Antarctic stratospheric chemistry of chlorine nitrate, hydrogen chloride, and ice - Release of active chlorine

NASA Technical Reports Server (NTRS)

Molina, Mario J.; Tso, Tai-Ly; Molina, Luisa T.; Wang, Frank C.-Y.

1987-01-01

The reaction rate between atmospheric hydrogen chloride (HCl) and chlorine nitrate (ClONO2) is greatly enhanced in the presence of ice particles; HCl dissolves readily into ice, and the collisional reaction probability for ClONO2 on the surface of ice with HCl in the mole fraction range from about 0.003 to 0.010 is in the range from about 0.05 to 0.1 for temperatures near 200 K. Chlorine is released into the gas phase on a time scale of at most a few milliseconds, whereas nitric acid (HNO3), the other product, remains in the condensed phase. This reaction could play an important role in explaining the observed depletion of ozone over Antarctica; it releases photolytically active chlorine from its most abundant reservoir species, and it promotes the formation of HNO3 and thus removes nitrogen dioxide from the gas phase. Hence it establishes the necessary conditions for the efficient catalytic destruction of ozone by halogenated free radicals.

Chlorination Revisited: Does Cl- Serve as a Catalyst in the Chlorination of Phenols?

PubMed

Lau, Stephanie S; Abraham, Sonali M; Roberts, A Lynn

2016-12-20

The aqueous chlorination of (chloro)phenols is one of the best-studied reactions in the environmental literature. Previous researchers have attributed these reactions to two chlorine species: HOCl (at circum-neutral and high pH) and H 2 OCl + (at low pH). In this study, we seek to examine the roles that two largely overlooked chlorine species, Cl 2 and Cl 2 O, may play in the chlorination of (chloro)phenols. Solution pH, chloride concentration, and chlorine dose were systematically varied in order to assess the importance of different chlorine species as chlorinating agents. Our findings indicate that chlorination rates at pH < 6 increase substantially when chloride is present, attributed to the formation of Cl 2 . At pH 6.0 and a chlorine dose representative of drinking water treatment, Cl 2 O is predicted to have at best a minor impact on chlorination reactions, whereas Cl 2 may contribute more than 80% to the overall chlorination rate depending on the (chloro)phenol identity and chloride concentration. While it is not possible to preclude H 2 OCl + as a chlorinating agent, we were able to model our low-pH data by considering Cl 2 only. Even traces of chloride can generate sufficient Cl 2 to influence chlorination kinetics, highlighting the role of chloride as a catalyst in chlorination reactions.

On the relevance of the methane oxidation cycle to ozone hole chemistry

NASA Technical Reports Server (NTRS)

Mueller, Rolf; Crutzen, Paul J.

1994-01-01

High concentrations of active chlorine are clearly responsible for the observed ozone depletion during the Antarctic polar spring. However, the mechanism behind the activation of chlorine from the reservoirs species HCl and ClONO2 and the maintenance of extremely high levels of active chlorine after polar sunrise is less well understood. Here, we focus on the influence of the methane oxidation cycle on 'ozone hole' chemistry through its effect on HOx and ClOx radicals. We demonstrate the great potential importance of the heterogeneous reaction HCl + HOCl yields Cl2 + H2O and the gasphase reaction ClO + CH3O2 yields ClOO + CH3O under sunlight conditions in polar spring. Under these conditions, the heterogeneous reaction is the main sink for HOx radicals. Through this channel, the HCl reservoir may be almost completely depleted. The gas phase reaction may control the levels of the CH3O2 radical, provided that high levels of ClO exist. Otherwise this radical initiates a sequence of reactions leading to a considerable loss of active chlorine. Moreover, the production of HOx radicals is reduced, and thereby the efficiency of the heterogeneous reaction limited. The two reactions together may accomplish the complete conversion of HCl into active chlorine, thereby leading to a rapid destruction of ozone.

Transformations of dissolved organic matter induced by UV photolysis, Hydroxyl radicals, chlorine radicals, and sulfate radicals in aqueous-phase UV-Based advanced oxidation processes.

PubMed

Varanasi, Lathika; Coscarelli, Erica; Khaksari, Maryam; Mazzoleni, Lynn R; Minakata, Daisuke

2018-05-15

Considering the increasing identification of trace organic contaminants in natural aquatic environments, the removal of trace organic contaminants from water or wastewater discharge is an urgent task. Ultraviolet (UV) and UV-based advanced oxidation processes (AOPs), such as UV/hydrogen peroxide (UV/H 2 O 2 ), UV/free chlorine and UV/persulfate, are attractive and promising approaches for the removal of these contaminants due to the high reactivity of active radical species produced in these UV-AOPs with a wide variety of organic contaminants. However, the removal efficiency of trace contaminants is greatly affected by the presence of background dissolved organic matter (DOM). In this study, we use ultrahigh resolution mass spectrometry to evaluate the transformation of a standard Suwanee River fulvic acid DOM isolate in UV photolysis and UV-AOPs. The use of probe compounds allows for the determination of the steady-state concentrations of active radical species in each UV-AOP. The changes in the H/C and O/C elemental ratios, double bond equivalents, and the low-molecular-weight transformation product concentrations of organic acids reveal that different DOM transformation patterns are induced by each UV-AOP. By comparison with the known reactivities of each radical species with specific organic compounds, we mechanistically and systematically elucidate the molecular-level DOM transformation pathways induced by hydroxyl, chlorine, and sulfate radicals in UV-AOPs. We find that there is a distinct transformation in the aliphatic components of DOM due to HO• in UV/H 2 O 2 and UV/free chlorine. Cl• induced transformation of olefinic species is also observed in the UV/free chlorine system. Transformation of aromatic and olefinic moieties by SO 4 •- are the predominant pathways in the UV/persulfate system. Copyright © 2018 Elsevier Ltd. All rights reserved.

Chlorin E6 phototoxicity in L. major and L. braziliensis promastigotes-In vitro study.

PubMed

Pinto, Juliana Guerra; Pereira, André Henrique Correia; de Oliveira, Marco Antonio; Kurachi, Cristina; Raniero, Leandro José; Ferreira-Strixino, Juliana

2016-09-01

Cutaneous leishmaniasis is a zoonosis caused by protozoa of the genus Leishmania. Conventional treatments are long and aggressive, and they trigger a diversity of side effects. Photodynamic Therapy was originally proposed as a treatment for cancer, and it now appears to be a promising therapy for local treatment with fewer side effects of infectious diseases. This study aimed to evaluate Chlorin e6 internalization by Leishmania major and Leishmania braziliensis promastigotes and its viability and effects on mitochondrial activity. Control groups were kept in the dark, while PDT groups received fluence of 10J/cm(2) (660nm). Chlorin internalization was evaluated using confocal microscopy after one hour of incubation for both species. The mitochondrial activity was evaluated by MTT assay, and viability was measured by the Trypan blue exclusion test. Giemsa staining was used to observe morphological changes. PS was internalized in both species and mitochondrial activity changed in all groups. However, the obtained MTT and Trypan results indicated that despite the change in mitochondrial activity in the dark groups, their viability was not affected, whereas the PDT treated groups had significantly reduced viability. Morphology was drastically altered in PDT treated groups, while groups kept in the dark exhibited the standard morphology. This study demonstrates that Chlorin has great potential for being used in PDT as a treatment for cutaneous leishmaniasis, although more studies are needed to determine in vivo application protocols. Copyright © 2016 Elsevier B.V. All rights reserved.

Highly enantioselective organocatalytic oxidative kinetic resolution of secondary alcohols using chiral alkoxyamines as precatalysts: catalyst structure, active species, and substrate scope.

PubMed

Murakami, Keiichi; Sasano, Yusuke; Tomizawa, Masaki; Shibuya, Masatoshi; Kwon, Eunsang; Iwabuchi, Yoshiharu

2014-12-17

The development and characterization of enantioselective organocatalytic oxidative kinetic resolution (OKR) of racemic secondary alcohols using chiral alkoxyamines as precatalysts are described. A number of chiral alkoxyamines have been synthesized, and their structure-enantioselectivity correlation study in OKR has led us to identify a promising precatalyst, namely, 7-benzyl-3-n-butyl-4-oxa-5-azahomoadamantane, which affords various chiral aliphatic secondary alcohols (ee up to >99%, k(rel) up to 296). In a mechanistic study, chlorine-containing oxoammonium species were identified as the active species generated in situ from the alkoxyamine precatalyst, and it was revealed that the chlorine atom is crucial for high reactivity and enantioselectivity. The present OKR is the first successful example applicable to various unactivated aliphatic secondary alcohols, including heterocyclic alcohols with high enantioselectivity, the synthetic application of which is demonstrated by the synthesis of a bioactive compound.

Heterogeneous chemistry on Antarctic polar stratospheric clouds - A microphysical estimate of the extent of chemical processing

NASA Technical Reports Server (NTRS)

Drdla, K.; Turco, R. P.; Elliott, S.

1993-01-01

A detailed model of polar stratospheric clouds (PSCs), which includes nucleation, condensational growth. and sedimentation processes, has been applied to the study of heterogeneous chemical reactions. For the first time, the extent of chemical processing during a polar winter has been estimated for an idealized air parcel in the Antarctic vortex by calculating in detail the rates of heterogeneous reactions on PSC particles. The resulting active chlorine and NO(x) concentrations at first sunrise are analyzed with respect to their influence upon the Antarctic ozone hole using a photochemical model. It is found that the species present at sunrise are primarily influenced by the relative values of the heterogeneous reaction rate constants and the initial gas concentrations. However, the extent of chlorine activation is also influenced by whether N2O5 is removed by reaction with HCl or H2O. The reaction of N2O5 with HCl, which occurs rapidly on type 1 PSCs, activates the chlorine contained in the reservoir species HCl. Hence the presence and surface area of type 1 PSCs early in the winter are crucial in determining ozone depletion.

Bacterial community changes in copper and PEX drinking water pipeline biofilms under extra disinfection and magnetic water treatment.

PubMed

Inkinen, J; Jayaprakash, B; Ahonen, M; Pitkänen, T; Mäkinen, R; Pursiainen, A; Santo Domingo, J W; Salonen, H; Elk, M; Keinänen-Toivola, M M

2018-02-01

To study the stability of biofilms and water quality in pilot scale drinking water copper and PEX pipes in changing conditions (extra disinfection, magnetic water treatment, MWT). Next-generation sequencing (NGS) of 16S ribosomal RNA genes (rDNA) to describe total bacterial community and ribosomal RNA (rRNA) to describe active bacterial members in addition to traditional microbiological methods were applied. Biofilms from control copper and PEX pipes shared same most abundant bacteria (Methylobacterium spp., Sphingomonas spp., Zymomonas spp.) and average species diversities (Shannon 3·8-4·2) in rDNA and rRNA libraries, whereas few of the taxa differed by their abundance such as lower total Mycobacterium spp. occurrence in copper (<0·02%) to PEX (<0·2%) pipes. Extra disinfection (total chlorine increase from c. 0·5 to 1 mg l -1 ) affected total and active population in biofilms seen as decrease in many bacterial species and diversity (Shannon 2·7, P < 0·01, rRNA) and increase in Sphingomonas spp. as compared to control samples. Furthermore, extra-disinfected copper and PEX samples formed separate clusters in unweighted non-metric multidimensional scaling plot (rRNA) similarly to MWT-treated biofilms of copper (but not PEX) pipes that instead showed higher species diversity (Shannon 4·8, P < 0·05 interaction). Minor chlorine dose addition increased selection pressure and many species were sensitive to chlorination. Pipe material seemed to affect mycobacteria occurrence, and bacterial communities with MWT in copper but not in PEX pipes. This study using rRNA showed that chlorination affects especially active fraction of bacterial communities. Copper and PEX differed by the occurrence of some bacterial members despite similar community profiles. © 2017 The Society for Applied Microbiology.

[Sporocidic activity of sodium hypochlorite and peracetic acid alone or combined against free or fixed spores or on biofilm].

PubMed

Samrakandi, M M; Roques, C; Michel, G

1994-05-01

In order to assess the sporocidal activity of chlorine and peracetic acid (PAA), alone and in combination, against a spored biofilm, the biofilms of two species (Bacillus subtilis ATCC 6633 and Bacillus megaterium ATCC 8245) were formed on inert support (tygon). A sporulation kinetic of these bacteria in biofilm was established. Sporocidal properties of chlorine and PAA were compared against free spores, spores fixed by drying and spores in biofilm. The combination of these two products was also tested. Minimal sporocidal concentrations (MSC) of the two products towards free spores were determined (contact time 5 mn). The efficacy of these MSC were evaluated in terms of contact time on adhered spores and on spores in biofilm. Chlorine and PAA exhibited an excellent sporocidal activity. The combination of PAA and chlorine, tested by checkerboard micromethod, was found to be synergistic in case of free or adhered spores. The spored biofilm showed a high resistance. The combination of these two products revealed then only an additive effect.

Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts

PubMed Central

Varnell, Jason A.; Tse, Edmund C. M.; Schulz, Charles E.; Fister, Tim T.; Haasch, Richard T.; Timoshenko, Janis; Frenkel, Anatoly I.; Gewirth, Andrew A.

2016-01-01

The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites. PMID:27538720

Phototoxicity of phenylenediamine hair dye chemicals in Salmonella typhimurium TA102 and human skin keratinocytes.

PubMed

Mosley-Foreman, Charity; Choi, Jaehwa; Wang, Shuguang; Yu, Hongtao

2008-12-01

Phenylenediamines (PD) are dye precursors used to manufacture hair dyes. The three PDs, 1,2-,1,3-, and 1,4-PD and three chlorinated PDs, 4-chloro-1,2-PD, 4-chloro-1,3-PD, and 4,5-dichloro-1,2-PD were studied for their mutagenic effect in Salmonella typhimurium TA 102, cytotoxicity in human skin keratinocyte cells, and for DNA cleavage. The results show that all six compounds are not toxic/mutagenic in TA 102 bacteria or skin cells, and do not cause DNA cleavage in PhiX 174 phage DNA. If the same tests are carried out by exposing them to light irradiation concurrently, all three chlorinated PDs cause mutation in TA 102 bacteria and single strand cleavage in PhiX174 phage DNA. This indicates that chlorination of the PDs makes these compounds more photochemically active and produces reactive species that cause DNA damage and mutation. For the photocytotoxicity test in skin cells, it appears there is no such structure-activity relationship. Two chlorinated PDs and two non-chlorinated PDs are cytotoxic at a fairly high concentration (1000microM) upon exposure to light irradiation.

Phenotypic and genetic diversity of chlorine-resistant Methylobacterium strains isolated from various environments.

PubMed Central

Hiraishi, A; Furuhata, K; Matsumoto, A; Koike, K A; Fukuyama, M; Tabuchi, K

1995-01-01

Strains of pink-pigmented facultative methylotrophs which were isolated previously from various environments and assigned tentatively to the genus Methylobacterium were characterized in comparison with authentic strains of previously known species of this genus. Most of the isolates derived from chlorinated water supplies exhibited resistance to chlorine, whereas 29 to 40% of the isolates from air, natural aquatic environments, and clinical materials were chlorine resistant. None of the tested authentic strains of Methylobacterium species obtained from culture collections exhibited chlorine resistance. Numerical analysis of phenotypic profiles showed that the test organisms tested were separated from each other except M. organophilum and M. rhodesianum. The chlorine-resistant isolates were randomly distributed among all clusters. The 16S ribosomal DNA (rDNA) sequence-based phylogenetic analyses showed that representatives of the isolates together with known Methylobacterium species formed a line of descent distinct from that of members of related genera in the alpha-2 subclass of the Proteobacteria and were divided into three subclusters within the Methylobacterium group. These results demonstrate that there is phenotypic and genetic diversity among chlorine-resistant Methylobacterium strains within the genus. PMID:7793931

Phenotypic and genetic diversity of chlorine-resistant Methylobacterium strains isolated from various environments.

PubMed

Hiraishi, A; Furuhata, K; Matsumoto, A; Koike, K A; Fukuyama, M; Tabuchi, K

1995-06-01

Strains of pink-pigmented facultative methylotrophs which were isolated previously from various environments and assigned tentatively to the genus Methylobacterium were characterized in comparison with authentic strains of previously known species of this genus. Most of the isolates derived from chlorinated water supplies exhibited resistance to chlorine, whereas 29 to 40% of the isolates from air, natural aquatic environments, and clinical materials were chlorine resistant. None of the tested authentic strains of Methylobacterium species obtained from culture collections exhibited chlorine resistance. Numerical analysis of phenotypic profiles showed that the test organisms tested were separated from each other except M. organophilum and M. rhodesianum. The chlorine-resistant isolates were randomly distributed among all clusters. The 16S ribosomal DNA (rDNA) sequence-based phylogenetic analyses showed that representatives of the isolates together with known Methylobacterium species formed a line of descent distinct from that of members of related genera in the alpha-2 subclass of the Proteobacteria and were divided into three subclusters within the Methylobacterium group. These results demonstrate that there is phenotypic and genetic diversity among chlorine-resistant Methylobacterium strains within the genus.

21 CFR 173.300 - Chlorine dioxide.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Chlorine dioxide. 173.300 Section 173.300 Food and... Additives § 173.300 Chlorine dioxide. Chlorine dioxide (CAS Reg. No. 10049-04-4) may be safely used in food... chlorine dioxide with respect to all chlorine species as determined by Method 4500-ClO2 E in the “Standard...

Formation of N-nitrosamines from chlorination and chloramination of molecular weight fractions of natural organic matter.

PubMed

Kristiana, Ina; Tan, Jace; Joll, Cynthia A; Heitz, Anna; von Gunten, Urs; Charrois, Jeffrey W A

2013-02-01

N-Nitrosamines are a class of disinfection by-products (DBPs) that have been reported to be more toxic than the most commonly detected and regulated DBPs. Only a few studies investigating the formation of N-nitrosamines from disinfection of natural waters have been reported, and little is known about the role of natural organic matter (NOM) and the effects of its nature and reactivity on the formation of N-nitrosamines. This study investigated the influence of the molecular weight (MW) characteristics of NOM on the formation of eight species of N-nitrosamines from chlorination and chloramination, and is the first to report on the formation of eight N-nitrosamines from chlorination and chloramination of MW fractions of NOM. Isolated NOM from three different source waters in Western Australia was fractionated into several apparent MW (AMW) fractions using preparative-scale high performance size exclusion chromatography. These AMW fractions of NOM were then treated with chlorine or chloramine, and analysed for eight species of N-nitrosamines. Among these N-nitrosamines, N-nitrosodimethylamine (NDMA) was the most frequently detected. All AMW fractions of NOM produced N-nitrosamines upon chlorination and chloramination. Regardless of AMW characteristics, chloramination demonstrated a higher potential to form N-nitrosamines than chlorination, and a higher frequency of detection of the N-nitrosamines species was also observed in chloramination. The results showed that inorganic nitrogen may play an important role in the formation of N-nitrosamines, while organic nitrogen is not necessarily a good indicator for their formation. Since chlorination has less potential to form N-nitrosamines, chloramination in pre-chlorination mode was recommended to minimise the formation of N-nitrosamines. There was no clear trend in the formation of N-nitrosamines from chlorination of AMW fractions of NOM. However, during chloramination, NOM fractions with AMW <2.5 kDa were found to produce higher concentrations of NDMA and total N-nitrosamines. The precursor materials of N-nitrosamines appeared to be more abundant in the low to medium MW fractions of NOM, which correspond to the fractions that are most difficult to remove using conventional drinking water treatment processes. Alternative or advanced treatment processes that target the removal of low to medium MW NOM including activated carbon adsorption, biofiltration, reverse osmosis, and nanofiltration, can be employed to minimise the formation of N-nitrosamines. Copyright © 2012 Elsevier Ltd. All rights reserved.

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

PubMed

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.

Lagrangian photochemical modeling studies of the 1987 Antarctic spring vortex. II - Seasonal trends in ozone

NASA Technical Reports Server (NTRS)

Austin, J.; Jones, R. L.; Mckenna, D. S.; Buckland, A. T.; Anderson, J. G.; Fahey, D. W.; Farmer, C. B.; Heidt, L. E.; Proffitt, M. H.; Vedder, J. F.

1989-01-01

A photochemical model consisting of 40 species and 107 reactions is integrated along 80-day air parcel trajectories calculated in the lower stratosphere for the springtime Antarctic. For the trajectory starting at 58 deg S, which may be regarded as outside the circumpolar vortex, only a small change in O3 occurs in the model. In contrast, for the air parcel starting in the vortex at 74 deg S, the O3 concentration is reduced by 93 percent during the 80 days from the beginning of August to late October. The model results for several species are compared with measurements from the Airborne Antarctic Ozone Experiment and, in general, good agreement is obtained. In the model, the dentrification of the air parcels in polar stratospheric clouds increases the amount of chlorine present in active form. Heterogeneous reactions maintain high active chlorine which destroys O3 via the formation of the ClO dimer. Results of calculations with reduced concentrations of inorganic chlorine show considerably reduced O3 destruction rates and compare favorably with the behavior of total O3 since the late 1970s. The remaining major uncertainties in the photochemical aspects of the Antarctic ozone hole are highlighted.

Chem 13 News Digest

ERIC Educational Resources Information Center

Friesen, R. J., Ed.

1975-01-01

Discusses the chlorination of water supplies. Includes a description of the chemical species present due to chlorination, and the dangers of and alternatives to the chlorination of water systems. (MLH)

Alkali and Chlorine Photochemistry in a Volcanically Driven Atmosphere on Io

NASA Astrophysics Data System (ADS)

Moses, Julianne I.; Zolotov, Mikhail Yu.; Fegley, Bruce

2002-03-01

Observations of the Io plasma torus and neutral clouds indicate that the extended ionian atmosphere must contain sodium, potassium, and chlorine in atomic and/or molecular form. Models that consider sublimation of pure sulfur dioxide frost as the sole mechanism for generating an atmosphere on Io cannot explain the presence of alkali and halogen species in the atmosphere—active volcanoes or surface sputtering must also be considered, or the alkali and halide species must be discharged along with the SO 2 as the frost sublimates. To determine how volcanic outgassing can affect the chemistry of Io's atmosphere, we have developed a one-dimensional photochemical model in which active volcanoes release a rich suite of S-, O-, Na-, K-, and Cl-bearing vapor and in which photolysis, chemical reactions, condensation, and vertical eddy and molecular diffusion affect the subsequent evolution of the volcanic gases. Observations of Pele plume constituents, along with thermochemical equilibrium calculations of the composition of volcanic gases exsolved from high-temperature silicate magmas on Io, are used to constrain the composition of the volcanic vapor. We find that NaCl, Na, Cl, KCl, and K will be the dominant alkali and chlorine gases in atmospheres generated from Pele-like plume eruptions on Io. Although the relative abundances of these species will depend on uncertain model parameters and initial conditions, these five species remain dominant for a wide variety of realistic conditions. Other sodium and chlorine molecules such as NaS, NaO, Na 2, NaS 2, NaO 2, NaOS, NaSO 2, SCl, ClO, Cl 2, S 2Cl, and SO 2Cl 2 will be only minor constituents in the ionian atmosphere because of their low volcanic emission rates and their efficient photochemical destruction mechanisms. Our modeling has implications for the general appearance, properties, and variability of the neutral sodium clouds and jets observed near Io. The neutral NaCl molecules present at high altitudes in atmosph eres generated by active volcanoes might provide the NaX + ion needed to help explain the morphology of the high-velocity sodium "stream" feature observed near Io.

Exploration of an urban lake management model to simulate chlorine interference based on the ecological relationships among aquatic species.

PubMed

Yan, Zhiqiang; Wang, Yafei; Wu, Di; Xia, Beicheng

2018-05-29

In eutrophic lakes, algae are known to be sensitive to chlorine, but the impact of chlorine on the wider ecosystem has not been investigated. To quantitatively investigate the effects of chlorine on the urban lake ecosystem and analyze the changes in the aquatic ecosystem structure, a dynamic response model of aquatic species to chlorine was constructed based on the biomass density dynamics of aquatic species of submerged macrophytes, phytoplankton, zooplankton, periphyton, and benthos. The parameters were calibrated using data from the literature and two simulative experiments. The model was then validated using field data from an urban lake with a surface area of approximately 8000 m 2 located in the downtown area of Guangzhou, South China. The correlation coefficient (R), root mean square error-observations standard deviation ratio (RSR) and index of agreement (IOA) were used to evaluate the accuracy and reliability of the model and the results were consistent with the observations (0.446 R < 0.985, RSR < 0.7, IOA > 0.6). Comparisons between the simulated and observed trends confirmed the feasibility of using this model to investigate the dynamics of aquatic species under chlorine interference. The model can help managers apply a modest amount of chlorine to control eutrophication and provides scientific support for the management of urban lakes.

Degradation of DEET and Caffeine under UV/Chlorine and Simulated Sunlight/Chlorine Conditions.

PubMed

Sun, Peizhe; Lee, Wan-Ning; Zhang, Ruochun; Huang, Ching-Hua

2016-12-20

Photoactivation of aqueous chlorine could promote degradation of chlorine-resistant and photochemically stable chemicals accumulated in swimming pools. This study investigated the degradation of two such chemicals, N,N-diethyl-3-methylbenzamide (DEET) and caffeine, by low pressure ultraviolet (UV) light and simulated sunlight (SS) activated free chlorine (FC) in different water matrices. Both DEET and caffeine were rapidly degraded by UV/FC and SS/FC but exhibited different kinetic behaviors. The degradation of DEET followed pseudo-first-order kinetics, whereas the degradation of caffeine accelerated with reaction. Mechanistic study revealed that, under UV/FC, ·OH and Cl· were responsible for degradation of DEET, whereas ClO· related reactive species (ClOrrs), generated by the reaction between FC and ·OH/Cl·, played a major role in addition to ·OH and Cl· in degrading caffeine. Reaction rate constants of DEET and caffeine with the respective radical species were estimated. The imidazole moiety of caffeine was critical for the special reactivity with ClOrrs. Water matrix such as pH had a stronger impact on the UV/FC process than the SS/FC process. In saltwater matrix under UV/FC and SS/FC, the degradation of DEET was significantly inhibited, but the degradation of caffeine was much faster than that in nonsalty solutions. The interaction between Br - and Cl - may play an important role in the degradation of caffeine by UV/FC in saltwater. Reaction product analysis showed similar product patterns by UV/FC and SS/FC and minimal formation of chlorinated intermediates and disinfection byproducts.

Implementation Of Palladized Iron-Impregnated Reactive Activated Carbon (RAC) System For PCBs Cleanup: Effects Of PCB Loading, Reaction pH, And Co-Existing NOM And Ionic Species

EPA Science Inventory

For the treatment of chlorinated organic compounds in the environment, such as polychlorinated biphenyls (PCBs), we have developed reactive activated carbon (RAC) impregnated with Fe/Pd bimetallic nanoparticles. The RAC system can couple adsorption of PCBs to activated carbon wi...

