential of the remaining DNAPL.

Carbon Dioxide↗

Assessment of biogeochemical natural attenuation and treatment of chlorinated solvents, Altus Air Force Base, Altus, Oklahoma.

Biogeochemical reductive dechlorination (BiRD) is a newly recognized method for the remediation or natural attenuation of chlorinated solvents. Chlorinated solvents are rapidly treated by abiotic reaction with reduced mineral iron sulfides. Iron sulfides are formed by naturally occurring sulfate-reducing bacteria when sufficient SO(4)(2-) and organic carbon are present or supplied to sediments containing mineral iron. An example of site characterization focusing on BiRD is presented focusing on mineral phases. Methods demonstrated here may be employed at other sites to evaluate naturally occurring BiRD or to evaluate an engineered BiRD remediation. A field investigation was performed at a TCE contaminated site at Altus AFB with naturally high concentrations of SO(4)(2-) and Fe(III) minerals and where an accidental fuel spill provided organic carbon. In the area of this fuel spill significant mineral iron sulfides were found, sulfate was almost completely removed, and TCE was absent. Only small amounts of daughter products were found, further indicating that the BiRD pathway was operative. Mass balance data indicates all of the remaining TCE (182 kg) could be treated by the remaining FeS (66.5 kg) in the upper aquifer; however, the FeS was not co-located with TCE to enable complete reaction. Laboratory microcosm tests with FeS amended and FeS-rich sediment from Altus AFB also suggest that BiRD is capable of destroying TCE. The results suggest that an engineered BiRD treatment is possible for this site.

Biodegradation, Environmental↗

Source-zone characterization of a chlorinated-solvent contaminated Superfund site in Tucson, AZ.

An extensive site-characterization project was conducted at a large chlorinated-solvent contaminated Superfund site in Tucson, AZ. The project consisted of several components, including traditional site-characterization activities, tracer tests, laboratory experiments conducted with core material collected from the site, and mathematical modeling. The primary focus of the work presented herein is the analysis of induced-gradient contaminant elution tests conducted in a source zone at the site, investigation of the potential occurrence of immiscible liquid in the saturated zone, characterization of the relationship between mass flux reduction and mass removal, and evaluation of the impact of source-zone management on site remediation. The results of the present study, along with those of prior work, indicate that immiscible liquid is likely present in the saturated zone at the site source zones. Extensive tailing and rebound was observed for the contaminant-elution tests, indicating nonideal transport and mass-transfer behavior. The elution data were analyzed with a source-zone-scale mathematical model, and the results indicated that nonideal immiscible-liquid dissolution was the primary cause of the observed behavior. The time-continuous relationship between mass flux reduction and mass removal associated with the plume-scale pump-and-treat operation exhibited an initial large drop in mass flux with minimal mass removed, followed by a period of minimal mass flux reduction and a second period of large reduction. This behavior reflects the impact of both source-zone and aqueous-plume mass removal dynamics. Ultimately, a greater than 90% reduction in mass flux was achieved for a mass removal of approximately 50%. The influence of source-zone management on site remediation was evaluated by conducting two predictive simulations, one for which the source zones were controlled and one for which they were not. A plume-scale model was used to simulate the composite contaminant concentrations associated with groundwater extracted with the pump-and-treat system, which were compared to measured data. The information generated from this study was used to enhance the site conceptual model, help optimize operation of the pump-and-treat system, and evaluate the utility of source-zone remediation.

Arizona↗

Upflow column reactor design for dechlorination of chlorinated pulping wastes by Penicillium camemberti.

A Penicillium camemberti strain isolated in our laboratory has been studied for its ability to degrade chlorinated pulping wastes, presumably containing a variety of chlorinated polyphenols. In batch tests, the highest removals (76% AOX, 61% color and 65% TOC) were obtained with 0.2 g/l feed acetate concentration. The tendency of the fungus to dechlorinate bleachery effluents better under non-shaking conditions and to attach onto surfaces suggested the use of immobilized cells rather than freely suspended ones in further exploitation of the process. An upflow glass wool packed column reactor established with this fungus could be operated for nearly two years in the laboratory. At best around 70% AOX could be removed from chlorinated pulping wastes in 7.3 h of contact with no aeration and with a minimal amount of carbon supplement (0.2 g/l). Finally, an asymptotic mathematical formula for determining Michaelis-Menten kinetic rates has been derived. The kinetic rates K(m) (the Michaelis constant or saturation constant for the substrate) and V(m) (the product of maximum rate for the enzymatic reaction and biomass concentration) were then calculated as 126.386 mg/l and 2.83017 mg/lh, respectively.

Bioreactors↗

Fuzzy synthetic evaluation of disinfection by-products--a risk-based indexing system.

Disinfection by-products (DBPs) are formed when disinfectants such as chlorine, chloramine, and ozone react with organic matter in water. Chlorine being the most common disinfectant used in the drinking water industry worldwide, significant attention has been focused on chlorinated DBPs. A new indexing method using fuzzy synthetic evaluation is proposed to determine the health risk associated with the two major groups of chlorinated DBPs--trihalomethanes (THMs) and haloacetic acids (HAAs). Initially, membership functions for cancer and non-cancer risks associated with THMs and HAAs are used to establish the fuzzy evaluation matrices. Subsequently, weighted evaluation matrices for both types of risks are established by performing cross products on the weighted vectors (founded on the analytic hierarchy process) and the fuzzy evaluation matrices. In the final stage, the weighted evaluation matrices of cancer and non-cancer risks are aggregated to determine the final risk rating. Two case studies are provided to demonstrate the application of this method.

Carcinogens↗

Kinetics and mechanism of chloride based chlorine dioxide generation process from acidic sodium chlorate.

The reaction between sodium chlorate and sodium chloride in presence of aqueous sulfuric acid is studied in a well stirred reactor at various temperatures and molar concentrations of chlorate, chloride and acid. The reaction rate is evaluated by analyzing the consumption of chlorate or chloride iodometrically or argentometrically. The rate law is established. Reaction has been found first and second order with respect to chlorate and chloride concentration, respectively. Reaction order is found about 13-14 with respect to molar concentration of sulfuric acid but it reduced to 2.4 when acidity function, h_, is substituted in place of molar concentration. The temperature dependence of the reaction is also investigated and pre-exponential Arrhenius parameter as well as activation energy are determined. It has been observed that ClO(2)/Cl(2) ratio is markedly affected by chlorate to chloride ratio. Reaction mechanism compatible with the reaction kinetics is proposed.

Chemical Industry↗