Bank security dye packs: synthesis, isolation, and characterization of chlorinated products of bleached 1-(methylamino)anthraquinone.

PubMed

Egan, James M; Rickenbach, Michael; Mooney, Kim E; Palenik, Chris S; Golombeck, Rebecca; Mueller, Karl T

2006-11-01

Banknote evidence is often submitted after a suspect has attempted to disguise or remove red dye stain that has been released because of an anti-theft device that activates after banknotes have been unlawfully removed from bank premises. Three chlorinated compounds have been synthesized as forensic chemical standards to indicate bank security dye bleaching as a suspect's intentional method for masking a robbery involving dye pack release on banknotes. A novel, facile synthetic method to provide three chlorinated derivatives of 1-(methylamino)anthraquinone (MAAQ) is presented. The synthetic route involved Ultra Clorox bleach as the chlorine source, iron chloride as the catalyst, and MAAQ as the starting material and resulted in a three-component product mixture. Two mono-chlorinated isomers (2-chloro-1-(methylamino)anthraquinone and 4-chloro-1-(methylamino)anthraquinone) and one di-chlorinated compound (2,4-dichloro-1-(methylamino)anthraquinone) of the MAAQ parent molecule were detected by gas chromatography mass spectrometry (GC-MS), and subsequently isolated by liquid chromatography (LC) with postcolumn fraction collection. Although GC-MS is sensitive enough to detect all of the chlorinated products, it is not definitive enough to identify the structural isomers. Liquid-state nuclear magnetic resonance (NMR) spectroscopy was utilized to elucidate structurally the ortho- and para-mono-chlorinated isomers once enough material was properly isolated. A reaction mechanism involving iron is proposed to explain the presence of chlorinated MAAQ species on stolen banknotes after attempted bleaching.

Reaction of Cl- ions in electrolyte solution induced electrical discharge plasma in the presence of argon fine bubbles

NASA Astrophysics Data System (ADS)

Hayashi, Yui; Takada, Noriharu; Wahyudiono, Kanda, Hideki; Goto, Motonobu

2017-05-01

Active chlorine species such as chlorine molecules and hypochlorous acid have been known as high performance sanitizers. They would act more reactive on chemical and biological substances when an electrical discharge was introduced in water containing an electrolyte substance. Here, the reaction of chloride (Cl-) ions were examined by introducing of a pulsed discharge plasma in sodium chloride (NaCl) solution as an electrolyte solution at room temperature. The results show that a large electrical current generated by the pulsed discharge plasma affected the reaction of Cl- ions to result available chlorine. The reaction pathway for available chlorine production was assumed similar with the reaction pathway as electrolysis. A pulsed discharge plasma in NaCl solution in the presence of argon (Ar) fine bubbles exhibited intense emissions and high electron density compared to when no Ar fine bubbles were introduced. At these conditions, the dissociation reaction rate of water increased drastically leads to the formation of 0 atoms. As a result, the reaction of Cl- ions and the available chlorine generation were also increased.

NemR Is a Bleach-sensing Transcription Factor*

PubMed Central

Gray, Michael J.; Wholey, Wei-Yun; Parker, Benjamin W.; Kim, Minwook; Jakob, Ursula

2013-01-01

Hypochlorous acid (HOCl), the active component of household bleach, also functions as a powerful antimicrobial during the innate immune response. Despite its widespread use, surprisingly little is known about how cells sense or respond to HOCl. We now demonstrate that Escherichia coli NemR is a redox-regulated transcriptional repressor, which uses the oxidation status of HOCl-sensitive cysteine residues to respond to bleach and related reactive chlorine species. NemR controls bleach-mediated expression of two enzymes required for detoxification of reactive electrophiles: glyoxalase I and N-ethylmaleimide reductase. Both enzymes contribute to bacterial bleach survival. These results provide evidence that bleach resistance relies on the capacity of organisms to specifically sense reactive chlorine species and respond with the up-regulation of enzymes dedicated to detoxification of methylglyoxal and other reactive electrophiles. PMID:23536188

Degradation of clofibric acid in UV/chlorine disinfection process: kinetics, reactive species contribution and pathways

PubMed Central

Tang, Yuqing; Shi, Xueting; Liu, Yongze; Zhang, Liqiu

2018-01-01

As a potential endocrine disruptor, clofibric acid (CA) was investigated in this study for its degradation kinetics and pathways in UV/chlorine process. The results showed that CA in both UV photolysis and UV/chlorine processes could be degraded via pseudo-first-order kinetics, while it almost could not be degraded in the dark chlorination process. The observed rate constant (kobs) in UV photolysis was 0.0078 min−1, and increased to 0.0107 min−1 combining with 0.1 mM chlorine. The kobs increased to 0.0447 min−1 with further increasing the chlorine dosage from 0.1 to 1.0 mM, and reached a plateau at higher dosage (greater than 1.0 mM). The higher kobs was obtained at acid solution rather than basic solution. Moreover, the calculated contributions of radical species to kobs indicated that the HO• contributed significantly to CA degradation in acidic conditions, while the reactive chlorine species and UV direct photolysis dominated in neutral and basic solution. The degradation of CA was slightly inhibited in the presence of HCO3− (1 ∼ 50 mM), barely affected by the presence of Cl− (1 ∼ 200 mM) and greatly suppressed by humic acid (0 ∼ 5 mg l−1). Thirteen main degradation intermediates and three degradation pathways of CA were identified during UV/chlorine process. PMID:29515853

Degradation of clofibric acid in UV/chlorine disinfection process: kinetics, reactive species contribution and pathways.

PubMed

Tang, Yuqing; Shi, Xueting; Liu, Yongze; Feng, Li; Zhang, Liqiu

2018-02-01

As a potential endocrine disruptor, clofibric acid (CA) was investigated in this study for its degradation kinetics and pathways in UV/chlorine process. The results showed that CA in both UV photolysis and UV/chlorine processes could be degraded via pseudo-first-order kinetics, while it almost could not be degraded in the dark chlorination process. The observed rate constant ( k obs ) in UV photolysis was 0.0078 min -1, and increased to 0.0107 min -1 combining with 0.1 mM chlorine. The k obs increased to 0.0447 min -1 with further increasing the chlorine dosage from 0.1 to 1.0 mM, and reached a plateau at higher dosage (greater than 1.0 mM). The higher k obs was obtained at acid solution rather than basic solution. Moreover, the calculated contributions of radical species to k obs indicated that the HO• contributed significantly to CA degradation in acidic conditions, while the reactive chlorine species and UV direct photolysis dominated in neutral and basic solution. The degradation of CA was slightly inhibited in the presence of [Formula: see text] (1 ∼ 50 mM), barely affected by the presence of Cl - (1 ∼ 200 mM) and greatly suppressed by humic acid (0 ∼ 5 mg l -1 ). Thirteen main degradation intermediates and three degradation pathways of CA were identified during UV/chlorine process.

Efficient interfacial charge transfer through plasmon sensitized Ag@Bi2O3 hierarchical photoanodes for photoelectrocatalytic degradation of chlorinated phenols.

PubMed

Eswar, Neerugatti KrishnaRao; Adhikari, Sangeeta; Ramamurthy, Praveen C; Madras, Giridhar

2018-01-31

The present work demonstrates an extremely proficient and robust study of efficient interfacial charge transfer through plasmonic Ag decorated Bi 2 O 3 hierarchical photoanodes for the photoelectrochemical treatment of chlorinated phenols. Unique 2D flake-like Bi 2 O 3 hierarchical nanostructures were grown onto a fluorine-doped tin oxide (FTO) substrate by a simple chemical bath deposition method using triethanolamine as complexing agent. The formation of Bi 2 O 3 on FTO was governed by the decomposition of a nucleated bismuth-hydroxyl complex (Bi 2 O 1-x (OH) x ) and modification to the electrode was carried out by the deposition of Ag via a chemical reduction method using hydrazine hydrate. Both the fabricated electrodes were well characterized for their photo- and electro-optical properties. Efficient charge separation was observed due to the surface plasmon resonance phenomenon of silver nanoparticles with the favorable intrinsic properties of Bi 2 O 3 under application of a small electric bias of 1 V preventing the recombination of charge carriers and thereby increasing the rate of photoelectrocatalytic degradation of the chlorinated phenols. PEC degradation using the Ag@Bi 2 O 3 photoelectrode followed the trend 4-CP < 2,4-DCP < 2,4,6-TCP < P-CP due to efficient attack at the chlorinated positions by reactive oxygen species with increasing chlorine substitution and also due to the absence of an expected chain reaction of the generated chlorine radicals (Cl˙) during the PEC reaction. The PEC activity of Ag@Bi 2 O 3 was 1.5 times higher than a Bi 2 O 3 nanoflake electrode for 4-CP over 2 h. The fabricated Ag@Bi 2 O 3 proved to be an efficient photoelectrode with synergistic solar-induced photoactivity. A detailed mechanistic study in the presence of scavengers suggests degradation by produced hydroxyl radical species. Thus, physical insights into the degradation of chlorinated phenols were obtained.

Discovery and characterization of a marine bacterial SAM-dependent chlorinase

PubMed Central

Eustáquio, Alessandra S; Pojer, Florence; Noel, Joseph P; Moore, Bradley S

2009-01-01

Halogen atom incorporation into a scaffold of bioactive compounds often amplifies biological activity, as is the case for the anticancer agent salinosporamide A (1), a chlorinated natural product from the marine bacterium Salinispora tropica. Significant effort in understanding enzymatic chlorination shows that oxidative routes predominate to form reactive electrophilic or radical chlorine species. Here we report the genetic, biochemical and structural characterization of the chlorinase SalL, which halogenates S-adenosyl-l-methionine (2) with chloride to generate 5′-chloro-5′-deoxyadenosine (3) and l-methionine (4) in a rarely observed nucleophilic substitution strategy analogous to that of Streptomyces cattleya fluorinase. Further metabolic tailoring produces a halogenated polyketide synthase substrate specific for salinosporamide A biosynthesis. SalL also accepts bromide and iodide as substrates, but not fluoride. High-resolution crystal structures of SalL and active site mutants complexed with substrates and products support the SN2 nucleophilic substitution mechanism and further illuminate halide specificity in this newly discovered halogenase family. PMID:18059261

Anaerobic microbial dehalogenation and its key players in the contaminated Bitterfeld-Wolfen megasite.

PubMed

Nijenhuis, Ivonne; Stollberg, Reiner; Lechner, Ute

2018-04-01

The megasite Bitterfeld-Wolfen is highly contaminated as a result of accidents and because of dumping of wastes from local chemical industries in the last century. A variety of contaminants including chlorinated ethenes and benzenes, hexachlorohexanes and chlorinated dioxins can still be found in the groundwater and (river) sediments. Investigations of the in situ microbial transformation of organohalides have been performed only over the last two decades at this megasite. In this review, we summarise the research on the activity of anaerobic dehalogenating bacteria at the field site in Bitterfeld-Wolfen, focusing on chlorinated ethenes, monochlorobenzene and chlorinated dioxins. Various methods and concepts were applied including ex situ cultivation and isolation, and in situ analysis of hydrochemical parameters, compound-specific stable isotope analysis of contaminants, 13C-tracer studies and molecular markers. Overall, biotransformation of organohalides is ongoing at the field site and Dehalococcoides mccartyi species play an important role in the detoxification process in the Bitterfeld-Wolfen region.

Effects of hypochlorous acid exposure on the rejection of salt, polyethylene glycols, boron and arsenic(V) by nanofiltration and reverse osmosis membranes.

PubMed

Do, Van Thanh; Tang, Chuyang Y; Reinhard, Martin; Leckie, James O

2012-10-15

The separation layer of polyamide-based (PA) thin film composite (TFC) membranes can be modified by active chlorine species. The PA-TFC membranes, NF90, BW30 and NF270, were exposed to different concentrations of sodium hypochlorite (NaOCl) at pH 5 for 24 h. Elemental composition obtained from X-ray Photoelectron Spectroscopy (XPS) showed that the chlorine content in the PA layer increased with the chlorine concentrations. Treatment of membranes with 10 ppm Cl increased the membrane hydrophilicity. By contrast, when treated with 1000 ppm Cl or more, the membranes became less hydrophilic. Water permeability values for all 3 membrane types declined with increased chlorine concentrations. Filtration of polyethylene glycols (PEGs) with molecular weights of 200, 400 and 600 Daltons (Da) was performed to investigate the influence of chlorine treatment on membrane molecular weight cut off (MWCO) and rejection by size exclusion. Treatment with 10 and 100 ppm Cl lowered the MWCO while treatment with higher concentrations increased the MWCO. All chlorinated membranes experienced higher NaCl rejection compared to virgin ones. The performance of NF90 was tested with respect to the rejection of inorganic contaminants including boron (H(3)BO(3)) and arsenic (H(2)AsO(4)(-)). The boron rejection results paralleled PEG rejection whereas those for arsenic followed NaCl rejection patterns. The changes in membrane performance due to chlorine treatment were explained in terms of competing mechanisms: membrane tightening, bond cleavage by N-chlorination and chlorination promoted polyamide hydrolysis. Copyright © 2012 Elsevier Ltd. All rights reserved.

A combined ToF-SIMS and XPS study for the elucidation of the role of water in the performances of a Post-Plasma Process using LaMnO3+δ as catalyst in the total oxidation of trichloroethylene

NASA Astrophysics Data System (ADS)

Nuns, N.; Beaurain, A.; Dinh, M. T. Nguyen; Vandenbroucke, A.; De Geyter, N.; Morent, R.; Leys, C.; Giraudon, J.-M.; Lamonier, J.-F.

2014-11-01

LaMnO3+δ which is an environment-friendly and inexpensive material has been previously used as catalyst in Post-Plasma Catalysis (PPC) in the total oxidation of trichloroethylene (TCE) which is a solvent widely used in dry cleaning and degreasing processes. It has been shown that the process efficiency increases in moist air (RH = 18%).The issue we want to address herein is the effect of water on the location of chlorine at the surface of the catalyst as chlorine is able to alter the catalyst structure, activity and stability. Therefore, a combined Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS) and X-ray Photoelectron Spectroscopy (XPS) study has been carried out on the fresh LaMnO3+δ catalyst (LM) and used catalysts after performing PPC with TCE diluted in dry synthetic air (LM0) or with industrial air containing water (LM18; 18 stands for the Relative Humidity) and CO2 (about 560 ppmv) at a temperature of 150 °C. XPS and ToF-SIMS results both show the presence of chlorine on the tested catalysts whose amount increases by exposure of the catalyst to the reactive mixture in dry synthetic air. XPS results reveal that chlorine is present as both chloride ion and covalent chlorine on LM0 while organic chlorinated residues are absent on LM18 catalyst. ToF-SIMS study indicates that lanthanum excess as oxide(hydroxide) partially covering the perovskite mainly transforms into LaOCl and to a minor extent into LaCl3. Extent of Mn chlorination seems to be favored over LM0 having a higher MnClx±/MnOCl± ionic ratio compared to LM18. Furthermore ToF-SIMS clearly identifies C1 chlorinated organic ions, mainly CH2Cl+ and CHCl2-, on LM0 which may contribute to the XPS Cl organic component. From the combined ToF-SIMS and XPS results it is found that water delays the surface degradation extent of the perovskite into related (oxy)(hydroxy)chlorinated inorganic phases by less molecular chlorine and related chlorine species on the catalyst surface. A reaction scheme of Cl removal over LaMnO3+δ emphasing the role of water is given taking into account the detection of ToF-SIMS ions representative of the successive Mn intermediate states. As a consequence water allows tuning the degradation pathways of the main intermediate of the reaction, dichloroacetyl chloride (DCAC), which decomposes to give phosgene, HCCl3 and CCl4 by a successive Cl incorporation over (oxy)(hydroxy)chorinated perovskite or/and Mn species while COx species are likely formed over the perovskite.

Disinfection efficacy of chlorine and peracetic acid alone or in combination against Aspergillus spp. and Candida albicans in drinking water.

PubMed

Sisti, Maurizio; Brandi, Giorgio; De Santi, Mauro; Rinaldi, Laura; Schiavano, Giuditta F

2012-03-01

The aim of the present study was to evaluate the fungicidal activity of chlorine and peracetic acid in drinking water against various pathogenic Aspergillus spp. and Candida albicans strains. A. nidulans exhibited the greatest resistance, requiring 10 ppm of chlorine for 30 min contact time for a complete inactivation. Under the same experimental conditions, peracetic acid was even less fungicidal. In this case, A. niger proved to be the most resistant species (50 ppm for 60 min for complete inactivation). All Aspergillus spp. were insensitive to 10 ppm even with extended exposure (>5 h). The combination of chlorine and peracetic acid against Aspergillus spp. did not show synergistic effects except in the case of A. flavus. Complete growth inhibition of C. albicans was observed after about 3 h contact time with 0.2 ppm. C. albicans was less sensitive to peracetic acid. Hence the concentrations of chlorine that are usually present in drinking water distribution systems are ineffective against several Aspergillus spp. and peracetic acid cannot be considered an alternative to chlorine for disinfecting drinking water. The combination of the two biocides is not very effective in eliminating filamentous fungi at the concentrations permitted for drinking water disinfection.

Combustion of chlorinated volatile organic compounds (VOCs) using bimetallic chromium-copper supported on modified H-ZSM-5 catalyst.

PubMed

Abdullah, Ahmad Zuhairi; Bakar, Mohamad Zailani Abu; Bhatia, Subhash

2006-02-28

The paper reports on the performance of chromium or/and copper supported on H-ZSM-5(Si/Al = 240) modified with silicon tetrachloride (Cr1.5/SiCl4-Z, Cu1.5/SiCl4-Z and Cr1.0Cu0.5/SiCl4-Z) as catalysts in the combustion of chlorinated VOCs (Cl-VOCs). A reactor operated at a gas hourly space velocity (GHSV) of 32,000 h(-1), a temperature between 100 and 500 degrees C with 2500 ppm of dichloromethane (DCM), trichloromethane (TCM) and trichloroethylene (TCE) is used for activity studies. The deactivation study is conducted at a GHSV of 3800 h(-1), at 400 degrees C for up to 12 h with a feed concentration of 35,000 ppm. Treatment with silicon tetrachloride improves the chemical resistance of H-ZSM-5 against hydrogen chloride. TCM is more reactive compared to DCM but it produces more by-products due to its high chlorine content. The stabilization of TCE is attributed to resonance effects. Water vapor increases the carbon dioxide yield through its role as hydrolysis agent forming reactive carbocations and acting as hydrogen-supplying agent to suppress chlorine-transfer reactions. The deactivation of Cr1.0Cu0.5/SiCl4-Z is mainly due to the chlorination of its metal species, especially with higher Cl/H feed. Coking is limited, particularly with DCM and TCM. In accordance with the Mars-van Krevelen model, the weakening of overall metal reducibility due to chlorination leads to a loss of catalytic activity.

CHARACTERIZATION OF CHLORINATION TRANSFORMATION PRODUCTS OF SELECTED PESTICIDES

EPA Science Inventory

Chlorination is a commonly-used disinfectant step in drinking water treatment. Should free chlorine be added to water used as a drinking water source, it is widely understood that many biological species in the water along with dissolved organic and inorganic chemicals will react...

The geochemistry of fluids from an active shallow submarine hydrothermal system: Milos island, Hellenic Volcanic Arc

NASA Astrophysics Data System (ADS)

Valsami-Jones, E.; Baltatzis, E.; Bailey, E. H.; Boyce, A. J.; Alexander, J. L.; Magganas, A.; Anderson, L.; Waldron, S.; Ragnarsdottir, K. V.

2005-10-01

Geothermal activity in the Aegean island of Milos (Greece), associated with island-arc volcanism, is abundant both on-and off-shore. Hydrothermal fluids venting from several sites, mainly shallow submarine (up to 10 m), but also just above seawater level in one locality, were sampled over four summer field seasons. Some of the discharging fluids are associated with the formation of hydrothermal edifices. Overall, the main characteristics of the hydrothermal fluids are low pH and variable chlorinity. The lowest recorded pH was 1.7, and chlorinity ranged from 0.1 to 2.5 times that of seawater. The highest fluid temperatures recorded on site were 115 °C. Two main types of fluids were identified: low-chlorinity fluids containing low concentrations of alkalis (potassium, lithium, sodium) and calcium, and high concentrations of silica and sulphate; and high-chlorinity fluids containing high concentrations of alkalis and calcium, and lower concentrations of silica and sulphate. The type locality of the high-chlorinity fluids is shallow submarine in Palaeochori, near the east end of the south coast of the island, whereas the type locality of the low-chlorinity fluids is a cave to the west of Palaeochori. The two fluid types are therefore often referred to as "submarine" and "cave" fluids respectively. Both fluid types had low magnesium and high metal concentrations but were otherwise consistently different from each other. The low-chlorinity fluids had the highest cobalt, nickel, aluminium, iron and chromium (up to 1.6 μM, 3.6 μM, 1586 μM, 936 μM and 3.0 μM, respectively) and the high-chlorinity fluids had the highest zinc, cadmium, manganese and lead (up to 4.1 μM, 1.0 μM, 230 μM and 32 μM, respectively). Geochemical modelling suggests that metals in the former are likely to have been transported as sulphate species or free ions and in the latter as chloride species or free ions. Isotopic values for both water types range between δD -12 to 33‰ and δ 18O 1.2 to 4.6‰. The range of fluid compositions and isotopic contents indicates a complex history of evolution for the system. Both types of fluids appear to be derived from seawater and thus are likely to represent end members of a single fluid phase that underwent phase separation at depth.

Analytical and biological characterization of halogenated gemfibrozil produced through chlorination of wastewater.

PubMed

Bulloch, Daryl N; Lavado, Ramon; Forsgren, Kristy L; Beni, Szabolcs; Schlenk, Daniel; Larive, Cynthia K

2012-05-15

The cholesterol-lowering pharmaceutical gemfibrozil is a relevant environmental contaminant because of its frequency of detection in U.S. wastewaters at concentrations which have been shown to disrupt endocrine function in aquatic species. The treatment of gemfibrozil solutions with sodium hypochlorite yielded a 4'-chlorinated gemfibrozil analog (chlorogemfibrozil). In the presence of bromide ion, as is often encountered in municipal wastewater, hypobromous acid generated through a halogen exchange reaction produced an additional 4'-brominated gemfibrozil product (bromogemfibrozil). Standards of chloro- and bromogemfibrozil were synthesized, isolated and characterized using mass spectrometry and NMR spectroscopy. Mass spectrometry was used to follow the in situ halogenation reaction of gemfibrozil in deionized water and wastewater matrices, and to measure levels of gemfibrozil (254 ± 20 ng/L), chlorogemfibrozil (166 ± 121 ng/L), and bromogemfibrozil (50 ± 11 ng/L) in advanced primary wastewater treatment effluent treated by chlorination. Chlorogemfibrozil demonstrated a significant (p < 0.05) reduction in the levels of 11-ketotestosterone at 55.1 μg/L and bromogemfibrozil demonstrated a significant (p < 0.05) reduction in the levels of testosterone at 58.8 μg/L in vivo in Japanese medaka in a 21 day exposure. These results indicated that aqueous exposure to halogenated degradates of gemfibrozil enhanced the antiandrogenicity of the parent compound in a model fish species, demonstrating that chlorination may increase the toxicity of pharmaceutically active compounds in surface water.

Factors affecting the roles of reactive species in the degradation of micropollutants by the UV/chlorine process.

PubMed

Wu, Zihao; Guo, Kaiheng; Fang, Jingyun; Yang, Xueqin; Xiao, Hong; Hou, Shaodong; Kong, Xiujuan; Shang, Chii; Yang, Xin; Meng, Fangang; Chen, Liwei

2017-12-01

The UV/chlorine process is an emerging advanced oxidation process (AOP) that produces various reactive species, such as hydroxyl radicals (HO) and reactive chlorine species (RCS). The effects of the treatment conditions, such as chlorine dosage and pH, and the water matrix components of natural organic matter (NOM), alkalinity, ammonia and halides, on the kinetics and reactive species in the degradation of four micropollutants, metronidazole (MDZ), nalidixic acid (NDA), diethyltoluamide (DEET) and caffeine (CAF), by the UV/chlorine process were investigated. The degradation of MDZ and CAF was primarily attributable to HO and ClO, respectively, while that of NDA was primarily attributable to both ClO and CO 3 - . HO, Cl and CO 3 - are important for the degradation of DEET. The second-order rate constants for ClO with CAF and CO 3 - with NDA were determined to be 5.1 (±0.2) × 10 7  M -1 s -1 and 1.4 (±0.1) × 10 7  M -1 s -1 , respectively. Increasing chlorine dosage slightly changed the contribution of HO but linearly increased that of ClO to micropollutant degradation. Increasing pH decreased the contribution of either HO or Cl but not that of ClO. Both NOM and bicarbonate decreased the contributions of HO and Cl, whereas NOM but not bicarbonate significantly decreased that of ClO. The contribution of either HO or Cl first rose and then fell as the molar ratio of ammonia to chlorine increased from 0 to 1:1, while that of ClO decreased. The co-presence of high concentrations of Cl - and Br - enhanced the contribution of ClBr - and BrCl. Copyright © 2017 Elsevier Ltd. All rights reserved.

Transformation of aminopyrine in the presence of free available chlorine: Kinetics, products, and reaction pathways.

PubMed

Cai, Mei-Quan; Feng, Li; Zhang, Li-Qiu

2017-03-01

Aminopyrine (AMP) has been frequently detected in the aquatic environment. In this study, the transformation mechanism of AMP by free available chlorine (FAC) oxidation was investigated. The results showed that FAC reacted with AMP rapidly, and a 74% elimination was achieved for 1.30 μM AMP after 2 min at 14.08 μM FAC dose. AMP chlorination was strongly pH-dependent, and its reaction included second- and third-order kinetic processes. Three active FAC species, including chlorine monoxide (Cl 2 O), molecular chlorine (Cl 2 ), and hypochlorous acid (HOCl), were observed to contribute to AMP degradation. The intrinsic rate constants of each FAC species with neutral (AMP 0 ) and cation (AMP + ) species were obtained by kinetic fitting. Cl 2 O exhibited the highest reactivity with AMP 0 (k AMP0, Cl2O  = (4.33 ± 1.4) × 10 9  M -1 s -1 ). In addition, Cl 2 showed high reactivity (10 6 -10 7  M -1 s -1 ) in the presence of chloride, compared with HOCl (k AMP+, HOCl  = (5.73 ± 0.23) × 10 2  M -1 s -1 , k AMP0, HOCl  = (9.68 ± 0.96) × 10 2  M -1 s -1 ). At pH 6.15 and 14.08 μM FAC dose without chloride addition, the contribution of Cl 2 O reached to the maximum (33.3%), but in the whole pH range, HOCl was the main contributor (>66.6%) for AMP degradation. The significance of Cl 2 was noticeable in water containing chloride. Moreover, 11 transformation products were identified, and the main transformation pathways included pyrazole ring breakage, hydroxylation, dehydrogenation, and halogenation. Copyright © 2016 Elsevier Ltd. All rights reserved.

ATRAZOME CHLORINATION TRANSFORMATION PRODUCTS UNDER DRINKING WATER DISTRIBUTION SYSTEM CONDITIONS

EPA Science Inventory

Chlorination is a commonly-used disinfectant step in drinking water treatment. Should free chlorine be added to water used as a drinking water source, it is widely understood that many biological species in the water, along with dissolved organic and inorganic chemicals, will rea...

Using the nuclear activation AMS method for determining chlorine in solids at ppb-levels and below

NASA Astrophysics Data System (ADS)

Winkler, Stephan R.; Eigl, Rosmarie; Forstner, Oliver; Martschini, Martin; Steier, Peter; Sterba, Johannes H.; Golser, Robin

2015-10-01

Neutron activation analysis using decay counting of the activated element is a well-established method in elemental analysis. However, for chlorine there is a better alternative to measuring decay of the short-lived activation product chlorine-38 (t1/2 = 37.24 min) - accelerator mass spectrometry (AMS) of 36Cl: the relatively high neutron capture cross section of chlorine-35 for thermal neutrons (43.7 b) and combined the AMS technique for chlorine-36 (t1/2 = 301 ka) allow for determination of chlorine down to ppb-levels using practical sample sizes and common exposure durations. The combination of neutron activation and AMS can be employed for a few other elements (nitrogen, thorium, and uranium) as well. For bulk solid samples an advantage of the method is that lab contamination can be rendered irrelevant. The chlorine-35 in the sample is activated to chlorine-36, and surface chlorine can be removed after the irradiation. Subsequent laboratory contamination, however, will not carry a prominent chlorine-36 signature. After sample dissolution and addition of sufficient amounts of stable chlorine carrier the produced chlorine-36 and thus the original chlorine-35 of the sample can be determined using AMS. We have developed and applied the method for analysis of chlorine in steel samples. The chlorine content of steel is of interest to nuclear industry, precisely because of above mentioned high neutron capture cross section for chlorine-35, which leads to accumulation of chlorine-36 as long-term nuclear waste. The samples were irradiated at the TRIGA Mark II reactor of the Atominstitut in Vienna and the 36Cl-AMS setup at the Vienna Environmental Research Accelerator (VERA) was used for 36Cl/Cl analysis.

DETERMINING ACTIVE OXIDANT SPECIES REACTING WITH ORGANOPHOSPHATE PESTICIDES IN CHLORINATED DRINKING WATER

EPA Science Inventory

Chlorpyrifos (CP) is an organophosphate (OP) pesticide that was used as a model compound to investigate the transformation of OP pesticides at low pH and in the presence of bromide and natural organic matter (NOM) under drinking water treatment conditions. Raman spectroscopy was...

Assessment of residual active chlorine in sodium hypochlorite solutions after dissolution of porcine incisor pulpal tissue.

PubMed

Clarkson, R M; Smith, T K; Kidd, B A; Evans, G E; Moule, A J

2013-12-01

In previous studies, surfactant-containing Hypochlor brands of sodium hypochlorite showed better tissue solubilizing abilities than Milton; differences not explained by original active chlorine content or presence of surfactant. It was postulated that exhaustion of active chlorine content could explain differences. This study aimed to assess whether Milton's poorer performance was due to exhaustion of active chlorine. Parallel experiments assessed the influence of titration methods, and the presence of chlorates, on active chlorine measurements. Time required to dissolve one or groups of 10 samples of porcine incisor pulp samples in Milton was determined. Residual active chlorine was assessed by thermometric titration. Iodometric and thermometric titration was carried out on samples of Milton. Chlorate content was also measured. Dissolution of single and 10 pulp samples caused a mean loss of 1% and 3% respectively of active chlorine, not being proportional to tissue dissolved. Thermometric ammonium ion titration resulted in 10% lower values than iodometric titration. Chlorate accounted for much of this difference. Depletion of active chlorine is not the reason for differences in tissue dissolving capabilities of Milton. Thermometric ammonium ion titration gives more accurate measurement of active chlorine content than iodometric titration. © 2013 Australian Dental Association.

Kinetics and pathways of ibuprofen degradation by the UV/chlorine advanced oxidation process.

PubMed

Xiang, Yingying; Fang, Jingyun; Shang, Chii

2016-03-01

The UV/chlorine advanced oxidation process (AOP), which forms reactive species such as hydroxyl radicals (HO) and reactive chlorine species (RCS) such as chlorine atoms (Cl) and Cl2(-), is being considered as an alternative to the UV/H2O2 AOP for the degradation of emerging contaminants. This study investigated the kinetics and pathways of the degradation of a recalcitrant pharmaceutical and personal care product (PPCP)-ibuprofen (IBP)-by the UV/chlorine AOP. The degradation of IBP followed the pseudo first-order kinetics. The first-order rate constant was 3.3 times higher in the UV/chlorine AOP than in the UV/H2O2 AOP for a given chemical molar dosage at pH 6. The first-order rate constant decreased from 3.1 × 10(-3) s(-1) to 5.5 × 10(-4) s(-1) with increasing pH from 6 to 9. Both HO and RCS contributed to the degradation, and the contribution of RCS increased from 22% to 30% with increasing pH from 6 to 9. The degradation was initiated by HO-induced hydroxylation and Cl-induced chlorine substitution, and sustained through decarboxylation, demethylation, chlorination and ring cleavage to form more stable products. Significant amounts of chlorinated intermediates/byproducts were formed from the UV/chlorine AOP, and four chlorinated products were newly identified. The yield of total organic chlorine (TOCl) was 31.6 μM after 90% degradation of 50 μM IBP under the experimental conditions. The known disinfection by-products (DBPs) comprised 17.4% of the TOCl. The effects of water matrix in filtered drinking water on the degradation were not significant, demonstrating the practicality of the UV/chlorine AOP for the control of some refractory PPCPs. However, the toxicity of the chlorinated products should be further assessed. Copyright © 2015 Elsevier Ltd. All rights reserved.

Quasi-Liquid Layer Formation on Ice under Stratospheric Conditions

NASA Technical Reports Server (NTRS)

McNeill, V. Faye; Loerting, Thomas; Trout, Bernhardt L.; Molina, Luisa T.; Molina, Mario J.

2004-01-01

Characterization of the interaction of hydrogen chloride (HCl) with ice is essential to understanding at a molecular level the processes responsible for ozone depletion involving polar stratospheric cloud (PSC) particles. To explain the catalytic role PSC particle surfaces play during chlorine activation, we proposed previously that HCl induces the formation of a disordered region on the ice surface, a quasi-liquid layer (QLL), at stratospheric conditions. The QLL is known to exist in pure ice crystals at temperatures near the melting point, but its existence at stratospheric temperatures (-85 C to -70 C) had not been reported yet. We studied the interaction of HCl with ice under stratospheric conditions using the complementary approach of a) ellipsometry to directly monitor the ice surface, using chemical ionization mass spectrometry (CIMS) to monitor the gas phase species present in the ellipsometry experiments, and b) flow-tube experiments with CIMS detection. Here we show that trace amounts of HCl induce QLL formation at stratospheric temperatures, and that the QLL enhances the chlorine-activation reaction of HCl with chlorine nitrate (ClONO2), and also enhances acetic acid (CH3COOH) adsorption.

Electrofabrication of functional materials: Chloramine-based antimicrobial film for infectious wound treatment.

PubMed

Qu, Xue; Liu, Huan; Zhang, Chuchu; Lei, Yu; Lei, Miao; Xu, Miao; Jin, Dawei; Li, Peng; Yin, Meng; Payne, Gregory F; Liu, Changsheng

2018-06-01

Electrical signals can be imposed with exquisite spatiotemporal control and provide exciting opportunities to create structure and confer function. Here, we report the use of electrical signals to program the fabrication of a chloramine wound dressing with high antimicrobial activity. This method involves two electrofabrication steps: (i) a cathodic electrodeposition of an aminopolysaccharide chitosan triggered by a localized region of high pH; and (ii) an anodic chlorination of the deposited film in the presence of chloride. This electrofabrication process is completed within several minutes and the chlorinated chitosan can be peeled from the electrode to yield a free-standing film. The presence of active NCl species in this electrofabricated film was confirmed with chlorination occurring first on the amine groups and then on the amide groups when large anodic charges were used. Electrofabrication is quantitatively controllable as the cathodic input controls film growth during deposition and the anodic input controls film chlorination. In vitro studies demonstrate that the chlorinated chitosan film has antimicrobial activities that depend on the chlorination degree. In vivo studies with a MRSA infected wound healing model indicate that the chlorinated chitosan film inhibited bacterial growth, induced less inflammation, developed reorganized epithelial and dermis structures, and thus promoted wound healing compared to a bare wound or wound treated with unmodified chitosan. These results demonstrate the fabrication of advanced functional materials (i.e., antimicrobial wound dressings) using controllable electrical signals to both organize structure through non-covalent interactions (i.e., induce chitosan's reversible self-assembly) and to initiate function-conferring covalent modifications (i.e., generate chloramine bonds). Potentially, electrofabrication may provide a simple, low cost and sustainable alternative for materials fabrication. We believe this work is novel because this is the first report (to our knowledge) that electronic signals enable the fabrication of advanced antimicrobial dressings with controlled structure and biological performance. We believe this work is significant because electrofabrication enables rapid, controllable and sustainable materials construction with reduced adverse environmental impacts while generating high performance materials for healthcare applications. More specifically, we report an electrofbrication of antimicrobial film that can promote wound healing. Copyright © 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Bromine-Chlorine Coupling in the Antarctic Ozone Hole

NASA Technical Reports Server (NTRS)

Danilin, Michael Y.; Sze, Nien-Dak; Ko, Malcolm K. W.; Rodriquez, Jose M.; Prather, Michael J.

1996-01-01

The contribution from the chlorine and bromine species in the formation of the Antarctic ozone hole is evaluated. Since chlorine and bromine compounds are of different industrial origin, it is desirable, from a policy point of view, to be able to attribute chlorine-catalyzed loss of ozone with those reactions directly involving chlorine species, and likewise for bromine-catalyzed loss. In the stratosphere, however, most of the chemical families are highly coupled, and, for example, changes in the chlorine abundance will alter the partitioninig in other families and thus the rate of ozone loss. This modeling study examines formation of the Antarctic ozone hole for a wide range of bromine concentrations (5 - 25 pptv) and for chlorine concentrations typical of the last two decades (1.5, 2.5 and 3.5 ppbv). We follow the photochemical evolution of a single parcel of air, typical of the inner Antarctic vortex (50 mbar, 70 deg. S, NO(sub y) = 2 ppbv, with Polar Stratospheric Clouds(PSC)) from August 1 to November 1. For all of these ranges of chlorine and bromine loading, we would predict a substantial ozone hole (local depletion greater than 90%) within the de-nitrified, PSC- perturbed vortex. The contributions of the different catalytic cycles responsible for ozone loss are tabulated. The deep minimum in ozone is driven primarily by the chlorine abundance. As bromine levels decrease, the magnitude of the chlorine-catalyzed ozone loss increases to take up the slack. This is because bromine suppresses ClO by accelerating the conversion of ClO an Cl2O2 back to HCI. For this range of conditions, the local relative efficiency of ozone destruction per bromine atom to that per chlorine atom (alpha-factor) ranges from 33 to 55, decreasing with increase of bromine.

[Influence of tap water treatment on perfluorinated compounds residue in the dissolved phase].

PubMed

Zhang, Hong; Chen, Qing-wu; Wang, Xin-xuan; Chai, Zhi-fang; Shen, Jin-can; Yang, Bo; Liu, Guo-qing

2013-09-01

To study the perfluorinated compounds (PFCs) residues through water treatments including flocculation, sedimentation, sand filtration, ozonation with activated carbon and chlorination, as well as the seasonal variation of PFCs in the raw water of waterworks, 13 PFCs species in the dissolved phase of raw water, finished water, as well as the water samples after flocculation, sedimentation, sand filtration, and ozonation with activated carbon filtration were measured by the high performance liquid chromatography-tandem mass spectrometry combined with solid phase extraction. Results indicated that sigma PFCs residue in water was higher in spring and summer than that in fall and winter. The vast majority of PFCs in samples were of short and medium chains (C < or = 10), and perfluorooctane sulfonate was the most typical residue species. Among the five water treatment stages, sedimentation, sand filtration and ozonation with activated carbon filtration can remove PFCs, while flocculation and chlorination significantly raise the levels of short- (C < or = 6) and medium-chain (10 > or = C > or = 7) PFCs, respectively, causing sigma PFCs increase in finished water by 10%-44% compared to raw water. However, the PFCs residues in finished water are still far below their limit values, posing no threat against human health.

Anticancer activity of the new photosensitizers: dose and cell type dependence

NASA Astrophysics Data System (ADS)

Gyulkhandanyan, Grigor V.; Ghambaryan, Sona S.; Amelyan, Gayane V.; Ghazaryan, Robert K.; Haroutiunian, Samvel G.; Gyulkhandanyan, Aram G.; Gasparyan, Gennadi H.

2005-04-01

The necessity of researches of antitumor efficiency of new photosensitizers (PS) is explained by the opportunity of their application in photodynamic therapy of tumors. PS, selectively accumulated in cancer cells and activated by the light, generate the active oxygen species that cause apoptosis. Earlier, it was shown that PS chlorin e6 (0.3-0.5 μg/ml) induces rat embryo fibroblast-like cell apoptosis. In present work antitumor activity of the new photosensitizers, water-soluble cationic porphyrins and their metal complexes, is investigated. The dose-dependent destruction of cancer cells was shown on PC-12 (pheochromocytoma, rat adrenal gland) and Jurkat (human lymphoma) cell lines. Meso-tetra-[4-N-(2 `- oxyethyl) pyridyl] porphyrin (TOEPyP) and chlorin e6 possessed the same toxicity at LD50 dose on PC-12 cell line, whereas phototoxicity of TOEPyP was 3 times less compared to chlorin e6(LD50=0.2 and 0.075 μg/ml accordingly). The results have shown weak photosensitizing effect of Zn-and Ag-derivatives of TOEPyP on PC-12 cell line. TOEPyP and Zn-TOEPyP (0.1 - 50 μg/ml) were non-toxic for Jurkat cell line, whereas Ag-TOEPyP was toxic at 10 μg/ml (LD90). TOEPyP and chlorin e6 have shown phototoxic effect in the same dose range (LD50=0.5 and 0.3 μg/ml accordingly). The investigation of toxic and phototoxic effects of the new porphyrins revealed significantly different sensitivity of various cell lines to PSs.

Myeloperoxidase scavenges peroxynitrite: A novel anti-inflammatory action of the heme enzyme

PubMed Central

Koyani, Chintan N.; Flemmig, Joerg; Malle, Ernst; Arnhold, Juergen

2015-01-01

Peroxynitrite, a potent pro-inflammatory and cytotoxic species, interacts with a variety of heme containing proteins. We addressed the question whether (i) the interaction of myeloperoxidase (MPO, an enzyme generating hypochlorous acid from hydrogen peroxide and chloride ions) with peroxynitrite affects the clearance of peroxynitrite, and (ii) if peroxynitrite could modulate the chlorinating activity of MPO. Our results show that this interaction promotes the decomposition of the highly reactive pro-inflammatory oxidant, whereby MPO Compound II (but not Compound I) is formed. The efficiency of MPO to remove peroxynitrite was enhanced by l-tyrosine, nitrite and (−)-epicatechin, substances known to reduce Compound II with high reaction rate. Next, peroxynitrite (added as reagent) diminished the chlorinating activity of MPO in the presence of hydrogen peroxide. Alternatively, SIN-1, a peroxynitrite donor, reduced hypochlorous acid formation by MPO, as measured by aminophenyl fluorescein oxidation (time kinetics) and taurine chloramine formation (end point measurement). At inflammatory loci, scavenging of peroxynitrite by MPO may overcome the uncontrolled peroxynitrite decomposition and formation of reactive species, which lead to cell/tissue damage. PMID:25731855

The RclR Protein Is a Reactive Chlorine-specific Transcription Factor in Escherichia coli *

PubMed Central

Parker, Benjamin W.; Schwessinger, Emily A.; Jakob, Ursula; Gray, Michael J.

2013-01-01

Reactive chlorine species (RCS) such as hypochlorous acid are powerful antimicrobial oxidants. Used extensively for disinfection in household and industrial settings (i.e. as bleach), RCS are also naturally generated in high quantities during the innate immune response. Bacterial responses to RCS are complex and differ substantially from the well characterized responses to other physiologically relevant oxidants, like peroxide or superoxide. Several RCS-sensitive transcription factors have been identified in bacteria, but most of them respond to multiple stressors whose damaging effects overlap with those of RCS, including reactive oxygen species and electrophiles. We have now used in vivo genetic and in vitro biochemical methods to identify and demonstrate that Escherichia coli RclR (formerly YkgD) is a redox-regulated transcriptional activator of the AraC family, whose highly conserved cysteine residues are specifically sensitive to oxidation by RCS. Oxidation of these cysteines leads to strong, highly specific activation of expression of genes required for survival of RCS stress. These results demonstrate the existence of a widely conserved bacterial regulon devoted specifically to RCS resistance. PMID:24078635

The RclR protein is a reactive chlorine-specific transcription factor in Escherichia coli.

PubMed

Parker, Benjamin W; Schwessinger, Emily A; Jakob, Ursula; Gray, Michael J

2013-11-08

Reactive chlorine species (RCS) such as hypochlorous acid are powerful antimicrobial oxidants. Used extensively for disinfection in household and industrial settings (i.e. as bleach), RCS are also naturally generated in high quantities during the innate immune response. Bacterial responses to RCS are complex and differ substantially from the well characterized responses to other physiologically relevant oxidants, like peroxide or superoxide. Several RCS-sensitive transcription factors have been identified in bacteria, but most of them respond to multiple stressors whose damaging effects overlap with those of RCS, including reactive oxygen species and electrophiles. We have now used in vivo genetic and in vitro biochemical methods to identify and demonstrate that Escherichia coli RclR (formerly YkgD) is a redox-regulated transcriptional activator of the AraC family, whose highly conserved cysteine residues are specifically sensitive to oxidation by RCS. Oxidation of these cysteines leads to strong, highly specific activation of expression of genes required for survival of RCS stress. These results demonstrate the existence of a widely conserved bacterial regulon devoted specifically to RCS resistance.

Combined toxicity effects of chlorine, ammonia, and temperature on marine plankton. Progress report, November 1976--31 January 1978

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goldman, J. C.

1978-02-01

Studies on the effects of chlorine, chloramines, and temperature on marine plankton have been carried out for three years. Species studied include marine phytoplankton, lobster larvae (Homarus americanus), oyster larvae (Crassostrea virginica), copepods (Acartia tonsa), rotifers (Brachionas plicatilis), grass shrimp (Palamonetes pugio) summer flounder larvae (Paralichthys dentatus), larval and juvenile killifish (Fundulus heteroclitus), juvenile scup (Stenotomus versicolor), and juvenile winter flounder (Pseudopleuronectes americanus). In addition extensive studies on chlorine chemistry in seawater have been carried out. The major conclusions are that entrainment effects on permanent plankton such as phytoplankton, copepods, and rotifers are temporary, that is those organisms surviving chlorinationmore » and temperature shocks are capable of renewed and unrestricted growth once returned to the receiving water. Because chlorine is only applied for short periods daily in most power plants, the total population of the above organisms actually exposed to chlorine is small and the effects may be hardly measurable in receiving waters. However, chlorination effects on larval species that spawn intermittently could be catastrophic. In addition, there are many unanswered questions regarding the fate of chlorine that is dissipated in marine waters. Are the losses real and, if so, do they pose a toxicity threat to marine biota.« less

An integrated (electro- and bio-oxidation) approach for remediation of industrial wastewater containing azo-dyes: Understanding the degradation mechanism and toxicity assessment.

PubMed

Aravind, Priyadharshini; Selvaraj, Hosimin; Ferro, Sergio; Sundaram, Maruthamuthu

2016-11-15

A hybrid approach for the remediation of recalcitrant dye wastewater is proposed. The chlorine-mediated electrochemical oxidation of real textile effluents and synthetic samples (using Ti/IrO2-RuO2-TiO2 anodes), lead to discoloration by 92% and 89%, respectively, in 100min, without significant mineralization. The remediation was obtained through biodegradation, after removing the residual bio-toxic active chlorine species via sunlight exposition. Results show that the electrochemical discoloration enhances the effluent biodegradability with about 90% COD removal employing acclimatized naphthalene-degrading bacterial consortia, within 144h. Based on results obtained through FT-IR and GC-MS, it is likely that azo group stripping and oxidative cleavage of dyes occur due to the nucleophilic attack of active chlorine species during electro-oxidation. This leads to generation of aromatic intermediates which are further desulfonated, deaminated or oxidized only at their functional groups. These aromatic intermediates were mineralized into simpler organic acids and aldehydes by bacterial consortia. Phyto-toxicity trials on Vigna radiata confirmed the toxic nature of the untreated dye solutions. An increase in root and shoot development was observed with the electrochemically treated solutions, the same was higher in case of bio-treated solutions. Overall, obtained results confirm the capability of the proposed hybrid oxidation scheme for the remediation of textile wastewater. Copyright © 2016 Elsevier B.V. All rights reserved.

Monsoon Circulations and Tropical Heterogeneous Chlorine Chemistry in the Stratosphere

NASA Astrophysics Data System (ADS)

Kinnison, Doug; Solomon, Susan; Garcia, Rolando; Bandoro, Justin; Wilka, Catherine; Neeley, Ryan, III; Schmidt, Anja; Barnes, John; Vernier, Jean-Paul; Höpfner, Michael; Mills, Michael

2017-04-01

Heterogeneous chlorine chemistry on and in liquid polar stratospheric particles is thought to play a significant role in polar and subpolar ozone depletion. Previous studies have not provided evidence for heterogeneous chlorine chemistry occurring in the tropical stratosphere. Using the current best understanding of liquid stratospheric particle chemistry in a state-of-the-art numerical model, we examine whether such processes should be expected to affect tropical composition, particularly at and slightly above the cold tropical tropopause, in association with the Asian and North American summer (June-July-August) monsoons. The Specified Dynamics version of the Community Earth System Model version 1 (CESM1) Whole Atmosphere Community Climate Model (WACCM) is used in this study. This model is nudged to externally specified dynamical fields for temperature, zonal and meridional winds, and surface pressure fields from the NASA Modern Era Retrospective Analysis for Research and Applications (MERRA). Model simulations suggest that transport processes associated with the summer monsoons bring increased abundances of hydrochloric acid (HCl) into contact with liquid sulfate aerosols in the cold tropical lowermost stratosphere, leading to heterogeneous chemical activation of chlorine species. The calculations indicate that the spatial and seasonal distributions of chlorine monoxide (ClO) and chlorine nitrate (ClONO2) near the monsoon regions of the northern hemisphere tropical and subtropical lowermost stratosphere could provide indicators of heterogeneous chlorine processing. In the model, these processes impact the local ozone budget and decrease ozone abundances, implying a chemical contribution to longer-term northern tropical ozone profile changes at 16-19 km.

Chlorination and chloramination of aminophenols in aqueous solution: oxidant demand and by-product formation.

PubMed

Mehrez, O Abou; Dossier-Berne, F; Legube, B

2015-01-01

Chlorination and monochloramination of aminophenols (AP) were carried out in aqueous solution at 25°C and at pH 8.5. Oxidant demand and disinfection by-product formation were determined in excess of oxidant. Experiments have shown that chlorine consumption of AP was 40-60% higher than monochloramine consumption. Compared with monochloramination, chlorination of AP formed more chloroform and haloacetic acids (HAA). Dichloroacetic acid was the major species of HAA. Chloroform and HAA represented, respectively, only 1-8% and 14-15% of adsorbable organic halides (AOX) by monochloramination but up to 29% and 39% of AOX by chlorination.

Importance of chlorine speciation on de novo formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans.

PubMed

Wikström, Evalena; Ryan, Shawn; Touati, Abderrahmane; Telfer, Marnie; Tabor, Dennis; Gullett, Brian K

2003-03-15

The role of chlorine speciation on de novo formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) has been studied thoroughly in an entrained flow reactor during simulated waste combustion. The effects of gas-phase chlorine species such as chlorine (Cl2), hydrogen chloride (HCl), and chlorine radicals (Cl*), as well as ash-bound chlorine, on PCDD/F de novo formation were isolated for investigation. The ash-bound chlorine alone was observed to be a sufficient chlorine source for PCDD/F formation. The addition of HCl to the system did not influence the yields of the PCDDs/Fs nor the degree of chlorination due to its poor chlorinating ability. Addition of 200 ppm of Cl2 to the ash-feed system resulted in increased PCDD/F yields, especially for the octa- and hepta-chlorinated congeners. Altering the reaction temperature to enable the presence of only Cl2 to the system did not change the yields of PCDD/F compared to those when both Cl2/Cl* were present. However, comparison between ash-bound and gas-phase chlorine, the latter at a concentration typical of a realistic combustion process, revealed ash-bound chlorine to be the more important chlorine source for de novo formation of PCDD/F in a full-scale incinerator.

Vitamin B12 effects on chlorinated methanes-degrading microcosms: Dual isotope and metabolically active microbial populations assessment.

PubMed

Rodríguez-Fernández, Diana; Torrentó, Clara; Guivernau, Miriam; Viñas, Marc; Hunkeler, Daniel; Soler, Albert; Domènech, Cristina; Rosell, Mònica

2018-04-15

Field-derived anoxic microcosms were used to characterize chloroform (CF) and carbon tetrachloride (CT) natural attenuation to compare it with biostimulation scenarios in which vitamin B 12 was added (B 12 /pollutant ratio of 0.01 and 0.1) by means of by-products, carbon and chlorine compound-specific stable-isotope analysis, and the active microbial community through 16S rRNA MiSeq high-throughput sequencing. Autoclaved slurry controls discarded abiotic degradation processes. B 12 catalyzed CF and CT biodegradation without the accumulation of dichloromethane, carbon disulphide, or CF. The carbon isotopic fractionation value of CF (ƐC CF ) with B 12 was -14±4‰, and the value for chlorine (ƐCl CF ) was -2.4±0.4‰. The carbon isotopic fractionation values of CT (ƐC CT ) were -16±6 with B 12 , and -13±2‰ without B 12 ; and the chlorine isotopic fractionation values of CT (ƐCl CT ) were -6±3 and -4±2‰, respectively. Acidovorax, Ancylobacter, and Pseudomonas were the most metabolically active genera, whereas Dehalobacter and Desulfitobacterium were below 0.1% of relative abundance. The dual C-Cl element isotope slope (Λ=Δδ 13 C/Δδ 37 Cl) for CF biodegradation (only detected with B 12 , 7±1) was similar to that reported for CF reduction by Fe(0) (8±2). Several reductive pathways might be competing in the tested CT scenarios, as evidenced by the lack of CF accumulation when B 12 was added, which might be linked to a major activity of Pseudomonas stutzeri; by different chlorine apparent kinetic isotope effect values and Λ which was statistically different with and without B 12 (5±1 vs 6.1±0.5), respectively. Thus, positive B 12 effects such as CT and CF degradation catalyst were quantified for the first time in isotopic terms, and confirmed with the major activity of species potentially capable of their degradation. Moreover, the indirect benefits of B 12 on the degradation of chlorinated ethenes were proved, creating a basis for remediation strategies in multi-contaminant polluted sites. Copyright © 2017 Elsevier B.V. All rights reserved.

Combustion of chlorinated VOC on nanostructured chromia aerogel as catalyst and catalyst support.

PubMed

Rotter, H; Landau, M V; Herskowitz, M

2005-09-01

The chromia-based catalysts have been reported to combine the high activity and resistance to deactivation in oxidative removal of chlorinated VOC. However, their activity is limited by the low amount of chromia that can be deposited on supports maintaining the optimal state of surface species and high surface area. The pure nanostructured chromia was used as a catalytically active support for noble metals and transition-metal oxide oxidation catalysts. High efficiency of Pt-promoted CrOOH aerogel with surface area of 500 m2*g(-1) was demonstrated in full combustion of 1,2-dichloroethane (DCE) and chlorobenzene (CB). At gas hour space velocity (GHSV) of 46 000 h(-1), the total conversion to CO2/H2O/HCl was achieved at 330 degrees C (DCE) and 380 degrees C (CB). The combustion rate constants measured at standard conditions with 0.5% Pt/CrOOH catalyst were 1 or 2 orders of magnitude higher than measured with 15%Cr2O3/Al2O3 or 0.5%Pt/Al2O3, respectively. The effects of Pt, Au, Mn, and Ce additives on the performance of CrOOH aerogel in combustion of chlorinated VOC were analyzed related to the materials structure.

Unexpected autumnal halogen activity in the lower troposphere at Neumayer III/Antarctica

NASA Astrophysics Data System (ADS)

Nasse, Jan-Marcus; Frieß, Udo; Pöhler, Denis; Schmitt, Stefan; Weller, Rolf; Schaefer, Thomas; Platt, Ulrich

2017-04-01

The influence of Reactive Halogen Species (RHS, like IO, BrO, ClO, etc.) on the lower polar troposphere has been subject of intense research for several decades. Ozone Depletion Events (ODEs) caused by the catalytic reaction of tropospheric ozone with inorganic halogen species or the oxidation of gaseous elemental mercury are well observed phenomena that occur during the respective springtime in both Arctic and Antarctica. Chlorine atoms also react more efficiently with hydrocarbons than e.g. OH radicals and all reactive halogen species can furthermore influence the atmospheric sulphur or nitrate cycles. While an autocatalytic release mechanism from salty surfaces, the so called bromine explosion, has been identified to rapidly increase inorganic bromine mixing ratios many aspects of atmospheric halogen chemistry in polar regions remains unclear. Since January 2016, we are operating an active Long Path DOAS instrument at Neumayer III on the Antarctic Ekström shelf ice designed for autonomous measurements. This instrument is able to detect a wide range of trace gases absorbing in the UV/Vis including ClO, BrO, OClO, IO, I2, OIO, ozone, NO2, H2O, O4, and SO2 at a temporal resolution of 5-30 minutes. The analysis of the first year of observations shows several surprising findings which give new insights into polar halogen chemistry. E.g. we observe surprisingly strong bromine activity in late summer and autumn (in addition to well-known springtime events) with mixing ratios often higher than 20 pptv. We could even observe peak mixing ratios of 110 pptv. The observed BrO levels could be the result of local/regional chemistry rather than long-range transport and modulated by the stability of the boundary layer. Also, there are hints for NOx - driven halogen activation. Furthermore, chlorine monoxide (ClO) and OClO mixing ratios of several ten pptv could be detected on a number of days, however the source mechanism for reactive chlorine remains unclear. We will give an overview of the entire time series and discuss interesting case studies with regard to chemistry, atmospheric conditions and transport.

Optimal design and operation of booster chlorination stations layout in water distribution systems.

PubMed

Ohar, Ziv; Ostfeld, Avi

2014-07-01

This study describes a new methodology for the disinfection booster design, placement, and operation problem in water distribution systems. Disinfectant residuals, which are in most cases chlorine residuals, are assumed to be sufficient to prevent growth of pathogenic bacteria, yet low enough to avoid taste and odor problems. Commonly, large quantities of disinfectants are released at the sources outlets for preserving minimum residual disinfectant concentrations throughout the network. Such an approach can cause taste and odor problems near the disinfectant injection locations, but more important hazardous excessive disinfectant by-product formations (DBPs) at the far network ends, of which some may be carcinogenic. To cope with these deficiencies booster chlorination stations were suggested to be placed at the distribution system itself and not just at the sources, motivating considerable research in recent years on placement, design, and operation of booster chlorination stations in water distribution systems. The model formulated and solved herein is aimed at setting the required chlorination dose of the boosters for delivering water at acceptable residual chlorine and TTHM concentrations for minimizing the overall cost of booster placement, construction, and operation under extended period hydraulic simulation conditions through utilizing a multi-species approach. The developed methodology links a genetic algorithm with EPANET-MSX, and is demonstrated through base runs and sensitivity analyses on a network example application. Two approaches are suggested for dealing with water quality initial conditions and species periodicity: (1) repetitive cyclical simulation (RCS), and (2) cyclical constrained species (CCS). RCS was found to be more robust but with longer computational time. Copyright © 2014 Elsevier Ltd. All rights reserved.

The maintenance of elevated active chlorine levels in the Antarctic lower stratosphere through HCl null cycles

NASA Astrophysics Data System (ADS)

Müller, Rolf; Grooß, Jens-Uwe; Mannan Zafar, Abdul; Robrecht, Sabine; Lehmann, Ralph

2018-03-01

The Antarctic ozone hole arises from ozone destruction driven by elevated levels of ozone destroying (active) chlorine in Antarctic spring. These elevated levels of active chlorine have to be formed first and then maintained throughout the period of ozone destruction. It is a matter of debate how this maintenance of active chlorine is brought about in Antarctic spring, when the rate of formation of HCl (considered to be the main chlorine deactivation mechanism in Antarctica) is extremely high. Here we show that in the heart of the ozone hole (16-18 km or 85-55 hPa, in the core of the vortex), high levels of active chlorine are maintained by effective chemical cycles (referred to as HCl null cycles hereafter). In these cycles, the formation of HCl is balanced by immediate reactivation, i.e. by immediate reformation of active chlorine. Under these conditions, polar stratospheric clouds sequester HNO3 and thereby cause NO2 concentrations to be low. These HCl null cycles allow active chlorine levels to be maintained in the Antarctic lower stratosphere and thus rapid ozone destruction to occur. For the observed almost complete activation of stratospheric chlorine in the lower stratosphere, the heterogeneous reaction HCl + HOCl is essential; the production of HOCl occurs via HO2 + ClO, with the HO2 resulting from CH2O photolysis. These results are important for assessing the impact of changes of the future stratospheric composition on the recovery of the ozone hole. Our simulations indicate that, in the lower stratosphere, future increased methane concentrations will not lead to enhanced chlorine deactivation (through the reaction CH4 + Cl → HCl + CH3) and that extreme ozone destruction to levels below ≈ 0.1 ppm will occur until mid-century.

Observations of denitrification and dehydration in the winter polar stratospheres

NASA Technical Reports Server (NTRS)

Fahey, D. W.; Kelly, K. K.; Kawa, S. R.; Tuck, A. F.; Loewenstein, M.

1990-01-01

It is argued that denitrification of the Arctic stratosphere can be explained by the selective growth and sedimentation of aerosol particles rich in nitric acid. Because reactive nitrogen species moderate the destruction of ozone by chlorine-catalyzed reactions by sequestering chlorine in reservoir species such as ClONO2, the possibility of the removal of reactive nitrogen without dehydration should be allowed for in attempts to model ozone depletion in the Arctic. Indeed, denitrification along with elevated concentrations of reactive chlorine observed in 1989 indicate that the Arctic was chemically primed for ozone destruction without an extended period of temperatures below the frost point, as is characteristic of the Antarctic.

Bulk chlorine uptake by polyamide active layers of thin-film composite membranes upon exposure to free chlorine-kinetics, mechanisms, and modeling.

PubMed

Powell, Joshua; Luh, Jeanne; Coronell, Orlando

2014-01-01

We studied the volume-averaged chlorine (Cl) uptake into the bulk region of the aromatic polyamide active layer of a reverse osmosis membrane upon exposure to free chlorine. Volume-averaged measurements were obtained using Rutherford backscattering spectrometry with samples prepared at a range of free chlorine concentrations, exposure times, and mixing, rinsing, and pH conditions. Our volume-averaged measurements complement previous studies that have quantified Cl uptake at the active layer surface (top ≈ 7 nm) and advance the mechanistic understanding of Cl uptake by aromatic polyamide active layers. Our results show that surface Cl uptake is representative of and underestimates volume-averaged Cl uptake under acidic conditions and alkaline conditions, respectively. Our results also support that (i) under acidic conditions, N-chlorination followed by Orton rearrangement is the dominant Cl uptake mechanism with N-chlorination as the rate-limiting step; (ii) under alkaline conditions, N-chlorination and dechlorination of N-chlorinated amide links by hydroxyl ion are the two dominant processes; and (iii) under neutral pH conditions, the rates of N-chlorination and Orton rearrangement are comparable. We propose a kinetic model that satisfactorily describes Cl uptake under acidic and alkaline conditions, with the largest discrepancies between model and experiment occurring under alkaline conditions at relatively high chlorine exposures.

Evidence That Chlorinated Auxin Is Restricted to the Fabaceae But Not to the Fabeae1[OPEN

PubMed Central

McAdam, Scott A.M.; McAdam, Erin L.

2015-01-01

Auxin is a pivotal plant hormone, usually occurring in the form of indole-3-acetic acid (IAA). However, in maturing pea (Pisum sativum) seeds, the level of the chlorinated auxin, 4-chloroindole-3-acetic acid (4-Cl-IAA), greatly exceeds that of IAA. A key issue is how plants produce halogenated compounds such as 4-Cl-IAA. To better understand this topic, we investigated the distribution of the chlorinated auxin. We show for the first time, to our knowledge, that 4-Cl-IAA is found in the seeds of Medicago truncatula, Melilotus indicus, and three species of Trifolium. Furthermore, we found no evidence that Pinus spp. synthesize 4-Cl-IAA in seeds, contrary to a previous report. The evidence indicates a single evolutionary origin of 4-Cl-IAA synthesis in the Fabaceae, which may provide an ideal model system to further investigate the action and activity of halogenating enzymes in plants. PMID:25971549

Evidence That Chlorinated Auxin Is Restricted to the Fabaceae But Not to the Fabeae.

PubMed

Lam, Hong Kiat; McAdam, Scott A M; McAdam, Erin L; Ross, John J

2015-07-01

Auxin is a pivotal plant hormone, usually occurring in the form of indole-3-acetic acid (IAA). However, in maturing pea (Pisum sativum) seeds, the level of the chlorinated auxin, 4-chloroindole-3-acetic acid (4-Cl-IAA), greatly exceeds that of IAA. A key issue is how plants produce halogenated compounds such as 4-Cl-IAA. To better understand this topic, we investigated the distribution of the chlorinated auxin. We show for the first time, to our knowledge, that 4-Cl-IAA is found in the seeds of Medicago truncatula, Melilotus indicus, and three species of Trifolium. Furthermore, we found no evidence that Pinus spp. synthesize 4-Cl-IAA in seeds, contrary to a previous report. The evidence indicates a single evolutionary origin of 4-Cl-IAA synthesis in the Fabaceae, which may provide an ideal model system to further investigate the action and activity of halogenating enzymes in plants. © 2015 American Society of Plant Biologists. All Rights Reserved.

Low Temperature Fluorine Chemistry of Electronegative Elements.

DTIC Science & Technology

1980-07-15

mixtures were prepared in a stainless steel vacuum line well-passivated with chlorine trifluoride (Matheson 98%). In most cases gas mixtures were prepared...niversit% of Tennessee." Knoxville, Tennessee 37916 Matrix Reactions of Fluorine with Chlorine , Bromine, and Iodine. Infrared Detlection of the XF 2, X2F...stainless sieel vacuum line well-passivated with chlorine trifluoride in the formation of these new mixed halogen species. (Matheson. 98.0%). Research

Military Smokes and Obscurants Fate and Effects: A Literature Review Relative to Threatened and Endangered Species

DTIC Science & Technology

2004-12-01

1999. Use of Aquatic Plants and Algae for Decontamination of Waters Pol- luted with Chlorinated Alkanes. Int J Phytoremediation . 1(3):203-226. An...Terres- trial Plants. Int J Phytoremediation . 3(1):13-40. Laboratory data from plant-mediated transformation of chlorinated and brominated alkanes...alkenes, and chlorinated pesticides, including phytotransformation data from field plants currently used in phytoremediation of trichloroethylene

Review of ultraviolet absorption cross sections of a series of alternative fluorocarbons

NASA Technical Reports Server (NTRS)

Molina, Mario J.

1990-01-01

Solar photolysis is likely to contribute to the stratospheric destruction of those alternative fluorocarbons (HFC's) which have two or more chlorine atoms bonded to the same carbon atom. Two of the eight HFC's considered here fall into this category, namely HFC-123 and HFC141b. For these two species there is good agreement among the various measurements of the ultraviolet cross sections in the wavelength region which is important for atmospheric photodissociation, that is, around 200 nm. There is also good agreement for HFC-124, HFC-22 and HFC-142b. These are the three species which contain one chlorine atom per molecule. The agreement in the measurements is poor for the other species, i.e., those that do not contain chlorine, except in so far as to corroborate that solar photolysis should be negligible relative to destruction by hydroxyl radicals.

OVERVIEW: DISINFECTION OF HELICOBACTER PYLORI AND AEROMONAS SPECIES

EPA Science Inventory

Helicobacter pylori and Aeromonas hydrophila are contaminants listed on the USEPA's 1998 Contaminant Candidate List (CCL).The sensitivity of H. pylori to chlorine and of Aeromonas spp. to inactivation by free chlorine, chloramine and ultraviolet (UV) was examined. Selective and...

MONITORING FOR AEROMONAS SPECIES AFTER TREATMENT WITH COMMON DRINKING WATER DISINFECTANTS

EPA Science Inventory

The sensitivity of Aeromonas spp. To free chlorine, chloramine and ultraviolet (UV) disinfection was determined. Aeromonas hydrophila is a contaminant listed on the USEPA's 1998 Contaminant Candidate List (CCL). Experiments using free chlorine indicated that the Aeromonas spp. ...

RELATIONSHIP BETWEEN DEHALOCOCCOIDES DNA AND DECHLORINATION RATES AT FIELD SITES

EPA Science Inventory

Chlorinated ethenes are common contaminants in groundwater. To date, Dehalococcoides species are the only known organisms capable of completely dechlorinating all chlorinated ethenes to non-toxic ethene. Studies in the laboratory have shown a good correlation between Dehalococco...

Granular Activated Carbon Treatment May Result in Higher Predicted Genotoxicity in the Presence of Bromide.

PubMed

Krasner, Stuart W; Lee, Tiffany Chih Fen; Westerhoff, Paul; Fischer, Natalia; Hanigan, David; Karanfil, Tanju; Beita-Sandí, Wilson; Taylor-Edmonds, Liz; Andrews, Robert C

2016-09-06

Certain unregulated disinfection byproducts (DBPs) are more of a health concern than regulated DBPs. Brominated species are typically more cytotoxic and genotoxic than their chlorinated analogs. The impact of granular activated carbon (GAC) on controlling the formation of regulated and selected unregulated DBPs following chlorine disinfection was evaluated. The predicted cyto- and genotoxicity of DBPs was calculated using published potencies based on the comet assay for Chinese hamster ovary cells (assesses the level of DNA strand breaks). Additionally, genotoxicity was measured using the SOS-Chromotest (detects DNA-damaging agents). The class sum concentrations of trihalomethanes, haloacetic acids, and unregulated DBPs, and the SOS genotoxicity followed the breakthrough of dissolved organic carbon (DOC), however the formation of brominated species did not. The bromide/DOC ratio was higher than the influent through much of the breakthrough curve (GAC does not remove bromide), which resulted in elevated brominated DBP concentrations in the effluent. Based on the potency of the haloacetonitriles and halonitromethanes, these nitrogen-containing DBPs were the driving agents of the predicted genotoxicity. GAC treatment of drinking or reclaimed waters with appreciable levels of bromide and dissolved organic nitrogen may not control the formation of unregulated DBPs with higher genotoxicity potencies.

Wintertime Reactive Chlorine Sources and Speciation in the Great Salt Lake, UT Region

NASA Astrophysics Data System (ADS)

Goldberger, L.; Franchin, A.; Middlebrook, A. M.; Brown, S.; Womack, C.; Moravek, A.; McDuffie, E. E.; Fibiger, D. L.; Baasandorj, M.; Thornton, J. A.

2017-12-01

Several chlorine species were measured in both gas and particle phase using a high-resolution time of flight chemical ionization mass spectrometer (HRToF-CIMS) and an Aerosol Mass Spectrometer (AMS) aboard the NOAA Twin Otter aircraft as part of the Utah Winter Fine Particle Study (UWFPS). The abundance and speciation of gas-phase reactive chlorine species are presented, evaluated during both night and day flights across a range of meteorological conditions and repeated flight paths conducted over the Great Salt Lake region from January 16th to February 12th 2017. Mean, or background, concentrations of HCl, Cl2, ClNO2, and HOCl are measured near zero or on order of tens of ppt. Maximum concentrations of these species are found consistently in Tooele County on order of several ppb to ppm. Elevated levels of HCl and ClNO2 (at night) on order of hundreds of ppt have been observed over urban areas in Salt Lake and Utah Counties as well. Both of these species can form by heterogeneous reactions of acidic gases with sodium chloride in salt particles. The high concentrations of HCl and ClNO2 indicate large point sources of these species or acidic gases in the region, which are characterized by enhancement ratios of species to NOx and SO2 measured by the CIMS and a cavity ring down spectrometer also on board the aircraft. The emission fluxes of these point sources are characterized and their contribution to the regional background of reactive chlorine are evaluated.

Heterogeneous processes: Laboratory, field, and modeling studies

NASA Technical Reports Server (NTRS)

Poole, Lamont R.; Kurylo, Michael J.; Jones, Rod L.; Wahner, Andreas; Calvert, Jack G.; Leu, M.-T.; Fried, A.; Molina, Mario J.; Hampson, Robert F.; Pitts, M. C.

1991-01-01

The efficiencies of chemical families such as ClO(x) and NO(x) for altering the total abundance and distribution of stratospheric ozone are controlled by a partitioning between reactive (active) and nonreactive (reservoir) compounds within each family. Gas phase thermodynamics, photochemistry, and kinetics would dictate, for example, that only about 1 percent of the chlorine resident in the lower stratosphere would be in the form of active Cl or ClO, the remainder existing in the reservoir compounds HCl and ClONO2. The consistency of this picture was recently challenged by the recognition that important chemical transformations take place on polar regions: the Airborne Antarctic Ozone Experiment (AAOE) and the Airborne Arctic Stratospheric Expedition (AASA). Following the discovery of the Antarctic ozone hole, Solomon et al. suggested that the heterogeneous chemical reaction: ClONO2(g)+HCl(s) yields Cl2(g)+HNO3(s) could play a key role in converting chlorine from inactive forms into a species (Cl2) that would rapidly dissociate in sunlight to liberate atomic chlorine and initiate ozone depletion. The symbols (s) and (g) denote solid phase, or adsorbed onto a solid surface, and gas phase, respectively, and represent the approach by which such a reaction is modeled rather than the microscopic details of the reaction. The reaction was expected to be most important at altitudes where PSC's were most prevalent (10 to 25 km), thereby extending the altitude range over which chlorine compounds can efficiently destroy ozone from the 35 to 45 km region (where concentrations of active chlorine are usually highest) to lower altitudes where the ozone concentration is at its peak. This chapter will briefly review the current state of knowledge of heterogeneous processes in the stratosphere, emphasizing those results obtained since the World Meteorological Organization (WMO) conference. Sections are included on laboratory investigations of heterogeneous reactions, the characteristics and climatology of PSC's, stratospheric sulfate aerosols, and evidence of heterogeneous chemical processing.

Tolerance of dormant and active cells in Pseudomonas aeruginosa PA01 biofilm to antimicrobial agents.

PubMed

Kim, Jaeeun; Hahn, Ji-Sook; Franklin, Michael J; Stewart, Philip S; Yoon, Jeyong

2009-01-01

The aim of the study was to determine the susceptibility of active and dormant cell populations from Pseudomonas aeruginosa biofilms to non-antibiotic antimicrobial agents such as chlorine, hydrogen peroxide and silver ions in comparison with antibiotics. Active cells in colony biofilm were differentially labelled by induction of a green fluorescent protein (GFP). Active and dormant cells were sorted in phosphate buffered solution by flow cytometry. Reductions in viability were determined with plate counts. The spatial pattern of metabolic activity in colony biofilm was verified, and the active and dormant cells were successfully sorted according to the GFP intensity. Active cells had bigger cell size and higher intracellular density than dormant cells. While dormant cells were more tolerant to tobramycin and silver ions, active cells were more tolerant to chlorine. Metabolically active cells contain denser intracellular components that can react with highly reactive oxidants such as chlorine, thereby reducing the available concentrations of chlorine. In contrast, the concentrations of silver ions and hydrogen peroxide were constant during treatment. Aerobically grown stationary cells were significantly more tolerant to chlorine unlike other antimicrobial agents. Chlorine was more effective in inactivation of metabolically inactive dormant cells and also more effective under anaerobic conditions. The high oxidative reactivity and rapid decay of chlorine might influence the different antimicrobial actions of chlorine compared with antibiotics. This study contributes to understanding the effects of dormancy and the presence of oxygen on the susceptibility of P. aeruginosa biofilm to a wide range of antimicrobial agents.

Chlorine Isotopes: As a Possible Tracer of Fluid/Bio-Activities on Mars and a Progress Report on Chlorine Isotope Analysis by TIMs

NASA Technical Reports Server (NTRS)

Nakamura, N.; Nyquist, L.E.; Reese, Y.; Shih, C-Y.; Numata, M.; Fujitani, T.; Okano, O.

2009-01-01

Significantly large mass fractionations between chlorine isotopes (Cl-35, Cl-37) have been reported for terrestrial materials including both geological samples and laboratory materials. Also, the chlorine isotopic composition can be used as a tracer for early solar system processes. Moreover, chlorine is ubiquitous on the Martian surface. Typical chlorine abundances in Gusev soils are approx.0.5 %. The global surface average chlorine abundance also is approx.0.5 %. Striking variations among outcrop rocks at Meridiani were reported with some chlorine abundances as high as approx.2%. Characterizing conditions under which chlorine isotopic fractionation may occur is clearly of interest to planetary science. Thus, we have initiated development of a chlorine isotopic analysis technique using TIMS at NASA-JSC. We present here a progress report on the current status of development at JSC and discuss the possible application of chlorine isotopic analysis to Martian meteorites in a search for fluid- and possibly biological activity on Mars.

Biological Evaluation of Methods for the Determination of Free Available Chlorine.

DTIC Science & Technology

1980-03-01

tri • :., t at pH 6.0, 20’C. Lowest C1 level for false positive, mg/l Chloramine Species Test NH2CI NHC1 2 NCI1 DPDT 4.8 b 0.8 DPDTSF 4.8 b 0.6 DPDP 1.1...Available Chlorine Chlorine Membrane Electrode T )PD FACTS biofac Amperometric titration 20. ASIST’IACT C’ntAtmoe so &eJie .b f nerandm Idenwlry by block...methods tested yielded false positive determinations of free chlorine with one or more of the inorganic chloramines . The FACTS procedure was the most

Chlorination of tramadol: Reaction kinetics, mechanism and genotoxicity evaluation.

PubMed

Cheng, Hanyang; Song, Dean; Chang, Yangyang; Liu, Huijuan; Qu, Jiuhui

2015-12-01

Tramadol (TRA) is one of the most detected analgesics in environmental matrices, and it is of high significance to study the reactivity of TRA during chlorination considering its potential toxicity to the environment. The chlorine/TRA reaction is first order with respect to the TRA concentration, and a combination of first-order and second-order with respect to chlorine concentration. The pH dependence of the observed rate constants (kobs) showed that the TRA oxidation reactivity increased with increasing pH. kobs can be quantitatively described by considering all active species including Cl2, Cl2O and HOCl, and the individual rate constants of HOCl/TRA(0), HOCl/TRAH(+), Cl2/TRA and Cl2O/TRA reactions were calculated to be (2.61±0.29)×10(3)M(-1)s(-1), 14.73±4.17M(-1)s(-1), (3.93±0.34)×10(5)M(-1)s(-1) and (5.66±1.83)×10(6)M(-1)s(-1), respectively. Eleven degradation products were detected with UPLC-Q-TOF-MS, and the corresponding structures of eight products found under various pH conditions were proposed. The amine group was proposed to be the initial attack site under alkaline pH conditions, where reaction of the deprotonated amine group with HOCl is favorable. Under acidic and neutral pH conditions, however, two possible reaction pathways were proposed. One is an electrophilic substitution on the aromatic ring, and another is an electrophilic substitution on the nitrogen, leading to an N-chlorinated intermediate, which can be further oxidized. Finally, the SOS/umu test showed that the genotoxicity of TRA chlorination products increased with increasing dosage of chlorine, which was mostly attributed to the formation of some chlorine substitution products. Copyright © 2015 Elsevier Ltd. All rights reserved.

Sarcoendoplasmic reticulum Ca(2+) ATPase. A critical target in chlorine inhalation-induced cardiotoxicity.

PubMed

Ahmad, Shama; Ahmad, Aftab; Hendry-Hofer, Tara B; Loader, Joan E; Claycomb, William C; Mozziconacci, Olivier; Schöneich, Christian; Reisdorph, Nichole; Powell, Roger L; Chandler, Joshua D; Day, Brian J; Veress, Livia A; White, Carl W

2015-04-01

Autopsy specimens from human victims or experimental animals that die due to acute chlorine gas exposure present features of cardiovascular pathology. We demonstrate acute chlorine inhalation-induced reduction in heart rate and oxygen saturation in rats. Chlorine inhalation elevated chlorine reactants, such as chlorotyrosine and chloramine, in blood plasma. Using heart tissue and primary cardiomyocytes, we demonstrated that acute high-concentration chlorine exposure in vivo (500 ppm for 30 min) caused decreased total ATP content and loss of sarcoendoplasmic reticulum calcium ATPase (SERCA) activity. Loss of SERCA activity was attributed to chlorination of tyrosine residues and oxidation of an important cysteine residue, cysteine-674, in SERCA, as demonstrated by immunoblots and mass spectrometry. Using cardiomyocytes, we found that chlorine-induced cell death and damage to SERCA could be decreased by thiocyanate, an important biological antioxidant, and by genetic SERCA2 overexpression. We also investigated a U.S. Food and Drug Administration-approved drug, ranolazine, used in treatment of cardiac diseases, and previously shown to stabilize SERCA in animal models of ischemia-reperfusion. Pretreatment with ranolazine or istaroxime, another SERCA activator, prevented chlorine-induced cardiomyocyte death. Further investigation of responsible mechanisms showed that ranolazine- and istaroxime-treated cells preserved mitochondrial membrane potential and ATP after chlorine exposure. Thus, these studies demonstrate a novel critical target for chlorine in the heart and identify potentially useful therapies to mitigate toxicity of acute chlorine exposure.

Sarcoendoplasmic Reticulum Ca2+ ATPase. A Critical Target in Chlorine Inhalation–Induced Cardiotoxicity

PubMed Central

Ahmad, Aftab; Hendry-Hofer, Tara B.; Loader, Joan E.; Claycomb, William C.; Mozziconacci, Olivier; Schöneich, Christian; Reisdorph, Nichole; Powell, Roger L.; Chandler, Joshua D.; Day, Brian J.; Veress, Livia A.; White, Carl W.

2015-01-01

Autopsy specimens from human victims or experimental animals that die due to acute chlorine gas exposure present features of cardiovascular pathology. We demonstrate acute chlorine inhalation–induced reduction in heart rate and oxygen saturation in rats. Chlorine inhalation elevated chlorine reactants, such as chlorotyrosine and chloramine, in blood plasma. Using heart tissue and primary cardiomyocytes, we demonstrated that acute high-concentration chlorine exposure in vivo (500 ppm for 30 min) caused decreased total ATP content and loss of sarcoendoplasmic reticulum calcium ATPase (SERCA) activity. Loss of SERCA activity was attributed to chlorination of tyrosine residues and oxidation of an important cysteine residue, cysteine-674, in SERCA, as demonstrated by immunoblots and mass spectrometry. Using cardiomyocytes, we found that chlorine-induced cell death and damage to SERCA could be decreased by thiocyanate, an important biological antioxidant, and by genetic SERCA2 overexpression. We also investigated a U.S. Food and Drug Administration–approved drug, ranolazine, used in treatment of cardiac diseases, and previously shown to stabilize SERCA in animal models of ischemia–reperfusion. Pretreatment with ranolazine or istaroxime, another SERCA activator, prevented chlorine-induced cardiomyocyte death. Further investigation of responsible mechanisms showed that ranolazine- and istaroxime-treated cells preserved mitochondrial membrane potential and ATP after chlorine exposure. Thus, these studies demonstrate a novel critical target for chlorine in the heart and identify potentially useful therapies to mitigate toxicity of acute chlorine exposure. PMID:25188881

A new method for calculation of the chlorine demand of natural and treated waters.

PubMed

Warton, Ben; Heitz, Anna; Joll, Cynthia; Kagi, Robert

2006-08-01

Conventional methods of calculating chlorine demand are dose dependent, making intercomparison of samples difficult, especially in cases where the samples contain substantially different concentrations of dissolved organic carbon (DOC), or other chlorine-consuming species. Using the method presented here, the values obtained for chlorine demand are normalised, allowing valid comparison of chlorine demand between samples, independent of the chlorine dose. Since the method is not dose dependent, samples with substantially differing water quality characteristics can be reliably compared. In our method, we dosed separate aliquots of a water sample with different chlorine concentrations, and periodically measured the residual chlorine concentrations in these subsamples. The chlorine decay data obtained in this way were then fitted to first-order exponential decay functions, corresponding to short-term demand (0-4h) and long-term demand (4-168 h). From the derived decay functions, the residual concentrations at a given time within the experimental time window were calculated and plotted against the corresponding initial chlorine concentrations, giving a linear relationship. From this linear function, it was then possible to determine the residual chlorine concentration for any initial concentration (i.e. dose). Thus, using this method, the initial chlorine dose required to give any residual chlorine concentration can be calculated for any time within the experimental time window, from a single set of experimental data.

Dominant Overall Chemical Reaction in a Chlorine Trifluoride Silicon Nitrogen System at Atmospheric Pressure

NASA Astrophysics Data System (ADS)

Habuka, Hitoshi; Otsuka, Toru; Qu, Wei-Feng

1999-11-01

This study evaluates the overall chemical reaction in a chlorine trifluoride silicon nitrogen system at atmospheric pressure, based on the observation of the dominant chemical species in the gas phase using a quadrupole mass spectra analyzer coupled with a horizontal cold-wall single-wafer epitaxial reactor. Chlorine trifluoride gas etches the silicon surface, producing two major products, silicon tetrafluoride gas and chlorine gas, at room temperature and 530 K. The production of chlorosilanes was not observed in this study. The results obtained in this study indicate that the dominant overall chemical reaction in a chlorine trifluoride silicon nitrogen system is 3Si + 4ClF3 →3SiF4 ↑+ 2Cl2 ↑.

New Generation of Photosensitizers: Conjugates of Chlorin e 6 With Diamond Nanoparticles

NASA Astrophysics Data System (ADS)

Lapina, V. A.; Bushuk, S. B.; Pavich, T. A.; Vorobey, A. V.

2016-07-01

Conjugates of chlorin e 6 with diamond nanoparticles were synthesized by two methods. The spectral and luminescent properties of the obtained conjugates were studied. It was shown that chlorin e 6 retained its photosensitizing activity in the conjugate. It was established that chlorin e 6 immobilized directly on diamond nanoparticles had higher photosensitizing activity than that conjugated using a spacer. It was observed that chlorin e 6 in the conjugate had higher photolytic stability than the free form.

DBP formation from degradation of DEET and ibuprofen by UV/chlorine process and subsequent post-chlorination.

PubMed

Aghdam, Ehsan; Xiang, Yingying; Sun, Jianliang; Shang, Chii; Yang, Xin; Fang, Jingyun

2017-08-01

The formation of disinfection by-products (DBPs) from the degradation of N,N-diethyl-3-methyl benzoyl amide (DEET) and ibuprofen (IBP) by the ultraviolet irradiation (UV)/chlorine process and subsequent post-chlorination was investigated and compared with the UV/H 2 O 2 process. The pseudo first-order rate constants of the degradation of DEET and IBP by the UV/chlorine process were 2 and 3.1 times higher than those by the UV/H 2 O 2 process, respectively, under the tested conditions. This was due to the significant contributions of both reactive chlorine species (RCS) and hydroxyl radicals (HO) in the UV/chlorine process. Trichloromethane, 1,1,1-trichloro-2-propanone and dichloroacetic acid were the major known DBPs formed after 90% of both DEET and IBP that were degraded by the UV/chlorine process. Their yields increased by over 50% after subsequent 1-day post-chlorination. The detected DBPs after the degradation of DEET and IBP comprised 13.5% and 19.8% of total organic chlorine (TOCl), respectively, and the proportions increased to 19.8% and 33.9% after subsequent chlorination, respectively. In comparison to the UV/H 2 O 2 process accompanied with post-chlorination, the formation of DBPs and TOCl in the UV/chlorine process together with post-chlorination was 5%-63% higher, likely due to the generation of more DBP precursors from the attack of RCS, in addition to HO. Copyright © 2017. Published by Elsevier B.V.

Potential for Chlorine Gas–induced Injury in the Extrapulmonary Vasculature

PubMed Central

Samal, Andrey; Honovar, Jaideep; White, C. Roger; Patel, Rakesh P.

2010-01-01

Exposure to chlorine gas (Cl2) primarily causes injury to the lung and is characterized by inflammation and oxidative stress mediated by reactive chlorine species. Reducing lung injury and improving respiratory function are the principal therapeutic goals in treating individuals exposed to Cl2 gas. Less is known on the potential for Cl2 gas exposure to cause injury to extrapulmonary tissues and specifically to mediate endothelial dysfunction. This concept is forwarded in this article on the basis that (1) many irritant gases whose reactivity is limited to the lung have now been shown to have effects that promote endothelial dysfunction in the systemic vasculature, and as such lead to the acute and chronic cardiovascular disease events (e.g., myocardial infarctions and atherosclerosis); and (2) that endogenously produced reactive chlorine species are now considered to be central in the development of cardiovascular diseases. This article discusses these two areas with the view of providing a framework in which potential extrapulmonary toxic effects of Cl2 gas exposure may be considered. PMID:20601634

Adsorption of chlorine dioxide gas on activated carbons.

PubMed

Wood, Joseph P; Ryan, Shawn P; Snyder, Emily Gibb; Serre, Shannon D; Touati, Abderrahmane; Clayton, Matthew J

2010-08-01

Research and field experience with chlorine dioxide (ClO2) gas to decontaminate structures contaminated with Bacillus anthracis spores and other microorganisms have demonstrated the effectiveness of this sterilant technology. However, because of its hazardous properties, the unreacted ClO2, gas must be contained and captured during fumigation events. Although activated carbon has been used during some decontamination events to capture the ClO2 gas, no data are available to quantify the performance of the activated carbon in terms of adsorption capacity and other sorbent property operational features. Laboratory experiments were conducted to determine and compare the ClO2 adsorption capacities of five different types of activated carbon as a function of the challenge ClO2 concentration. Tests were also conducted to investigate other sorbent properties, including screening tests to determine gaseous species desorbed from the saturated sorbent upon warming (to provide an indication of how immobile the ClO2 gas and related compounds are once captured on the sorbent). In the adsorption tests, ClO2 gas was measured continuously using a photometric-based instrument, and these measurements were verified with a noncontinuous method utilizing wet chemistry analysis. The results show that the simple activated carbons (not impregnated or containing other activated sorbent materials) were the most effective, with maximum adsorption capacities of approximately 110 mg/g. In the desorption tests, there was minimal release of ClO(2) from all sorbents tested, but desorption levels of chlorine (Cl2) gas (detected as chloride) varied, with a maximum release of nearly 15% of the mass of ClO2 adsorbed.

Tracking Dietary Sources of Short- and Medium-Chain Chlorinated Paraffins in Marine Mammals through a Subtropical Marine Food Web.

PubMed

Zeng, Lixi; Lam, James C W; Chen, Hui; Du, Bibai; Leung, Kenneth M Y; Lam, Paul K S

2017-09-05

Our previous study revealed an elevated accumulation of short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs) in marine mammals from Hong Kong waters in the South China Sea. To examine the bioaccumulation potential and biomagnification in these apex predators, we sampled the dietary items of marine mammals and tracked the sources of SCCPs and MCCPs through a marine food web in this region. Sixteen fish species, seven crustacean species, and four mollusk species were collected, and the main prey species were identified for two species of marine mammals. Concentrations of ∑SCCPs and ∑MCCPs in these collected species suggested a moderate pollution level in Hong Kong waters compared to the global range. Lipid content was found to mediate congener-specific bioaccumulation in these marine species. Significantly positive correlations were observed between trophic levels and concentrations of ∑SCCPs or ∑MCCPs (p < 0.05). Trophic magnification factors for ∑SCCPs and ∑MCCPs were 4.29 and 4.79, indicating that both of them have trophic magnification potentials. Elevated biomagnification of SCCPs and MCCPs from prey species to marine mammals was observed. This is the first report of dietary source tracking of SCCPs and MCCPs in marine mammals. The elevated biomagnification between prey and marine mammals raises environmental concerns about these contaminants.

PPCP degradation by chlorine-UV processes in ammoniacal water: new reaction insights, kinetic modeling and DBP formation.

PubMed

Zhang, Ruochun; Meng, Tan; Huang, Ching-Hua; Ben, Weiwei; Yao, Hong; Liu, Ruini; Sun, Peizhe

2018-06-15

The combination of chlorine and UV (i.e. chlorine-UV process) has been attracting more attentions in recent years due to its ready incorporation into existing water treatment facilities to remove PPCPs. However, limited information is available on the impact of total ammonia nitrogen (TAN). This study investigated two model PPCPs, N,N-diethyl-3-toluamide (DEET) and caffeine (CAF), in the two stages of chlorine-UV process (i.e. chlorination and UV/chlor(am)ine) to elucidate the impact of TAN. During chlorination, the degradation of DEET and CAF was positively correlated with the overall consumption of total chlorine by TAN. Reactive nitrogen intermediates, including HNO/NO- and ONOOH/ONOO-, along with OH were identified as major contributors to the removal of DEET and CAF. During UV irradiation, DEET and CAF were degraded under UV/chlorine or UV/NH2Cl conditions. OH and Cl were the major reactive species to degrade DEET and CAF under UV/NH2Cl conditions, whereas OCl played a major role for degrading CAF under UV/chlorine conditions. Numerical models were developed to predict the removal of DEET and CAF under chlorination-UV process. Chlorinated disinfection byproducts were detected. Overall, this study presented kinetic features and mechanistic insights on the degradation of PPCPs under chlorine-UV process in ammoniacal water.

Assessment of the bacteriological activity associated with granular activated carbon treatment of drinking water.

PubMed Central

Stewart, M H; Wolfe, R L; Means, E G

1990-01-01

Bacteriological analyses were performed on the effluent from a conventional water treatment pilot plant in which granular activated carbon (GAC) had been used as the final process to assess the impact of GAC on the microbial quality of the water produced. Samples were collected twice weekly for 160 days from the effluents of six GAC columns, each of which used one of four different empty-bed contact times (7.5, 15, 30, and 60 min). The samples were analyzed for heterotrophic plate counts and total coliforms. Effluent samples were also exposed to chloramines and free chlorine for 60 min (pH 8.2, 23 degrees C). Bacterial identifications were performed on the disinfected and nondisinfected effluents. Additional studies were conducted to assess the bacteriological activity associated with released GAC particles. The results indicated that heterotrophic plate counts in the effluents from all columns increased to 10(5) CFU/ml within 5 days and subsequently stabilized at 10(4) CFU/ml. The heterotrophic plate counts did not differ at different empty-bed contact times. Coliforms (identified as Enterobacter spp.) were recovered from the nondisinfected effluent on only two occasions. The disinfection results indicated that 1.5 mg of chloramines per liter inactivated approximately 50% more bacteria than did 1.0 mg of free chlorine per liter after 1 h of contact time. Chloramines and chlorine selected for the development of different bacterial species--Pseudomonas spp. and Flavobacterium spp., respectively.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:2082828

Ground water chlorinated ethenes in tree trunks: Case studies, influence of recharge, and potential degradation mechanism

USGS Publications Warehouse

Vroblesky, D.A.; Clinton, B.D.; Vose, J.M.; Casey, C.C.; Harvey, G.J.; Bradley, P.M.

2004-01-01

Trichloroethene (TCE) was detected in cores of trees growing above TCE-contaminated ground at three sites: the Carswell Golf Course in Texas, Air Force Plant PJKS in Colorado, and Naval Weapons Station Charleston in South Carolina. This was true even when the depth to water was 7.9 m or when the contaminated aquifer was confined beneath ???3 m of clay. Additional ground water contaminants detected in the tree cores were cis-1,2-dichloroethene at two sites and tetrachloroethene at one site. Thus, tree coring can be a rapid and effective means of locating shallow subsurface chlorinated ethenes and possibly identifying zones of active TCE dechlorination. Tree cores collected over time were useful in identifying the onset of ground water contamination. Several factors affecting chlorinated ethene concentrations in tree cores were identified in this investigation. The factors include ground water chlorinated ethene concentrations and depth to ground water contamination. In addition, differing TCE concentrations around the trunk of some trees appear to be related to the roots deriving water from differing areas. Opportunistic uptake of infiltrating rainfall can dilute prerain TCE concentrations in the trunk. TCE concentrations in core headspace may differ among some tree species. In some trees, infestation of bacteria in decaying heartwood may provide a TCE dechlorination mechanism within the trunk.

The single evolutionary origin of chlorinated auxin provides a phylogenetically informative trait in the Fabaceae.

PubMed

Lam, Hong Kiat; Ross, John J; McAdam, Erin L; McAdam, Scott A M

2016-07-02

Chlorinated auxin (4-chloroindole-3-acetic acid, 4-Cl-IAA), a highly potent plant hormone, was once thought to be restricted to species of the tribe Fabeae within the Fabaceae, until we recently detected this hormone in the seeds of Medicago, Melilotus and Trifolium species. The absence of 4-Cl-IAA in the seeds of the cultivated species Cicer aeritinum from the Cicerae tribe, immediately basal to the Fabeae and Trifolieae tribes, suggested a single evolutionary origin of 4-Cl-IAA. Here, we provide a more robust phylogenetic placement of the ability to produce chlorinated auxin by screening key species spanning this evolutionary transition. We report no detectable level of 4-Cl-IAA in Cicer echinospermum (a wild relative of C. aeritinum) and 4 species (Galega officinalis, Parochetus communis, Astragalus propinquus and A. sinicus) from tribes or clades more basal or sister to the Cicerae tribe. We did detect 4-Cl-IAA in the dry seeds of 4 species from the genus Ononis that are either basal to the genera Medicago, Melilotus and Trigonella or basal to, but still within, the Fabeae and Trifolieae (ex. Parochetus) clades. We conclude that the single evolutionary origin of this hormone in seeds can be used as a phylogenetically informative trait within the Fabaceae.

The single evolutionary origin of chlorinated auxin provides a phylogenetically informative trait in the Fabaceae

PubMed Central

Lam, Hong Kiat; Ross, John J.; McAdam, Erin L.; McAdam, Scott A. M.

2016-01-01

ABSTRACT Chlorinated auxin (4-chloroindole-3-acetic acid, 4-Cl-IAA), a highly potent plant hormone, was once thought to be restricted to species of the tribe Fabeae within the Fabaceae, until we recently detected this hormone in the seeds of Medicago, Melilotus and Trifolium species. The absence of 4-Cl-IAA in the seeds of the cultivated species Cicer aeritinum from the Cicerae tribe, immediately basal to the Fabeae and Trifolieae tribes, suggested a single evolutionary origin of 4-Cl-IAA. Here, we provide a more robust phylogenetic placement of the ability to produce chlorinated auxin by screening key species spanning this evolutionary transition. We report no detectable level of 4-Cl-IAA in Cicer echinospermum (a wild relative of C. aeritinum) and 4 species (Galega officinalis, Parochetus communis, Astragalus propinquus and A. sinicus) from tribes or clades more basal or sister to the Cicerae tribe. We did detect 4-Cl-IAA in the dry seeds of 4 species from the genus Ononis that are either basal to the genera Medicago, Melilotus and Trigonella or basal to, but still within, the Fabeae and Trifolieae (ex. Parochetus) clades. We conclude that the single evolutionary origin of this hormone in seeds can be used as a phylogenetically informative trait within the Fabaceae. PMID:27302610

Depletion of chlorine into HCl ice in a protostellar core. The CHESS spectral survey of OMC-2 FIR 4

NASA Astrophysics Data System (ADS)

Kama, M.; Caux, E.; López-Sepulcre, A.; Wakelam, V.; Dominik, C.; Ceccarelli, C.; Lanza, M.; Lique, F.; Ochsendorf, B. B.; Lis, D. C.; Caballero, R. N.; Tielens, A. G. G. M.

2015-02-01

Context. The freezeout of gas-phase species onto cold dust grains can drastically alter the chemistry and the heating-cooling balance of protostellar material. In contrast to well-known species such as carbon monoxide (CO), the freezeout of various carriers of elements with abundances <10-5 has not yet been well studied. Aims: Our aim here is to study the depletion of chlorine in the protostellar core, OMC-2 FIR 4. Methods: We observed transitions of HCl and H2Cl+ towards OMC-2 FIR 4 using the Herschel Space Observatory and Caltech Submillimeter Observatory facilities. Our analysis makes use of state of the art chlorine gas-grain chemical models and newly calculated HCl-H2 hyperfine collisional excitation rate coefficients. Results: A narrow emission component in the HCl lines traces the extended envelope, and a broad one traces a more compact central region. The gas-phase HCl abundance in FIR 4 is 9 × 10-11, a factor of only 10-3 that of volatile elemental chlorine. The H2Cl+ lines are detected in absorption and trace a tenuous foreground cloud, where we find no depletion of volatile chlorine. Conclusions: Gas-phase HCl is the tip of the chlorine iceberg in protostellar cores. Using a gas-grain chemical model, we show that the hydrogenation of atomic chlorine on grain surfaces in the dark cloud stage sequesters at least 90% of the volatile chlorine into HCl ice, where it remains in the protostellar stage. About 10% of chlorine is in gaseous atomic form. Gas-phase HCl is a minor, but diagnostically key reservoir, with an abundance of ≲10-10 in most of the protostellar core. We find the [35Cl]/[37Cl] ratio in OMC-2 FIR 4 to be 3.2 ± 0.1, consistent with the solar system value. Appendices are available in electronic form at http://www.aanda.org

Experimental evidence of large changes in terrestrial chlorine cycling following altered tree species composition.

PubMed

Montelius, Malin; Thiry, Yves; Marang, Laura; Ranger, Jacques; Cornelis, Jean-Thomas; Svensson, Teresia; Bastviken, David

2015-04-21

Organochlorine molecules (Clorg) are surprisingly abundant in soils and frequently exceed chloride (Cl(-)) levels. Despite the widespread abundance of Clorg and the common ability of microorganisms to produce Clorg, we lack fundamental knowledge about how overall chlorine cycling is regulated in forested ecosystems. Here we present data from a long-term reforestation experiment where native forest was cleared and replaced with five different tree species. Our results show that the abundance and residence times of Cl(-) and Clorg after 30 years were highly dependent on which tree species were planted on the nearby plots. Average Cl(-) and Clorg content in soil humus were higher, at experimental plots with coniferous trees than in those with deciduous trees. Plots with Norway spruce had the highest net accumulation of Cl(-) and Clorg over the experiment period, and showed a 10 and 4 times higher Cl(-) and Clorg storage (kg ha(-1)) in the biomass, respectively, and 7 and 9 times higher storage of Cl(-) and Clorg in the soil humus layer, compared to plots with oak. The results can explain why local soil chlorine levels are frequently independent of atmospheric deposition, and provide opportunities for improved modeling of chlorine distribution and cycling in terrestrial ecosystems.

[Combined use of active chlorine and coagulants for drinking water purification and disinfection].

PubMed

Rakhmanin, Iu A; Zholdakova, Z I; Poliakova, E E; Kir'ianova, L F; Miasnikov, I N; Tul'skaia, E A; Artemova, T Z; Ivanova, L V; Dmitrieva, R A; Doskina, T V

2004-01-01

The authors made an experimental study of the efficiency of water purification procedures based on the combined use of active chlorine and coagulants and hygienically evaluated the procedures. The study included the evaluation of water disinfection with various coagulants and active chlorine; the investigation of the processes of production of deleterious organic chlorine compounds; the assessment of the quality of water after its treatment. The coagulants representing aluminum polyoxychloride: RAX-10 (AQUA-AURATE 10) and RAX-18 (AQUA-AURATE 18), and aluminum sulfate, technically pure grade were tested. The treatment of river water with the coagulants RAX-10 and RAX-18, followed by precipitation, filtration, and chlorination under laboratory conditions, was shown to result in water disinfection to the levels complying with the requirements described in SanPiN 2.1.4.1074-01. RAX-18 showed the best disinfecting activity against total and heat-tolerant coliform bacteria, but also to the highly chlorine-resistant microrganisms--the spores of sulfite-reducing Clostridia, phages, and viruses. Since the coagulants have an increased sorptive capacity relative to humus and other organic substances, substitution of primary chlorination for coagulant treatment may induce a reduction in the risk of formation of oncogenically and mutagenically hazardous chlorinated hydrocarbons.

Application of activated carbons from coal and coconut shell for removing free residual chlorine.

PubMed

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.

Amide Link Scission in the Polyamide Active Layers of Thin-Film Composite Membranes upon Exposure to Free Chlorine: Kinetics and Mechanisms.

PubMed

Powell, Joshua; Luh, Jeanne; Coronell, Orlando

2015-10-20

The volume-averaged amide link scission in the aromatic polyamide active layer of a reverse osmosis membrane upon exposure to free chlorine was quantified at a variety of free chlorine exposure times, concentrations, and pH and rinsing conditions. The results showed that (i) hydroxyl ions are needed for scission to occur, (ii) hydroxide-induced amide link scission is a strong function of exposure to hypochlorous acid, (iii) the ratio between amide links broken and chlorine atoms taken up increased with the chlorination pH and reached a maximum of ∼25%, (iv) polyamide disintegration occurs when high free chlorine concentrations, alkaline conditions, and high exposure times are combined, (v) amide link scission promotes further chlorine uptake, and (vi) scission at the membrane surface is unrepresentative of volume-averaged scission in the active layer. Our observations are consistent with previously proposed mechanisms describing amide link scission as a result of the hydrolysis of the N-chlorinated amidic N-C bond due to nucleophilic attack by hydroxyl ions. This study increases the understanding of the physicochemical changes that could occur for membranes in treatment plants using chlorine as an upstream disinfectant and the extent and rate at which those changes would occur.

Study of degradation intermediates formed during electrochemical oxidation of pesticide residue 2,6-dichlorobenzamide (BAM) in chloride medium at boron doped diamond (BDD) and platinum anodes.

PubMed

Madsen, Henrik Tækker; Søgaard, Erik Gydesen; Muff, Jens

2015-02-01

For electrochemical oxidation to become applicable in water treatment outside of laboratories, a number of challenges must be elucidated. One is the formation and fate of degradation intermediates of targeted organics. In this study the degradation of the pesticide residue 2,6-dichlorobenzamide, an important groundwater pollutant, was investigated in a chloride rich solution with the purpose of studying the effect of active chlorine on the degradation pathway. To study the relative importance of the anodic oxidation and active chlorine oxidation in the bulk solution, a non-active BDD and an active Pt anode were compared. Also, the effect of the active chlorine oxidation on the total amount of degradation intermediates was investigated. We found that for 2,6-dichlorobenzamide, active chlorine oxidation was determining for the initial step of the degradation, and therefore yielded a completely different set of degradation intermediates compared to an inert electrolyte. For the Pt anode, the further degradation of the intermediates was also largely dependent on active chlorine oxidation, while for the BDD anode anodic oxidation was most important. It was also found that the presence of active chlorine led to fewer degradation intermediates compared to treatment in an inert electrolyte. Copyright © 2014 Elsevier Ltd. All rights reserved.

Degradation of natural organic matter by UV/chlorine oxidation: Molecular decomposition, formation of oxidation byproducts and cytotoxicity.

PubMed

Wang, Wen-Long; Zhang, Xue; Wu, Qian-Yuan; Du, Ye; Hu, Hong-Ying

2017-11-01

The degradation of natural organic matters (NOMs) by the combination of UV and chlorine (UV/chlorine) was investigated in this study. UV/chlorine oxidation can effectively degrade NOMs, with the degradation of chromophores (∼80%) and fluorophores (76.4-80.8%) being more efficient than that of DOC (15.1-18.6%). This effect was attributed to the chromophores and fluorophores (double bonds, aromatic groups and phenolic groups) being preferentially degraded by UV/chlorine oxidation, particularly reactive groups with high electron donating capacity. Radical species •OH and •Cl were generated during UV/chlorine oxidation, with the contribution of •OH 1.4 times as high as that of •Cl. The degradation kinetics of different molecular weight (MW) fractions suggests that UV/chlorine oxidation degrades high MW fractions into low MW fractions, with the degradation rates of high MW fractions (>3000 Da) 4.5 times of those of medium MW fractions (1000-3000 Da). In comparison with chlorination alone, UV/chlorine oxidation did not increase the formation (30 min) and formation potential (24 h) of trihalomethanes, but instead promoted the formation and formation potential of haloacetic acids and chloral hydrate. Adsorbable organic halogen (AOX) formed from UV/chlorine oxidation of NOM were 0.8 times higher than those formed from chlorination. Cytotoxicity studies indicated that the cytotoxicity of NOM increased after both chlorination and UV/chlorine oxidation, which may be due to the formation of AOX. Copyright © 2017 Elsevier Ltd. All rights reserved.

Novel pathways for elimination of chlorine atoms from growing Si(100) surfaces in CVD reactors

NASA Astrophysics Data System (ADS)

Kunioshi, Nílson; Hagino, Sho; Fuwa, Akio; Yamaguchi, Katsunori

2018-05-01

Reactions leading to elimination of chlorine atoms from growing Si(100) surfaces were simulated using clusters of silicon atoms of different sizes and shapes, and at the UB3LYP/6-31 g(d,p) level of theory. The reactions of type SiCl2(s) + 2 H2(g), where (s) indicates an adsorbed species at the surface and (g) a gas-phase species, were found to proceed in two steps: SiCl2(s) + H2(g) → SiHCl(s) + HCl(g) and SiHCl(s) + H2(g) → SiH2(s) + HCl(g), each having activation energies around 55 kcal/mol, a value which is comparable to experimental values published in the literature. In addition, the results suggested that H-passivation of Si(100) surfaces support reactions leading to canonical epitaxial growth, providing a plausible explanation for the convenience of passivating the surfaces prior to silicon deposition. The reactions analyzed here can therefore be seen as important steps in the mechanism of epitaxial growth of Si(100) surfaces.

STUDY OF THE EFFECT OF CHLORINE ADDITION ON MERCURY OXIDATION BY SCR CATALYST UNDER SIMULATED SUBBITUMINOUS COAL FLUE GAS

EPA Science Inventory

An entrained flow reactor is used to study the effect of addition of chlorine-containing species on the oxidation of elemental mercury (Hgo)by a selective catalytic reduction (SCR) catalyst in simulated subbituminous coal combustion flue gas. The combustion flue gas was doped wit...

ASCORBIC ACID REDUCTION OF RESIDUAL ACTIVE CHLORINE IN POTABLE WATER PRIOR TO HALOCARBOXYLATE DETERMINATION

EPA Science Inventory

In studies on the formation of disinfection byproducts (DBPs), it is necessary to scavenge residual active (oxidizing) chlorine in order to fix the chlorination byproducts (such as haloethanoates) at a point in time. Thus, methods designed for compliance monitoring are not alway...

ASCORBIC ACID REDUCTION ON RESIDUAL ACTIVE CHLORINE IN POTABLE WATER PRIOR TO HALOCARBOXYLATE DETERMINATION

EPA Science Inventory

In studies on the formation of disinfection byproducts (DBPs), it is necessary to scavenge residual active (odxidizing) chlorine in order to fix the chlorination byproducts (such as haloethanoates) at a point in time . Such research projects often have distinct needs from requi...

Relationship between antibiotic- and disinfectant-resistance profiles in bacteria harvested from tap water.

PubMed

Khan, Sadia; Beattie, Tara K; Knapp, Charles W

2016-06-01

Chlorination is commonly used to control levels of bacteria in drinking water; however, viable bacteria may remain due to chlorine resistance. What is concerning is that surviving bacteria, due to co-selection factors, may also have increased resistance to common antibiotics. This would pose a public health risk as it could link resistant bacteria in the natural environment to human population. Here, we investigated the relationship between chlorine- and antibiotic-resistances by harvesting 148 surviving bacteria from chlorinated drinking-water systems and compared their susceptibilities against chlorine disinfectants and antibiotics. Twenty-two genera were isolated, including members of Paenibacillus, Burkholderia, Escherichia, Sphingomonas and Dermacoccus species. Weak (but significant) correlations were found between chlorine-tolerance and minimum inhibitory concentrations against the antibiotics tetracycline, sulfamethoxazole and amoxicillin, but not against ciprofloxacin; this suggest that chlorine-tolerant bacteria are more likely to also be antibiotic resistant. Further, antibiotic-resistant bacteria survived longer than antibiotic-sensitive organisms when exposed to free chlorine in a contact-time assay; however, there were little differences in susceptibility when exposed to monochloramine. Irrespective of antibiotic-resistance, spore-forming bacteria had higher tolerance against disinfection compounds. The presence of chlorine-resistant bacteria surviving in drinking-water systems may carry additional risk of antibiotic resistance. Copyright © 2016 Elsevier Ltd. All rights reserved.

A temperature-programmed X-ray photoelectron spectroscopy (TPXPS) study of chlorine adsorption and diffusion on Ag(1 1 1)

NASA Astrophysics Data System (ADS)

Piao, H.; Adib, K.; Barteau, Mark A.

2004-05-01

Synchrotron-based temperature programmed X-ray photoelectron spectroscopy (TPXPS) has been used to investigate the surface chloridation of Ag(1 1 1) to monolayer coverages. At 100 K both atomic and molecular chlorine species are present on the surface; adsorption at 300 K or annealing the adlayer at 100 K to this temperature generates adsorbed Cl atoms. As the surface is heated from 300 to 600 K, chlorine atoms diffuse below the surface, as demonstrated by attenuation of the Cl2p signals in TPXPS experiments. Quantitative analysis of the extent of attenuation is consistent with chlorine diffusion below the topmost silver layer. For coverages in the monolayer and sub-monolayer regime, chlorine diffusion to and from the bulk appears not to be significant, in contrast to previous results obtained at higher chlorine loadings. Chlorine is removed from the surface at 650-780 K by desorption as AgCl. These results demonstrate that chlorine diffusion beneath the surface does occur at coverages and temperatures relevant to olefin epoxidation processes carried out on silver catalysts with chlorine promoters. The surface sensitivity advantages of synchrotron-based XPS experiments were critical to observing Cl diffusion to the sub-surface at low coverages.

Monte Carlo analysis of uncertainty propagation in a stratospheric model. 1: Development of a concise stratospheric model

NASA Technical Reports Server (NTRS)

Rundel, R. D.; Butler, D. M.; Stolarski, R. S.

1977-01-01

A concise model has been developed to analyze uncertainties in stratospheric perturbations, yet uses a minimum of computer time and is complete enough to represent the results of more complex models. The steady state model applies iteration to achieve coupling between interacting species. The species are determined from diffusion equations with appropriate sources and sinks. Diurnal effects due to chlorine nitrate formation are accounted for by analytic approximation. The model has been used to evaluate steady state perturbations due to injections of chlorine and NO(X).

Comparative evaluation of effects of ozonated and chlorinated thermal discharges on estuarine and fresh water organisms. First quarterly progress report, April 1979

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guerra, C.R.; DelMonaco, J.L.; Singletary, J.H.

1979-01-01

The biological evaluation program incorporates three types of experimental tests: acute (96 hour) toxicity studies; behavioral (avoidance) response studies; and physiological (cough) response studies. In addition, specimens used in testing are examined for physical damage resulting from exposure to chlorine or ozoen. The objective of the acute (96 hour) toxicity study is to determine the respective lethal levels (LC/sub 50/) of chlorinated and ozonated waters. The objective of the behavioral (avoidance) response study is to determine what (if any) concentrations of ozone and of chlorine will be avoided. The objective of physiological (cough) response study is to determine what concentrationsmore » of ozone and of chlorine are physiologically detected. Ozonated and chlorinated waters were evaluated in all studies for both the addition of increased temperature and without it. Results indicate that ozone is less toxic than chlorine under the test conditions used. The lethal levels vary according to species of water quality measurements at Bergen Generating Station, New York are tabulated. (JBG)« less

Mutagenic activities of a chlorination by-product of butamifos, its structural isomer, and their related compounds.

PubMed

Kamoshita, Masahiro; Kosaka, Koji; Endo, Osamu; Asami, Mari; Aizawa, Takako

2010-01-01

The mutagenic activities of 5-methyl-2-nitrophenol (5M2NP), a chlorination by-product of butamifos, its structural isomer 2-methyl-5-nitrophenol (2M5NP), and related compounds were evaluated by the Ames assay. The mutagenic activities of 5M2NP and 2M5NP were negative or not particularly high. However, those of their chlorinated derivatives were increased in Salmonella typhimurium strain TA100 and the overproducer strains YG1026, and YG1029 in the absence and/or presence of a rat liver metabolic activation system (S9 mix), particularly for YG1029. The mutagenic activities of 6-chloro-2-methyl-5-nitrophenol (6C2M5NP) in YG1029 in the absence and presence of S9 mix were 70000 and 110000 revertants mg(-1), respectively. When nitro functions of 6C2M5NP and 4-chloro-5-methyl-2-nitrophenol (4C5M2NP) were reduced to amino functions, their mutagenic activities were markedly decreased. The mutagenic activities of 5M2NP and 4C5M2NP were lower than those of 2M5NP and 6C2M5NP, respectively. Thus, it was shown that substituent position is a key factor for the mutagenic activities of methylnitrophenols (MNPs) and related compounds. The mutagenic activities of the extracts of 2M5NP in chlorination increased early during the reaction time and then decreased. The main chlorination by-product contributing to the mutagenic activities of the extracts of 2M5NP in chlorination was 6C2M5NP. The results of chlorination of 2M5NP suggested that MNPs were present as their dichlorinated derivatives or further chlorination by-products in drinking water. Copyright 2009 Elsevier Ltd. All rights reserved.

Highly selective transformation of ammonia nitrogen to N2 based on a novel solar-driven photoelectrocatalytic-chlorine radical reactions system.

PubMed

Ji, Youzhi; Bai, Jing; Li, Jinhua; Luo, Tao; Qiao, Li; Zeng, Qingyi; Zhou, Baoxue

2017-11-15

A highly selective method for transforming ammonia nitrogen to N 2 was proposed, based on a novel solar-driven photoelectrocatalytic-chlorine radical reactions (PEC-chlorine) system. The PEC-chlorine system was facilitated by a visible light response WO 3 nanoplate array (NPA) electrode in an ammonia solution containing chloride ions (Cl - ). Under illumination, photoholes from WO 3 promote the oxidation of Cl - to chlorine radical (Cl). This radical can selectively transform ammonia nitrogen to N 2 (79.9%) and NO 3 - (19.2%), similar to the breakpoint chlorination reaction. The ammonia nitrogen removal efficiency increased from 10.6% (PEC without Cl - ) to 99.9% with the PEC-chlorine system within 90 min operation, which can be attributed to the cyclic reactions between Cl - /Cl and the reaction intermediates (NH 2 , NHCl, etc.) that expand the degradation reactions from the surface of the electrodes to the whole solution system. Moreover, Cl is the main radical species contributing to the transformation of ammonia nitrogen to N 2 , which is confirmed by the tBuOH capture experiment. Compared to conventional breakpoint chlorination, the PEC-chlorine system is a more economical and efficient means for ammonia nitrogen degradation because of the fast removal rate, no additional chlorine cost, and its use of clean energy (since it is solar-driven). Copyright © 2017 Elsevier Ltd. All rights reserved.

Altered UV absorbance and cytotoxicity of chlorinated sunscreen agents.

PubMed

Sherwood, Vaughn F; Kennedy, Steven; Zhang, Hualin; Purser, Gordon H; Sheaff, Robert J

2012-12-01

Sunscreens are widely utilized due to the adverse effects of ultraviolet (UV) radiation on human health. The safety of their active ingredients as well as that of any modified versions generated during use is thus of concern. Chlorine is used as a chemical disinfectant in swimming pools. Its reactivity suggests sunscreen components might be chlorinated, altering their absorptive and/or cytotoxic properties. To test this hypothesis, the UV-filters oxybenzone, dioxybenzone, and sulisobenzone were reacted with chlorinating agents and their UV spectra analyzed. In all cases, a decrease in UV absorbance was observed. Given that chlorinated compounds can be cytotoxic, the effect of modified UV-filters on cell viability was examined. Chlorinated oxybenzone and dioxybenzone caused significantly more cell death than unchlorinated controls. In contrast, chlorination of sulisobenzone actually reduced cytotoxicity of the parent compound. Exposing a commercially available sunscreen product to chlorine also resulted in decreased UV absorbance, loss of UV protection, and enhanced cytotoxicity. These observations show chlorination of sunscreen active ingredients can dramatically decrease UV absorption and generate derivatives with altered biological properties.

Comparative toxicity of insecticides to Choristoneura species (Lepidoptera: Tortricidae)

Treesearch

Jacqueline L. Robertson; Nancy L. Gillette; Barbara A. Lucas; Robert M. Russell; N.E. Savin

1978-01-01

Selected carbamate, chlorinated hydrocarbon, organophosphorous, and pyrethroid insecticides were tested on six Choristoneura species: conflictana (Walker), fumiferana (Clemens), lambertiana ponderosana Obraztsov, occidentalis Freeman, pinus Freeman, and...

Photodynamic tissue adhesion with chlorin(e6) protein conjugates.

PubMed

Khadem, J; Veloso, A A; Tolentino, F; Hasan, T; Hamblin, M R

1999-12-01

To test the hypothesis that a photodynamic laser-activated tissue solder would perform better in sealing scleral incisions when the photosensitizer was covalently linked to the protein than when it was noncovalently mixed. Conjugates and mixtures were prepared between the photosensitizer chlorin(e6) and various proteins (albumin, fibrinogen, and gelatin) in different ratios and used to weld penetrating scleral incisions made in human cadaveric eyes. A blue-green (488-514 nm) argon laser activated the adhesive, and the strength of the closure was measured by increasing the intraocular pressure until the wound showed leakage. Both covalent conjugates and noncovalent mixtures showed a light dose-dependent increase in leaking pressure. A preparation of albumin chlorin(e6) conjugate with additional albumin added (2.5 protein to chlorin(e6) molar ratio) showed significantly higher weld strength than other protein conjugates and mixtures. This is the first report of dye-protein conjugates as tissue solders. These conjugates may have applications in ophthalmology.

Structure-activity relationships of selected phenazines against Mycobacterium leprae in vitro.

PubMed Central

Franzblau, S G; O'Sullivan, J F

1988-01-01

Structure-activity relationships of phenazines against Mycobacterium leprae were investigated by using an in vitro radiorespirometric assay. In general, activity in ascending order was observed in compounds containing no chlorine atoms, a monochlorinated phenazine nucleus, and chlorines in the para positions of both the anilino and phenyl rings. The most active compounds contained a 2,2,6,6-tetramethylpiperidine substitution at the imino nitrogen. Most of these chlorinated phenazines were considerably more active in vitro than clofazimine (B663). PMID:3056241

Degradation of chloramphenicol by UV/chlorine treatment: Kinetics, mechanism and enhanced formation of halonitromethanes.

PubMed

Dong, Huiyu; Qiang, Zhimin; Hu, Jun; Qu, Jiuhui

2017-09-15

Ultraviolet (UV)/chlorine process is considered as an emerging advanced oxidation process for the degradation of micropollutants. This study investigated the degradation of chloramphenicol (CAP) and formation of disinfection by-products (DBPs) during the UV/chlorine treatment. It was found that CAP degradation was enhanced by combined UV/chlorine treatment compared to that of UV and chlorination treatment alone. The pseudo-first-order rate constant of the UV/chlorine process at pH 7.0 reached 0.016 s -1 , which was 10.0 and 2.0 folds that observed from UV and chlorination alone, respectively. The enhancement can be attributed to the formation of diverse radicals (HO and reactive chlorine species (RCSs)), and the contribution of RCSs maintained more stable than that of HO at pH 5.5-8.5. Meanwhile, enhanced DBPs formation during the UV/chlorine treatment was observed. Both the simultaneous formation and 24-h halonitromethanes formation potential (HNMsFP) were positively correlated with the UV/chlorine treatment time. Although the simultaneous trichloronitromethane (TCNM) formation decreased with the prolonged UV irradiation, TCNM dominated the formation of HNMs after 24 h (>97.0%). According to structural analysis of transformation by-products, both the accelerated CAP degradation and enhanced HNMs formation steps were proposed. Overall, the formation of diverse radicals during the UV/chlorine treatment accelerated the degradation of CAP, while also enhanced the formation of DBPs simultaneously, indicating the need for DBPs evaluation before the application of combined UV/chlorine process. Copyright © 2017 Elsevier Ltd. All rights reserved.

Pesticide contaminants in selected species of edible wild mushrooms from the north-eastern part of Poland.

PubMed

Gałgowska, Michalina; Pietrzak-Fiećko, Renata

2017-03-04

The aim of this study was to determine the level of chlorinated hydrocarbon residues in selected edible mushrooms from north-eastern Poland. The experiment was carried out on 45 samples consisting of 15 fruiting bodies each of the following species: Boletus edulis, Imleria badia and Cantharellus cibarius. Dried samples were subjected to extraction of lipids with a Soxhlet and a standard procedure-based on the decomposition of lipids by concentrated sulfuric acid and the release of organic insecticides to the hexane layer-was used to determine chlorinated hydrocarbons. The quantitative determination of DDT, DDE, DDD and γ-HCH were conducted using gas chromatography with electron capture detection (GC-ECD). Chlorinated hydrocarbons were found in all tested samples. The contents of these compounds varied between all three species. Mean content of γ-HCH in B. edulis, I. badia and C. cibarius was: 2.60; 4.83; 7.52 µg kg -1 of lipids, while the content of ΣDDT was: 57.02; 25.20; 127.10 µg kg -1 of lipids, respectively. These results show that mushrooms from the north-eastern part of Poland can be used as potential bio-indicators of environmental contamination with chlorinated hydrocarbons. Moreover, the studied fungi could still be used as food due to the low levels of analyzed organochlorine compounds.

Comparison of an Assay for Dehalococcoides DNA and a Microcosm Study in Predicting Reductive Dechlorination of Chlorinated Ethenes in the field

EPA Science Inventory

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 ethylenes in ground water at hazardous waste sites. A total of 72 ground water samples were coll...

Evaluation of disinfection by-product formation potential (DBPFP) during chlorination of two algae species--Blue-green Microcystis aeruginosa and diatom Cyclotella meneghiniana.

PubMed

Liao, Xiaobin; Liu, Jinjin; Yang, Mingli; Ma, Hongfang; Yuan, Baoling; Huang, Ching-Hua

2015-11-01

Microcystis aeruginosa (blue-green alga) commonly blooms in summer and Cyclotella meneghiniana (diatom) outbreaks in fall in the reservoirs that serve as drinking water sources in Southeast China. Herein, an evaluation of disinfection by-product formation potential (DBPFP) from them during chlorination should be conducted. Five DBPs including trichloromethane (TCM), trichloronitromethane (TCNM), dichloroacetonitrile (DCAN), 1,1-dichloropropanone (1,1-DCP) and 1,1,1-trichloropropanone (1,1,1-TCP) were monitored. The formation potential of TCM and TCNM was enhanced with the increase of reaction time and chlorine dosage, whereas that of DCAN, 1,1-DCP and 1,1,1-TCP increased first and then fell with continuing reaction time. M. aeruginosa showed higher DBPFP than C. meneghiniana, the yield of DBPs varied with components of algal cells. The DBPFP order from components of M. aeruginosa was cell suspension (CS) ≈ intracellular organic matter (IOM) > extracellular organic matter (EOM) > cell debris (CD), which indicated that IOM was the main DBP precursors for M. aeruginosa. The yields of DBPs from components of C. meneghiniana were in the order of CS>IOM≈ CD ≈ EOM, suggesting that three components made similar contributions to the total DBP formation. The amount of IOM with higher DBPFP leaked from both algae species increased with the chlorine dosage, indicating that chlorine dosage should be considered carefully in the treatment of eutrophic water for less destroying of the cell integrity. Though fluorescence substances contained in both algae species varied significantly, the soluble microbial products (SMPs) and aromatic protein-like substances were the main cellular components that contributed to DBP formation for both algae. Copyright © 2015 Elsevier B.V. All rights reserved.

Quantum Chemical Examination of the Sequential Halogen Incorporation Scheme for the Modeling of Speciation of I/Br/Cl-Containing Trihalomethanes.

PubMed

Zhang, Chenyang; Li, Maodong; Han, Xuze; Yan, Mingquan

2018-02-20

The recently developed three-step ternary halogenation model interprets the incorporation of chlorine, bromine, and iodine ions into natural organic matter (NOM) and formation of iodine-, bromine-, and chlorine-containing trihalomethanes (THMs) based on the competition of iodine, bromine, and chlorine species at each node of the halogenation sequence. This competition is accounted for using the dimensionless ratios (denoted as γ) of kinetic rates of reactions of the initial attack sites or halogenated intermediates with chlorine, bromine, and iodine ions. However, correlations between the model predictions made and mechanistic aspects of the incorporation of halogen species need to be ascertained in more detail. In this study, quantum chemistry calculations were first used to probe the formation mechanism of 10 species of Cl-/Br-/I- THMs. The HOMO energy (E HOMO ) of each mono-, bi-, or trihalomethanes were calculated by B3LYP method in Gaussian 09 software. Linear correlations were found to exist between the logarithms of experimentally determined kinetic preference coefficients γ reported in prior research and, on the other hand, differences of E HOMO values between brominated/iodinated and chlorinated halomethanes. One notable exception from this trend was that observed for the incorporation of iodine into mono- and di-iodinated intermediates. These observations confirm the three-step halogen incorporation sequence and the factor γ in the statistical model. The combined use of quantum chemistry calculations and the ternary sequential halogenation model provides a new insight into the microscopic nature of NOM-halogen interactions and the trends seen in the behavior of γ factors incorporated in the THM speciation models.

Aniline chlorination by in situ formed Ag-Cl complexes under simulated solar light irradiation.

PubMed

Hu, Xuefeng; Wang, Xiaowen; Dong, Liuliu; Chang, Fei; Luo, Yongming

2015-01-01

Ag speciation in a chloride medium was dependent upon the Cl/Ag ratio after releasing into surface water. In this study, the photoreaction of in situ formed Ag-Cl species and their effects on aniline photochlorination were systematically investigated. Our results suggested that formation of chloroaniline was strongly relevant to the Cl/Ag ratio and could be interpreted using the thermodynamically expected speciation of Ag in the presence of Cl-. AgCl was the main species responsible for the photochlorination of aniline. Both photoinduced hole and •OH drove the oxidation of Cl- to radical •Cl, which promoted the chlorination of aniline. Ag0 formation was observed from the surface plasmon resonance absorption during AgCl photoreaction. This study revealed that Ag+ released into Cl--containing water may result in the formation of chlorinated intermediates of organic compounds under solar light irradiation.

Grape pomace compost harbors organohalide-respiring Dehalogenimonas species with novel reductive dehalogenase genes

DOE PAGES

Yang, Yi; Higgins, Steven A.; Yan, Jun; ...

2017-08-15

Here, organohalide-respiring bacteria play key roles in the natural chlorine cycle; however, most of the current knowledge is based on cultures from contaminated environments. We demonstrate that grape pomace compost without prior exposure to chlorinated solvents harbors a Dehalogenimonas ( Dhgm) species capable of using chlorinated ethenes, including the human carcinogen and common groundwater pollutant vinyl chloride (VC) as electron acceptors. Grape pomace microcosms and derived solid-free enrichment cultures were able to dechlorinate trichloroethene (TCE) to less chlorinated daughter products including ethene. 16S rRNA gene amplicon and qPCR analyses revealed the predominance of Dhgm sequences, but no Dehalococcoides mccartyi (more » Dhc) biomarker genes were detected. The enumeration of Dhgm 16S rRNA genes demonstrated VC-dependent growth, and 6.55 ± 0.64 x 10 8 cells were produced per µmole of chloride released. Metagenome sequencing enabled the assembly of a Dhgm draft genome, and 52 putative reductive dehalogenase (RDase) genes were identified. Proteomic workflows identified a putative VC RDase with 49% and 56.1% amino acid similarity to the known VC RDases VcrA and BvcA, respectively. A survey of 1,173 groundwater samples collected from 111 chlorinated solvent-contaminated sites revealed that Dhgm 16S rRNA genes were frequently detected and outnumbered Dhc in 65% of the samples. Dhgm may be more relevant contributors to chlorinated solvent reductive dechlorination in contaminated aquifers than is currently recognized, and non-polluted environments are a source of strictly organohalide-respiring bacteria with novel RDase genes.« less

Grape pomace compost harbors organohalide-respiring Dehalogenimonas species with novel reductive dehalogenase genes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Yi; Higgins, Steven A.; Yan, Jun

Here, organohalide-respiring bacteria play key roles in the natural chlorine cycle; however, most of the current knowledge is based on cultures from contaminated environments. We demonstrate that grape pomace compost without prior exposure to chlorinated solvents harbors a Dehalogenimonas ( Dhgm) species capable of using chlorinated ethenes, including the human carcinogen and common groundwater pollutant vinyl chloride (VC) as electron acceptors. Grape pomace microcosms and derived solid-free enrichment cultures were able to dechlorinate trichloroethene (TCE) to less chlorinated daughter products including ethene. 16S rRNA gene amplicon and qPCR analyses revealed the predominance of Dhgm sequences, but no Dehalococcoides mccartyi (more » Dhc) biomarker genes were detected. The enumeration of Dhgm 16S rRNA genes demonstrated VC-dependent growth, and 6.55 ± 0.64 x 10 8 cells were produced per µmole of chloride released. Metagenome sequencing enabled the assembly of a Dhgm draft genome, and 52 putative reductive dehalogenase (RDase) genes were identified. Proteomic workflows identified a putative VC RDase with 49% and 56.1% amino acid similarity to the known VC RDases VcrA and BvcA, respectively. A survey of 1,173 groundwater samples collected from 111 chlorinated solvent-contaminated sites revealed that Dhgm 16S rRNA genes were frequently detected and outnumbered Dhc in 65% of the samples. Dhgm may be more relevant contributors to chlorinated solvent reductive dechlorination in contaminated aquifers than is currently recognized, and non-polluted environments are a source of strictly organohalide-respiring bacteria with novel RDase genes.« less

Shifts in spinach microbial communities after chlorine washing and storage at compliant and abusive temperatures.

PubMed

Gu, Ganyu; Ottesen, Andrea; Bolten, Samantha; Ramachandran, Padmini; Reed, Elizabeth; Rideout, Steve; Luo, Yaguang; Patel, Jitendra; Brown, Eric; Nou, Xiangwu

2018-08-01

Fresh produce, like spinach, harbors diverse bacterial populations, including spoilage and potentially pathogenic bacteria. This study examined the effects of produce washing in chlorinated water and subsequent storage on the microbiota of spinach. Baby spinach leaves from a commercial fresh-cut produce processor were assessed before and after washing in chlorinated water, and then after one week's storage at 4, 10, and 15 °C. Microbial communities on spinach were analyzed by non-selective plating, qPCR, and 16S rDNA amplicon sequencing. Bacterial populations on spinach, averaging 6.12 ± 0.61 log CFU/g, were reduced by 1.33 ± 0.57 log after washing. However, populations increased by 1.77-3.24 log after storage, with larger increases occurring at higher temperature (15 > 10 > 4 °C). The predominant phylum identified on unwashed spinach leaves was Proteobacteria; dominant genera were Pseudomonas and Sphingomonas. Bacterial communities shifted significantly after chlorine washing and storage. Several Proteobacteria species, such as Stenotrophomonas sp. and Erwinia sp., were relatively tolerant of chlorine treatment, while species of Flavobacterium and Pedobacter (phylum Bacteroidetes) grew rapidly during storage, especially at abusive temperatures. Cupriavidus sp. and Ralstonia sp. showed significant increases after washing. After storage, microbial communities on spinach appeared to shift back toward the pre-washing distributions. Copyright © 2018. Published by Elsevier Ltd.

Chlorine Disinfection of Atypical Mycobacteria Isolated from a Water Distribution System

PubMed Central

Le Dantec, Corinne; Duguet, Jean-Pierre; Montiel, Antoine; Dumoutier, Nadine; Dubrou, Sylvie; Vincent, Véronique

2002-01-01

We studied the resistance of various mycobacteria isolated from a water distribution system to chlorine. Chlorine disinfection efficiency is expressed as the coefficient of lethality (liters per minute per milligram) as follows: Mycobacterium fortuitum (0.02) > M. chelonae (0.03) > M. gordonae (0.09) > M. aurum (0.19). For a C · t value (product of the disinfectant concentration and contact time) of 60 mg · min · liter−1, frequently used in water treatment lines, chlorine disinfection inactivates over 4 log units of M. gordonae and 1.5 log units of M. fortuitum or M. chelonae. C · t values determined under similar conditions show that even the most susceptible species, M. aurum and M. gordonae, are 100 and 330 times more resistant to chlorine than Escherichia coli. We also investigated the effects of different parameters (medium, pH, and temperature) on chlorine disinfection in a chlorine-resistant M. gordonae model. Our experimental results follow the Arrhenius equation, allowing the inactivation rate to be predicted at different temperatures. Our results show that M. gordonae is more resistant to chlorine in low-nutrient media, such as those encountered in water, and that an increase in temperature (from 4°C to 25°C) and a decrease in pH result in better inactivation. PMID:11872446

Effects of free and combined chlorine and exposure duration on rainbow trout, channel catfish, and emerald shiners

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brooks, A.S.; Bartos, J.M.

1984-11-01

Laboratory bioassays to determine the acute toxicity of monochloramine, dichloramine, hypochlorous acid, and hypochlorite ion to emerald shiners Notropis atherinoides, channel catfish Ictalurus punctatus, and rainbow trout Salmo gairdneri were conducted. Four exposure regimes typical of chlorination schedules at operating steam electric power plants were used. Fish were exposed for single 15-minute, 30-minute, 120-minute, and 4 x 30-minute periods. Based on median lethal concentrations (LC50s), the nominal solution of hypochlorous acid was the most toxic, followed closely by the solution dominated by dichloramine; nominal monochloramine and hypochlorite ion solutions had a third to a quarter the toxicity of the othermore » two. On the average, emerald shiners were 1.8 times more sensitive than channel catfish and 3.3 times more sensitive than rainbow trout to the four forms of chlorine. The fish were most tolerant of chlorine during short-duration exposures and least tolerant during the continuous 120-minute exposures. The differences in toxicity noted among the chlorine forms suggest that, when chlorination regimes and regulations are established, careful attention should be paid not only to total residual chlorine but to both the chlorine forms and fish species present and the duration of exposure. 24 references, 1 figure, 1 table.« less

Chlorine dioxide as a post-disinfectant for Dutch drinking water.

PubMed

Wondergem, E; van Dijk-Looijaard, A M

1991-02-01

Chlorine dioxide has some important advantages over chlorine with respect to water quality (no formation of trihalomethanes, no impairment of taste and no odor) and stability when used for oxidation/disinfection of drinking water. In this paper, results are presented of experiments into the consumption and reaction kinetics of chlorine dioxide in a number of (drinking) waters in The Netherlands. It was found that chlorine dioxide consumption is related to the dissolved oxygen content (DOC) of the water and the reaction time. Water samples from a plant that applied ozonation and activated carbon filtration had a very low chlorine dioxide consumption. Other water quality parameters, including pH and CO3(2-), did not have any influence on consumption. The temporary advised Dutch guidelines of 0.2 mg l-1 (dosage) is sufficient for activated carbon treated water. For other Dutch drinking waters, however, none of the 0.2 mg l-1 chlorine dioxide remained after a reaction time of 10 min, as was also found for the water of Dutch pumping stations where chlorine dioxide is at present used for disinfection.

Removal of endocrine disruptors and non-steroidal anti-inflammatory drugs through wastewater chlorination: the effect of pH, total suspended solids and humic acids and identification of degradation by-products.

PubMed

Noutsopoulos, Constantinos; Koumaki, Elena; Mamais, Daniel; Nika, Maria-Christina; Bletsou, Anna A; Thomaidis, Nikolaos S

2015-01-01

Endocrine disrupting chemicals (EDCs) and non-steroidal anti-inflammatory drugs (NSAIDs) are two groups of emerging pollutants the significance of which rests on their persistent detection in the aquatic environment and their possible adverse effects. Wastewater treatment plants are one of the major ways for transporting such chemicals in the aquatic environment. Chlorination is usually the last stage of treatment before wastewater being disposed to the aquatic environment. This work focuses on the evaluation of the effect of chlorine dose and specific wastewater characteristics (pH, total suspended solids and humic acids) on the removal of target EDCs and NSAIDs through chlorination. Another objective of this study is the identification of chlorination by-products of specific EDCs and NSAIDs and their dependence on contact time. Based on the results it is concluded that the effect of chlorine dose and humic acids concentration on the degradation of target compounds during chlorination is minimal. On the contrary, pH is a critical parameter which highly affects process performance. Moreover, it is concluded that not only the free available chlorine species, but also the properties of EDCs and NSAIDs under different pH conditions can affect chlorination process performance. The effect of TSS on the degradation of the target compounds during chlorination is more profound for chemicals with high Kow values and therefore higher affinity to partition to the particulate phase (i.e. nonylphenols, triclosan). Several degradation by-products were identified through chlorination of nonylphenol, bisphenol A and diclofenac. The dependence of these by-products on chlorination contact time is also demonstrated. Copyright © 2014 Elsevier Ltd. All rights reserved.

Bromate formation from the oxidation of bromide in the UV/chlorine process with low pressure and medium pressure UV lamps.

PubMed

Fang, Jingyun; Zhao, Quan; Fan, Chihhao; Shang, Chii; Fu, Yun; Zhang, Xiangru

2017-09-01

When a bromide-containing water is treated by the ultraviolet (UV)/chlorine process, hydroxyl radicals (HO) and halogen radicals such as Cl or Br are formed due to the UV photolysis of free halogens. These reactive species may induce the formation of bromate, which is a probable human carcinogen. Bromate formation in the UV/chlorine process using low pressure (LP) and medium pressure (MP) lamps in the presence of bromide was investigated in the present study. The UV/chlorine process significantly enhanced bromate formation as compared to dark chlorination. The bromate formation was elevated with increasing UV fluence, bromide concentration, and pH values under both LP and MP UV irradiations. It was significantly enhanced at pH 9 compared to those at pH 6 and 7 with MP UV irradiation, while it was slightly enhanced at pH 9 with LP UV. The formation by UV/chlorine process started with the formation of free bromine (HOBr/OBr - ) through the reaction of chlorine and bromide, followed by a subsequent oxidation of free bromine and formation of BrO and bromate by reacting with radicals. Copyright © 2017 Elsevier Ltd. All rights reserved.

Enhanced photo-activated luminescence for screening polychlorobiphenyls (PCBs) and other related chlorinated compounds

DOEpatents

Vo-Dinh, Tuan

1994-01-01

The presence of polychlorinated biphenyls and other chlorinated compounds in a sample is determined by treating the sample with a photo-activator and then exposing the treated sample to a UV light source. The UV light produces a photo-product complex, which is subsequently excited with UV light to cause luminescence of the complex. The luminescence is detected and characteristics of the luminescence spectra are used to determine the presence of chlorinated compounds and also the quantity of the chlorine in the compounds

Enhanced photo-activated luminescence for screening polychlorobiphenyls (PCBs) and other related chlorinated compounds

DOEpatents

Vo-Dinh, Tuan

1993-01-01

The presence of polychlorinated biphenyls and other chlorinated compounds in a sample is determined by treating the sample with a photo-activator and then exposing the treated sample to a UV light source. The UV light produces a photo-product complex, which is subsequently excited with UV light to cause luminescence of the complex. The luminescence is detected and characteristics of the luminescence spectra are used to determine the presence of chlorinated compounds and also the quantity of the chlorine in the compounds.

Enhanced photo-activated luminescence for screening polychlorobiphenyls (PCBs) and other related chlorinated compounds

DOEpatents

Vo-Dinh, T.

1994-06-07

The presence of polychlorinated biphenyls and other chlorinated compounds in a sample is determined by treating the sample with a photo-activator and then exposing the treated sample to a UV light source. The UV light produces a photo-product complex, which is subsequently excited with UV light to cause luminescence of the complex. The luminescence is detected and characteristics of the luminescence spectra are used to determine the presence of chlorinated compounds and also the quantity of the chlorine in the compounds. 14 figs.

Enhanced photo-activated luminescence for screening polychlorobiphenyls (PCBs) and other related chlorinated compounds

DOEpatents

Tuan Vodinh.

1993-12-21

The presence of polychlorinated biphenyls and other chlorinated compounds in a sample is determined by treating the sample with a photo-activator and then exposing the treated sample to a UV light source. The UV light produces a photo-product complex, which is subsequently excited with UV light to cause luminescence of the complex. The luminescence is detected and characteristics of the luminescence spectra are used to determine the presence of chlorinated compounds and also the quantity of the chlorine in the compounds. 14 figures.

Comparing the chlorine disinfection of detached biofilm clusters with those of sessile biofilms and planktonic cells in single- and dual-species cultures.

PubMed

Behnke, Sabrina; Parker, Albert E; Woodall, Dawn; Camper, Anne K

2011-10-01

Although the detachment of cells from biofilms is of fundamental importance to the dissemination of organisms in both public health and clinical settings, the disinfection efficacies of commonly used biocides on detached biofilm particles have not been investigated. Therefore, the question arises whether cells in detached aggregates can be killed with disinfectant concentrations sufficient to inactivate planktonic cells. Burkholderia cepacia and Pseudomonas aeruginosa were grown in standardized laboratory reactors as single species and in coculture. Cluster size distributions in chemostats and biofilm reactor effluent were measured. Chlorine susceptibility was assessed for planktonic cultures, attached biofilm, and particles and cells detached from the biofilm. Disinfection tolerance generally increased with a higher percentage of larger cell clusters in the chemostat and detached biofilm. Samples with a lower percentage of large clusters were more easily disinfected. Thus, disinfection tolerance depended on the cluster size distribution rather than sample type for chemostat and detached biofilm. Intact biofilms were more tolerant to chlorine independent of species. Homogenization of samples led to significantly increased susceptibility in all biofilm samples as well as detached clusters for single-species B. cepacia, B. cepacia in coculture, and P. aeruginosa in coculture. The disinfection efficacy was also dependent on species composition; coculture was advantageous to the survival of both species when grown as a biofilm or as clusters detached from biofilm but, surprisingly, resulted in a lower disinfection tolerance when they were grown as a mixed planktonic culture.

Microbial based chlorinated ethene destruction

DOEpatents

Bagwell, Christopher E [Aiken, SC; Freedman, David L [Clemson, SC; Brigmon, Robin L [North Augusta, SC; Bratt, William B [Atlanta, GA; Wood, Elizabeth A [Marietta, GA

2009-11-10

A mixed culture of Dehalococcoides species is provided that has an ability to catalyze the complete dechlorination of polychlorinated ethenes such as PCE, TCE, cDCE, 1,1-DCE and vinyl chloride as well as halogenated ethanes such as 1,2-DCA and EDB. The mixed culture demonstrates the ability to achieve dechlorination even in the presence of high source concentrations of chlorinated ethenes.

Water purification by electrical discharges

NASA Astrophysics Data System (ADS)

Arif Malik, Muhammad; Ghaffar, Abdul; Akbar Malik, Salman

2001-02-01

There is a continuing need for the development of effective, cheap and environmentally friendly processes for the disinfection and degradation of organic pollutants from water. Ozonation processes are now replacing conventional chlorination processes because ozone is a stronger oxidizing agent and a more effective disinfectant without any side effects. However, the fact that the cost of ozonation processes is higher than chlorination processes is their main disadvantage. In this paper recent developments targeted to make ozonation processes cheaper by improving the efficiency of ozone generation, for example, by incorporation of catalytic packing in the ozone generator, better dispersion of ozone in water and faster conversion of dissolved ozone to free radicals are described. The synthesis of ozone in electrical discharges is discussed. Furthermore, the generation and plasma chemical reactions of several chemically active species, such as H2O2, Obullet, OHbullet, HO2bullet, O3*, N2*, e-, O2-, O-, O2+, etc, which are produced in the electrical discharges are described. Most of these species are stronger oxidizers than ozone. Therefore, water treatment by direct electrical discharges may provide a means to utilize these species in addition to ozone. Much research and development activity has been devoted to achieve these targets in the recent past. An overview of these techniques and important developments that have taken place in this area are discussed. In particular, pulsed corona discharge, dielectric barrier discharge and contact glow discharge electrolysis techniques are being studied for the purpose of cleaning water. The units based on electrical discharges in water or close to the water level are being tested at industrial-scale water treatment plants.}

UV/chlorine as an advanced oxidation process for the degradation of benzalkonium chloride: Synergistic effect, transformation products and toxicity evaluation.

PubMed

Huang, Nan; Wang, Ting; Wang, Wen-Long; Wu, Qian-Yuan; Li, Ang; Hu, Hong-Ying

2017-05-01

Benzalkonium chlorides (BACs), as typical cationic surfactants and biocides widely applied in household and industrial products, have been frequently detected as micropollutants in many aquatic environments. In this study, the combination of UV irradiation and chlorine (UV/chlorine), a newly interested advanced oxidation process, was used to degrade dodecylbenzyldimethylammonium chloride (DDBAC). UV/chlorine showed synergistic effects on DDBAC degradation comparing to UV irradiation or chlorination alone. Radical quenching experiments indicated that degradation of DDBAC by UV/chlorine involved both UV photolysis and radical species oxidation, which accounted for 48.4% and 51.6%, respectively. Chlorine dosage and pH are essential parameters affecting the treatment efficiency of UV/chlorine. The pseudo first order rate constant (k obs, DDBAC ) increased from 0.046 min -1 to 0.123 min -1 in response to chlorine dosage at 0-150 mg/L, and the degradation percentage of DDBAC within 12 min decreased from 81.4% to 56.6% at pH 3.6-9.5. Five main intermediates were identified and semi-quantified using HPLC-MS/MS and a possible degradation pathway was proposed. The degradation mechanisms of DDBAC by UV/chlorine included cleavage of the benzyl-nitrogen bond and hydrogen abstraction of the alkyl chain. Trichloromethane (TCM), chloral hydrate (CH), trichloropropanone (TCP), dichloropropanone (DCP) and dichloroacetonitrile (DCAN) were detected using GC-ECD. The formation of chlorinated products increased rapidly initially, then decreased (TCM, TCP, DCP and DCAN) or remained stable (CH) with extended treatment. The actual formation of TCM peaked at 30 min (50.3 μg/L), while other chlorinated products did not exceed 10 μg/L throughout the process. Based on the luminescent bacterial assay, DDBAC solution underwent almost complete detoxification subjected to UV/chlorine treatment for 120 min, which is more effective than UV irradiation or chlorination alone. Copyright © 2017 Elsevier Ltd. All rights reserved.

Breathtaking TRP Channels: TRPA1 and TRPV1 in Airway Chemosensation and Reflex Control

PubMed Central

Bessac, Bret F.; Jordt, Sven-Eric

2009-01-01

New studies have revealed an essential role for TRPA1, a sensory neuronal TRP ion channel, in airway chemosensation and inflammation. TRPA1 is activated by chlorine, reactive oxygen species and noxious constituents of smoke and smog, initiating irritation and airway reflex responses. Together with TRPV1, the capsaicin receptor, TRPA1 may contribute to chemical hypersensitivity, chronic cough and airway inflammation in asthma, COPD and reactive airway dysfunction syndrome. PMID:19074743

Persistent effects of chlorine inhalation on respiratory health

PubMed Central

Hoyle, Gary W.; Svendsen, Erik R.

2016-01-01

Chlorine gas is a toxic respiratory irritant that is considered a chemical threat agent because of the potential for release in industrial accidents or terrorist attacks. Chlorine inhalation damages the respiratory tract, including the airways and distal lung, and can result in acute lung injury. Some individuals exposed to chlorine experience a full recovery from acute injury, whereas others develop persistent adverse effects, such as respiratory symptoms, inflammation, and lung-function decrements. In animal models, chlorine can produce persistent inflammation, remodeling, and obstruction in large or small airways, depending on species. Airways with pseudostratified epithelium are repaired efficiently, with surviving basal epithelial cells serving as progenitor cells that repopulate the complement of differentiated cell types. Distal airways lacking basal cells are repaired less efficiently, leading to chronic inflammation and fibrosis at these sites. Persistent chlorine-induced airway disease in humans is treated with asthma medication to relieve symptoms. However, such treatment does not ameliorate the underlying disease pathogenesis, so treatments that are more effective at preventing initial development of airway disease after irritant gas exposure and at reversing established disease are needed. PMID:27385061

Viking Helmet Corroles: Activating Inert Oxidometal Corroles.

PubMed

Schweyen, Peter; Brandhorst, Kai; Hoffmann, Martin; Wolfram, Benedikt; Zaretzke, Marc-Kevin; Bröring, Martin

2017-10-09

Chemically inert oxidometal(V) corrols of molybdenum and rhenium undergo clean ligand-exchange reactions upon the action of SiCl 4 . The resulting dichlorido complexes show trigonal prismatic coordination of the metal ion with the chlorine atoms residing in a cis configuration, and were studied by optical and resonance spectroscopy as well as DFT calculations. In situ reactivity studies with carbon nucleophiles indicate high reactivity for chlorine replacement. Treatment with sodium cyclopentadienide paves the way to robust molybdenum corrolocene half-sandwich complexes. These organometallic compounds are the first corrole species that stabilize an air-stable and diamagnetic low spin d 2 -Mo IV center. Structural, spectroelectrochemical, and chemical investigations prove a reversible Mo IV /Mo V redox couple close to the Fc/Fc + potential for these systems. The high stability of the compounds in both redox states calls for future applications in catalysis and as redox switch. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Acute toxicity of copper, ammonia, and chlorine to glochidia and juveniles of freshwater mussels (Unionidae)

USGS Publications Warehouse

Wang, N.; Ingersoll, C.G.; Hardesty, D.K.; Ivey, C.D.; Kunz, J.L.; May, T.W.; Dwyer, F.J.; Roberts, A.D.; Augspurger, T.; Kane, C.M.; Neves, R.J.; Barnhart, M.C.

2007-01-01

The objective of the present study was to determine acute toxicity of copper, ammonia, or chlorine to larval (glochidia) and juvenile mussels using the recently published American Society for Testing and Materials (ASTM) Standard guide for conducting laboratory toxicity tests with freshwater mussels. Toxicity tests were conducted with glochidia (24- to 48-h exposures) and juveniles (96-h exposures) of up to 11 mussel species in reconstituted ASTM hard water using copper, ammonia, or chlorine as a toxicant. Copper and ammonia tests also were conducted with five commonly tested species, including cladocerans (Daphnia magna and Ceriodaphnia dubia; 48-h exposures), amphipod (Hyalella azteca; 48-h exposures), rainbow trout (Oncorhynchus mykiss; 96-h exposures), and fathead minnow (Pimephales promelas; 96-h exposures). Median effective concentrations (EC50s) for commonly tested species were >58 ??g Cu/L (except 15 ??g Cu/L for C. dubia) and >13 mg total ammonia N/L, whereas the EC50s for mussels in most cases were 40 ??g/L and above the FAV in the WQC for chlorine. The results indicate that the early life stages of mussels generally were more sensitive to copper and ammonia than other organisms and that, including mussel toxicity data in a revision to the WQC, would lower the WQC for copper or ammonia. Furthermore, including additional mussel data in 2007 WQC for copper based on biotic ligand model would further lower the WQC. ?? 2007 SETAC.

Formation and control of disinfection byproducts and toxicity during reclaimed water chlorination: A review.

PubMed

Du, Ye; Lv, Xiao-Tong; Wu, Qian-Yuan; Zhang, Da-Yin; Zhou, Yu-Ting; Peng, Lu; Hu, Hong-Ying

2017-08-01

Chlorination is essential to the safety of reclaimed water; however, this process leads to concern regarding the formation of disinfection byproducts (DBPs) and toxicity. This study reviewed the formation and control strategies for DBPs and toxicity in reclaimed water during chlorination. Both regulated and emerging DBPs have been frequently detected in reclaimed water during chlorination at a higher level than those in drinking water, indicating they pose a greater risk to humans. Luminescent bacteria and Daphnia magna acute toxicity, anti-estrogenic activity and cytotoxicity generally increased after chlorination because of the formation of DBPs. Genotoxicity by umu-test and estrogenic activity were decreased after chlorination because of destruction of toxic chemicals. During chlorination, water quality significantly impacted changes in toxicity. Ammonium tended to attenuate toxicity changes by reacting with chlorine to form chloramine, while bromide tended to aggravate toxicity changes by forming hypobromous acid. During pretreatment by ozonation and coagulation, disinfection byproduct formation potential (DBPFP) and toxicity formation potential (TFP) occasionally increase, which is accompanied by DOC removal; thus, the decrease of DOC was limited to indicate the decrease of DBPFP and TFP. It is more important to eliminate the key fraction of precursors such as hydrophobic acid and hydrophilic neutrals. During chlorination, toxicities can increase with the increasing chlorine dose and contact time. To control the excessive toxicity formation, a relatively low chlorine dose and short contact time were required. Quenching chlorine residual with reductive reagents also effectively abated the formation of toxic compounds. Copyright © 2017. Published by Elsevier B.V.

Mechanistic aspects of ingested chlorine dioxide on thyroid function: impact of oxidants on iodide metabolism.

PubMed Central

Bercz, J P; Jones, L L; Harrington, R M; Bawa, R; Condie, L

1986-01-01

Toxicological studies dealing with recent findings of health effects of drinking water disinfectants are reviewed. Experiments with monkeys and rodents indicate that the biological activity of ingested disinfectants is expressed via their chemical interaction with the mucosal epithelia, secretory products, and nutritional contents of the alimentary tract. Evidence exists that a principal partner of this redox interaction is the iodide of nutritional origin that is ubiquitous in the gastrointestinal tract. Thus the observation that subchronic exposure to chlorine dioxide (ClO2) in drinking water decreases serum thyroxine levels in mammalian species can be best explained with changes produced in the chemical form of the bioavailable iodide. Ongoing and previously reported mechanistic studies indicate that oxidizing agents such as chlorine-based disinfectants oxidize the basal iodide content of the gastrointestinal tract. The resulting reactive iodine species readily attaches to organic matter by covalent bonding. Evidence suggests that the extent to which such iodinated organics are formed is proportional to the magnitude of the electromotive force and stoichiometry of the redox couple between iodide and the disinfectant. Because the extent of thyroid uptake of the bioavailable iodide does not decrease during ClO2 ingestion, it seems that ClO2 does not cause iodide deficiency of sufficient magnitude to account for the decrease in hormonogenesis. Absorption of one or more of iodinated molecules, e.g., nutrients, hormones, or cellular constituents of the alimentary tract having thyromimetic or thyroid inhibitory properties, is a better hypothesis for the effects seen. Images FIGURE 1. a FIGURE 1. b FIGURE 1. c PMID:3816729

[The sodium-potassium-chloride cotransport of the cell membrane].

PubMed

Urazaev, A Kh

1998-01-01

Discovery and active exploration of the furosemid-sensitive derived-active co-transport of sodium-potassium-chlorine ions took place in the end of 1970-es-1980-es. This transportation mechanism was discovered in various types of cells, both of plant and of animal origin. This review describes properties of the transportation process, which was most comprehensive explored in experiments with erythrocytes, epithelium cells and muscles. The review covers the following properties: anion and cation selectivity of the chlorine transportation, its sensitivity to the specific blocking agents (furocemid, bumetanid, etc.), stoichiometry of the transportation process, etc. For energy source, the chlorine transportation is based on transmembrane electrochemical gradient for sodium ions. The article provides the most recent results of investigation of the chemical nature of the molecule of the chlorine membrane transport. Based on various studies, the molecule of this protein weighs from 120 to 200 kD, includes about 1200 amino acid residua, and forms long cytoplasmatic NH2 and COOH-termini. The gene encoding the amino acid sequence has been cloned. The article discusses the issues of regulation of the chlorine transportation. Humoral control of intensity of the chlorine transportation has been mostly studied in experiments with plain muscles, the issues related to nervous regulation--with only skeleton muscle fibers. The article provides specific data on the mechanisms of the above types of the physiological regulation of active chlorine transportation. In general, the humoral factors, which increase the intracellular concentration of cAMF stimulate chlorine transportation. On the contrary, the hormones, which increase concentration of cGMF in cytoplasm reduce its activity in plain muscles. The discussion of the mechanisms of the nervous controls of the chlorine transportation in the skeleton muscles includes the original results of the author. These results indicate that the suppressive influence of the motor innervation on intensity of the chlorine transportation involves the non-quantum acetilcholine and glutamate secreted from the motor nerves. These agents produce Ca(2+)-dependent molecules of nitrogen oxide in sarcoplasm, which act in the retrograde mode on the nervous terminal and activate there the synthesis of cGMF. Disruption of this bilateral transsynaptic signalization resulting from cutting a nerve of blocking of its axoflow creates more active chlorine transportation and subsequent de-innervation changes in properties of the muscle fibers. The functions of chlorine transportation, which are best studies as of today and therefore, discussed in more detail in the review, include participation of this process in the regulatory rehabilitation of the volume of various cells in non-isotonic medium, and the role of chlorine transportation in development of a negative charge at the interior side of membrane of the skeleton muscle fibers. The former function essentially means that dehydration of a cell in the hypertonic medium increases activity of the sodium, potassium and chlorine co-transport directed to the cell, resulting in increase of the amount of the osmosis-active cytoplasm material, and inflow of water, which fully restores the cell volume in these conditions. Starting from the pioneer studies by Hodgkin and Horowicz [correction of Hojkin and Gorovits], the role of chlorine ions in forming a charge on the membrane of excited cells has been generally interpreted as exclusively passive. I.e., distribution of these ions over both sides of membrane was assumed as equilibrium with the existing values of the membrane potential in the non-excited state. The review provides data obtained in the recent decade, which have proved that the non-excited membrane potential in muscle fibers is co-created by the diffusional potassium and chlorine potential. (ABSTRACT TRUNCATED)

Biocidal Polyester

DTIC Science & Technology

2002-01-01

chlorinated sample having antibacterial activity ; absence of “Cl” indicates an unchlorinated control. bThe challenge of S. aureus was 1.3 109 CFU (9.1...Table 1 show that when a very high challenge load of S. aureus (9.1 logs) was employed, the chlorinated samples showed rea- sonable antibacterial ...Table IV Regeneration of Antibacterial Activity Sample Chlorination Microbiological Performance (Log Reduction)a PETHCl-1 First: 50% Clorox 9.0 PETH None

Rapid Hydrogen and Oxygen Atom Transfer by a High-Valent Nickel-Oxygen Species.

PubMed

Corona, Teresa; Draksharapu, Apparao; Padamati, Sandeep K; Gamba, Ilaria; Martin-Diaconescu, Vlad; Acuña-Parés, Ferran; Browne, Wesley R; Company, Anna

2016-10-05

Terminal high-valent metal-oxygen species are key reaction intermediates in the catalytic cycle of both enzymes (e.g., oxygenases) and synthetic oxidation catalysts. While tremendous efforts have been directed toward the characterization of the biologically relevant terminal manganese-oxygen and iron-oxygen species, the corresponding analogues based on late-transition metals such as cobalt, nickel or copper are relatively scarce. This scarcity is in part related to the "Oxo Wall" concept, which predicts that late transition metals cannot support a terminal oxido ligand in a tetragonal environment. Here, the nickel(II) complex (1) of the tetradentate macrocyclic ligand bearing a 2,6-pyridinedicarboxamidate unit is shown to be an effective catalyst in the chlorination and oxidation of C-H bonds with sodium hypochlorite as terminal oxidant in the presence of acetic acid (AcOH). Insight into the active species responsible for the observed reactivity was gained through the study of the reaction of 1 with ClO - at low temperature by UV-vis absorption, resonance Raman, EPR, ESI-MS, and XAS analyses. DFT calculations aided the assignment of the trapped chromophoric species (3) as a nickel-hypochlorite species. Despite the fact that the formal oxidation state of the nickel in 3 is +4, experimental and computational analysis indicate that 3 is best formulated as a Ni III complex with one unpaired electron delocalized in the ligands surrounding the metal center. Most remarkably, 3 reacts rapidly with a range of substrates including those with strong aliphatic C-H bonds, indicating the direct involvement of 3 in the oxidation/chlorination reactions observed in the 1/ClO - /AcOH catalytic system.

Impact of water quality on chlorine demand of corroding copper.

PubMed

Lytle, Darren A; Liggett, Jennifer

2016-04-01

Copper is widely used in drinking water premise plumbing system materials. In buildings such as hospitals, large and complicated plumbing networks make it difficult to maintain good water quality. Sustaining safe disinfectant residuals throughout a building to protect against waterborne pathogens such as Legionella is particularly challenging since copper and other reactive distribution system materials can exert considerable demands. The objective of this work was to evaluate the impact of pH and orthophosphate on the consumption of free chlorine associated with corroding copper pipes over time. A copper test-loop pilot system was used to control test conditions and systematically meet the study objectives. Chlorine consumption trends attributed to abiotic reactions with copper over time were different for each pH condition tested, and the total amount of chlorine consumed over the test runs increased with increasing pH. Orthophosphate eliminated chlorine consumption trends with elapsed time (i.e., chlorine demand was consistent across entire test runs). Orthophosphate also greatly reduced the total amount of chlorine consumed over the test runs. Interestingly, the total amount of chlorine consumed and the consumption rate were not pH dependent when orthophosphate was present. The findings reflect the complex and competing reactions at the copper pipe wall including corrosion, oxidation of Cu(I) minerals and ions, and possible oxidation of Cu(II) minerals, and the change in chlorine species all as a function of pH. The work has practical applications for maintaining chlorine residuals in premise plumbing drinking water systems including large buildings such as hospitals. Published by Elsevier Ltd.

Validation Study for Crediting Chlorine in Criticality Analyses for US Spent Nuclear Fuel Disposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sobes, Vladimir; Scaglione, John M.; Wagner, John C.

2015-01-01

Spent nuclear fuel (SNF) management practices in the United States rely on dry storage systems that include both canister- and cask-based systems. The United States Department of Energy Used Fuel Disposition Campaign is examining the feasibility of direct disposal of dual-purpose (storage and transportation) canisters (DPCs) in a geological repository. One of the major technical challenges for direct disposal is the ability to demonstrate the subcriticality of the DPCs loaded with SNF for the repository performance period (e.g., 10,000 years or more) as the DPCs may undergo degradation over time. Specifically, groundwater ingress into the DPC (i.e., flooding) could allowmore » the system to achieve criticality in scenarios where the neutron absorber plates in the DPC basket have degraded. However, as was shown by Banerjee et al., some aqueous species in the groundwater provide noticeable reactivity reduction for these systems. For certain amounts of particular aqueous species (e.g., chlorine, lithium) in the groundwater, subcriticality can be demonstrated even for DPCs with complete degradation of the neutron absorber plates or a degraded fuel basket configuration. It has been demonstrated that chlorine is the leading impurity, as indicated by significant neutron absorption in the water that is available in reasonable quantities for the deep geological repository media under consideration. This paper presents the results of an investigation of the available integral experiments worldwide that could be used to validate DPC disposal criticality evaluations, including credit for chlorine. Due to the small number of applicable critical configurations, validation through traditional trending analysis was not possible. The bias in the eigenvalue of the application systems due only to the chlorine was calculated using TSURFER analysis and found to be on the order of 100 percent mille (1 pcm = 10 -5 k eff). This study investigated the design of a series of critical configurations with varying amounts of chlorine to address validation gaps. Such integral experiments would support the crediting of the chlorine neutron-absorption properties in groundwater and the demonstration of subcriticality for DPCs in deep geologic repositories with sufficient chlorine availability.« less

Urea degradation by electrochemically generated reactive chlorine species: products and reaction pathways.

PubMed

Cho, Kangwoo; Hoffmann, Michael R

2014-10-07

This study investigated the transformation of urea by electrochemically generated reactive chlorine species (RCS). Solutions of urea with chloride ions were electrolyzed using a bismuth doped TiO2 (BiOx/TiO2) anode coupled with a stainless steel cathode at applied anodic potentials (Ea) of either +2.2 V or +3.0 V versus the normal hydrogen electrode. In NaCl solution, the current efficiency of RCS generation was near 30% at both potentials. In divided cell experiments, the pseudo-first-order rate of total nitrogen decay was an order of magnitude higher at Ea of +3.0 V than at +2.2 V, presumably because dichlorine radical (Cl2(-)·) ions facilitate the urea transformation primary driven by free chlorine. Quadrupole mass spectrometer analysis of the reactor headspace revealed that N2 and CO2 are the primary gaseous products of the oxidation of urea, whose urea-N was completely transformed into N2 (91%) and NO3(-) (9%). The higher reaction selectivity with respect to N2 production can be ascribed to a low operational ratio of free available chlorine to N. The mass-balance analysis recovered urea-C as CO2 at 77%, while CO generation most likely accounts for the residual carbon. In light of these results, we propose a reaction mechanism involving chloramines and chloramides as reaction intermediates, where the initial chlorination is the rate-determining step in the overall sequence of reactions.

[Development and application of a multi-species water quality model for water distribution systems with EPANET-MSX].

PubMed

Sun, Fu; Chen, Ji-ning; Zeng, Si-yu

2008-12-01

A conceptual multi-species water quality model for water distribution systems was developed on the basis of the toolkit of the EPANET-MSX software. The model divided the pipe segment into four compartments including pipe wall, biofilm, boundary layer and bulk liquid. The involved processes were substrate utilization and microbial growth, decay and inactivation of microorganisms, mass transfer of soluble components through the boundary layer, adsorption and desorption of particular components between bulk liquid and biofilm, oxidation and halogenation of organic matter by residual chlorine, and chlorine consumption by pipe wall. The fifteen simulated variables included the seven common variables both in the biofilm and in the bulk liquid, i.e. soluble organic matter, particular organic matter, ammonia nitrogen, residual chlorine, heterotrophic bacteria, autotrophic bacteria and inert solids, as well as biofilm thickness on the pipe wall. The model was validated against the data from a series of pilot experiments, and the simulation accuracy for residual chlorine and turbidity were 0.1 mg/L and 0.3 NTU respectively. A case study showed that the model could reasonably reflect the dynamic variation of residual chlorine and turbidity in the studied water distribution system, while Monte Carlo simulation, taking into account both the variability of finished water from the waterworks and the uncertainties of model parameters, could be performed to assess the violation risk of water quality in the water distribution system.

The Chlorine Isotopic Composition Of Lunar UrKREEP

NASA Technical Reports Server (NTRS)

Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

2016-01-01

Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. However, the current models for the Moon’s formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon. In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes, using NanoSIMS (Nanoscale Secondary Ion Mass Spectrometry) of lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

Oxidation of chlorinated ethenes by heat-activated persulfate: kinetics and products.

PubMed

Waldemer, Rachel H; Tratnyek, Paul G; Johnson, Richard L; Nurmi, James T

2007-02-01

In situ chemical oxidation (ISCO) and in situ thermal remediation (ISTR) are applicable to treatment of groundwater contaminated with chlorinated ethenes. ISCO with persulfate (S2O8(2-)) requires activation, and this can be achieved with the heat from ISTR, so there may be advantages to combining these technologies. To explore this possibility, we determined the kinetics and products of chlorinated ethene oxidation with heat-activated persulfate and compared them to the temperature dependence of other degradation pathways. The kinetics of chlorinated ethene disappearance were pseudo-first-order for 1-2 half-lives, and the resulting rate constants-measured from 30 to 70 degrees C--fit the Arrhenius equation, yielding apparent activation energies of 101 +/- 4 kJ mol(-1) for tetrachloroethene (PCE), 108 +/- 3 kJ mol(-1) for trichloroethene (TCE), 144 +/- 5 kJ mol(-1) for cis-1,2-dichloroethene (cis-DCE), and 141 +/- 2 kJ mol(-1) for trans-1,2-dichloroethene (trans-DCE). Chlorinated byproducts were observed, but most of the parent material was completely dechlorinated. Arrhenius parameters for hydrolysis and oxidation by persulfate or permanganate were used to calculate rates of chlorinated ethene degradation by these processes over the range of temperatures relevant to ISTR and the range of oxidant concentrations and pH relevant to ISCO.

Revisiting Antarctic Ozone Depletion

NASA Astrophysics Data System (ADS)

Grooß, Jens-Uwe; Tritscher, Ines; Müller, Rolf

2015-04-01

Antarctic ozone depletion is known for almost three decades and it has been well settled that it is caused by chlorine catalysed ozone depletion inside the polar vortex. However, there are still some details, which need to be clarified. In particular, there is a current debate on the relative importance of liquid aerosol and crystalline NAT and ice particles for chlorine activation. Particles have a threefold impact on polar chlorine chemistry, temporary removal of HNO3 from the gas-phase (uptake), permanent removal of HNO3 from the atmosphere (denitrification), and chlorine activation through heterogeneous reactions. We have performed simulations with the Chemical Lagrangian Model of the Stratosphere (CLaMS) employing a recently developed algorithm for saturation-dependent NAT nucleation for the Antarctic winters 2011 and 2012. The simulation results are compared with different satellite observations. With the help of these simulations, we investigate the role of the different processes responsible for chlorine activation and ozone depletion. Especially the sensitivity with respect to the particle type has been investigated. If temperatures are artificially forced to only allow cold binary liquid aerosol, the simulation still shows significant chlorine activation and ozone depletion. The results of the 3-D Chemical Transport Model CLaMS simulations differ from purely Lagrangian longtime trajectory box model simulations which indicates the importance of mixing processes.

Bromine Incorporation in Regulated and Emerging DBPs and the Relative Predominance of Mono-, Di-, and Trihalogenated DBPs

EPA Science Inventory

Brominated disinfection by-products (DBPs) (in general) appear to be more cytotoxic and genotoxic than the chlorinated species, and some of the dihalogenated species are more toxic than the trihalogenated analogues; however, many of the more toxic species are not routinely measur...

Studies on toxicity of OTEC plant components on marine animals from the Gulf of Mexico. Final report, September 1, 1978-November 30, 1980

DOE Office of Scientific and Technical Information (OSTI.GOV)

Venkataramiah, A.; Lakshmi, G.J.; Best, C.

1981-06-01

Ammonia and chlorine were chosen for toxicity studies as they pose the greatest potential environmental threat. Acute and chronic bioassays determined the LT/sub 50/, LC/sub 50/ and the behavior of mullet (Mugil cephalus), sargassum shrimp (Latreutes focorum) and filefish (Monocanthus hispidus). The chronic bioassays were carried out mainly in sublethal concentrations of ammonia and chlorine. The findings indicate that high concentrations of ammonia and chlorine from the OTEC plants are toxic to marine animals. Also the level of toxicity is related to the species, their habitats and life stages.

Comparing the Chlorine Disinfection of Detached Biofilm Clusters with Those of Sessile Biofilms and Planktonic Cells in Single- and Dual-Species Cultures ▿ †

PubMed Central

Behnke, Sabrina; Parker, Albert E.; Woodall, Dawn; Camper, Anne K.

2011-01-01

Although the detachment of cells from biofilms is of fundamental importance to the dissemination of organisms in both public health and clinical settings, the disinfection efficacies of commonly used biocides on detached biofilm particles have not been investigated. Therefore, the question arises whether cells in detached aggregates can be killed with disinfectant concentrations sufficient to inactivate planktonic cells. Burkholderia cepacia and Pseudomonas aeruginosa were grown in standardized laboratory reactors as single species and in coculture. Cluster size distributions in chemostats and biofilm reactor effluent were measured. Chlorine susceptibility was assessed for planktonic cultures, attached biofilm, and particles and cells detached from the biofilm. Disinfection tolerance generally increased with a higher percentage of larger cell clusters in the chemostat and detached biofilm. Samples with a lower percentage of large clusters were more easily disinfected. Thus, disinfection tolerance depended on the cluster size distribution rather than sample type for chemostat and detached biofilm. Intact biofilms were more tolerant to chlorine independent of species. Homogenization of samples led to significantly increased susceptibility in all biofilm samples as well as detached clusters for single-species B. cepacia, B. cepacia in coculture, and P. aeruginosa in coculture. The disinfection efficacy was also dependent on species composition; coculture was advantageous to the survival of both species when grown as a biofilm or as clusters detached from biofilm but, surprisingly, resulted in a lower disinfection tolerance when they were grown as a mixed planktonic culture. PMID:21856824

Occurrence of non-fermenting gram negative bacteria in drinking water dispensed from point-of-use microfiltration devices.

PubMed

Zanetti, Franza; de Luca, Giovanna; Leoni, Erica; Sacchetti, Rossella

2014-01-01

Many devices have been marketed in order to improve the organoleptic characteristics of tap water resulting from disinfection with chlorine derivates. The aim of the presented study was to assess the degree of contamination by non-fermenting Gram-negative bacteria (NF-GNB) of drinking water dispensed from microfiltration devices at point-of-use. Water samples were collected from 94 point-of-use water devices fitted with a filter (0.5 μm pore size) containing powdered activated carbon. The microbiological contamination of water entering and leaving the microfiltered water dispensers was compared. The NF-GNB loads were correlated to Total Heterotrophic Counts (HPCs) at 37 and 22 °C, residua chlorine, and some structural and functional features of the devices. NF-GNB were detected from 23% of supply water samples, 33% of still unchilled water, 33% of still chilled water and 18% of carbonated chilled water. The most frequent isolates were Pseudomonadaceae: Steno.maltophilia 30.2% of isolates, Pseudomonas 20.5%, Delftia acidovorans 13.4%, while the species more largely distributed was Ps. aeruginosa recovered from 13% of samples. The distribution of the various NF-GNB was different in the water entering and in that leaving the devices. Ps.aeruginosa and Steno.maltophilia were the predominant species in water leaving the microfiltration dispensers, probably due to their capacity to colonize the circuits and to prevail over the others. Recovery of NF-GNB was favoured by the reduction in residual chlorine of the supply water, occasional use, the absence of a bacteriostatic element in the filter and inadequate disinfection of the water lines. The presence of high concentrations of potentially pathogenic species of NF-GNB (Ps.aeruginosa, Steno. maltophilia, Burkhol.cepacia) in the water dispensed from microfiltration devices represents a risk of waterborne infections for vulnerable individuals. When these devices are used in environments such as hospitals, nursing homes for the elderly, etc., microbiological monitoring for the detection of NF-GNB is advisable.

A comparison of six different ballast water treatment systems based on UV radiation, electrochlorination and chlorine dioxide.

PubMed

Stehouwer, Peter Paul; Buma, Anita; Peperzak, Louis

2015-01-01

The spread of aquatic invasive species through ballast water is a major ecological and economical threat. Because of this, the International Maritime Organization (IMO) set limits to the concentrations of organisms allowed in ballast water. To meet these limits, ballast water treatment systems (BWTSs) were developed. The main techniques used for ballast water treatment are ultraviolet (UV) radiation and electrochlorination (EC). In this study, phytoplankton regrowth after treatment was followed for six BWTSs. Natural plankton communities were treated and incubated for 20 days. Growth, photosystem II efficiency and species composition were followed. The three UV systems all showed similar patterns of decrease in phytoplankton concentrations followed by regrowth. The two EC and the chlorine dioxide systems showed comparable results. However, UV- and chlorine-based treatment systems showed significantly different responses. Overall, all BWTSs reduced phytoplankton concentrations to below the IMO limits, which represents a reduced risk of aquatic invasions through ballast water.

Mass accommodation coefficient measurements for HNO3, HCl and N2O5 on water, ice and aqueous sulfuric acid droplet surfaces

NASA Technical Reports Server (NTRS)

Worsnop, Douglas; Zahniser, Mark; Kolb, Charles; Watson, Lyn; Vandoren, Jane; Jayne, John; Davidovits, Paul

1988-01-01

Preliminary results are reported of the direct measurement of accommodation coefficients for HNO3, N2O5 and HCl on water drops, aqueous sulfuric acid drops and ice particles. The heterogeneous chemistry of these species together with ClONO2 has been implicated in the ozone depletion observed in the Antarctic stratosphere during the spring in the last eight years. The most plausible chemical mechanism involves the removal of nitrogen oxide species via condensation on ice particles in polar stratospheric clouds resulting in a increase in the active chlorine species responsible for the ozone depletion. The observation of low NO2 and high ClO densities in the Antarctic stratosphere last summer appear to be consistent with such a mechanism.

Effects of Starvation on Physiological Activity and Chlorine Disinfection Resistance in Escherichia coli O157:H7

PubMed Central

Lisle, John T.; Broadaway, Susan C.; Prescott, Annette M.; Pyle, Barry H.; Fricker, Colin; McFeters, Gordon A.

1998-01-01

Escherichia coli O157:H7 can persist for days to weeks in microcosms simulating natural conditions. In this study, we used a suite of fluorescent, in situ stains and probes to assess the influence of starvation on physiological activity based on membrane potential (rhodamine 123 assay), membrane integrity (LIVE/DEAD BacLight kit), respiratory activity (5-cyano-2,3-di-4-tolyl-tetrazolium chloride assay), intracellular esterase activity (ScanRDI assay), and 16S rRNA content. Growth-dependent assays were also used to assess substrate responsiveness (direct viable count [DVC] assay), ATP activity (MicroStar assay), and culturability (R2A agar assay). In addition, resistance to chlorine disinfection was assessed. After 14 days of starvation, the DVC values decreased, while the values in all other assays remained relatively constant and equivalent to each other. Chlorine resistance progressively increased through the starvation period. After 29 days of starvation, there was no significant difference in chlorine resistance between control cultures that had not been exposed to the disinfectant and cultures that had been exposed. This study demonstrates that E. coli O157:H7 adapts to starvation conditions by developing a chlorine resistance phenotype. PMID:9835545

Effects of starvation on physiological activity and chlorine disinfection resistance in Escherichia coli O157:H7

NASA Technical Reports Server (NTRS)

Lisle, J. T.; Broadaway, S. C.; Prescott, A. M.; Pyle, B. H.; Fricker, C.; McFeters, G. A.

1998-01-01

Escherichia coli O157:H7 can persist for days to weeks in microcosms simulating natural conditions. In this study, we used a suite of fluorescent, in situ stains and probes to assess the influence of starvation on physiological activity based on membrane potential (rhodamine 123 assay), membrane integrity (LIVE/DEAD BacLight kit), respiratory activity (5-cyano-2,3-di-4-tolyl-tetrazolium chloride assay), intracellular esterase activity (ScanRDI assay), and 16S rRNA content. Growth-dependent assays were also used to assess substrate responsiveness (direct viable count [DVC] assay), ATP activity (MicroStar assay), and culturability (R2A agar assay). In addition, resistance to chlorine disinfection was assessed. After 14 days of starvation, the DVC values decreased, while the values in all other assays remained relatively constant and equivalent to each other. Chlorine resistance progressively increased through the starvation period. After 29 days of starvation, there was no significant difference in chlorine resistance between control cultures that had not been exposed to the disinfectant and cultures that had been exposed. This study demonstrates that E. coli O157:H7 adapts to starvation conditions by developing a chlorine resistance phenotype.

Efficacy of electrolyzed oxidizing water in inactivating Salmonella on alfalfa seeds and sprouts.

PubMed

Kim, Chyer; Hung, Yen-Con; Brackett, Robert E; Lin, Chyi-Shen

2003-02-01

Studies have demonstrated that electrolyzed oxidizing (EO) water is effective in reducing foodborne pathogens on fresh produce. This study was undertaken to determine the efficacy of EO water and two different forms of chlorinated water (chlorine water from Cl2 and Ca(OCl)2 as sources of chlorine) in inactivating Salmonella on alfalfa seeds and sprouts. Tengram sets of alfalfa seeds inoculated with a five-strain cocktail of Salmonella (6.3 x 10(4) CFU/g) were subjected to 90 ml of deionized water (control), EO water (84 mg/liter of active chlorine), chlorine water (84 mg/liter of active chlorine), and Ca(OCl)2 solutions at 90 and 20,000 mg/liter of active chlorine for 10 min at 24 +/- 2 degrees C. The application of EO water, chlorinated water, and 90 mg/liter of Ca(OCl)2 to alfalfa seeds for 10 min reduced initial populations of Salmonella by at least 1.5 log10 CFU/g. For seed sprouting, alfalfa seeds were soaked in the different treatment solutions described above for 3 h. Ca(OCl)2 (20,000 mg/liter of active chlorine) was the most effective treatment in reducing the populations of Salmonella and non-Salmonella microflora (4.6 and 7.0 log10 CFU/g, respectively). However, the use of high concentrations of chlorine generates worker safety concerns. Also, the Ca(OCl)2 treatment significantly reduced seed germination rates (70% versus 90 to 96%). For alfalfa sprouts, higher bacterial populations were recovered from treated sprouts containing seed coats than from sprouts with seed coats removed. The effectiveness of EO water improved when soaking treatments were applied to sprouts in conjunction with sonication and seed coat removal. The combined treatment achieved 2.3- and 1.5-log10 CFU/g greater reductions than EO water alone in populations of Salmonella and non-Salmonella microflora, respectively. This combination treatment resulted in a 3.3-log10 CFU/g greater reduction in Salmonella populations than the control (deionized water) treatment.

Effects of Processing on MOS Radiation Hardening

DTIC Science & Technology

1992-09-01

magnitude) impurity inclusion for Fluorine sources vs. Chlorine sources, many of the other beneficial effects on point defects, traps, MOS quality, etc...profiles. The addition of percent concentrations of a chlorine rates from 1 to 10 ml/nmr. This corresponded to fluorine bearing compound to the silicon...computes the partial roethane and gaseous nitrogen trifluoride . The alphatic liq- pres-ures of all the possible species in equilibrium in the uid

Short chain chlorinated paraffins in mollusks from coastal waters in the Chinese Bohai Sea.

PubMed

Yuan, Bo; Wang, Thanh; Zhu, Nali; Zhang, Kegang; Zeng, Lixi; Fu, Jianjie; Wang, Yawei; Jiang, Guibin

2012-06-19

As an extremely complex group of persistent organic pollutants (POPs) candidates in the Stockholm Convention, short chain chlorinated paraffins (SCCPs) have been of extensive concern in recent years. In this study, nine bivalve and two gastropod species were collected in 2009 to evaluate the spatial distributions and potential factors influencing the bioaccumulation of SCCPs in mollusks in the Chinese Bohai Sea. The concentrations of ∑ SCCPs in the mollusks were in the range 64.9-5510 ng/g (dry weight) with an average chlorine content of 61.1%. C(10) and C(11) were the predominant homologue groups of SCCPs, which accounted for about 29.7% and 34.9% of ∑ SCCPs, respectively. Six and seven chlorinated substituents were the main congener groups. Mya arenaria (Mya), Mactra veneriformis (Mac), and Crassostrea talienwhanensis (Oyster, Ost) had higher average concentrations of SCCPs than other species, implying that these bivalves could be used as sentinels to indicate SCCPs contamination in this coastal region. A significant positive linear relationship was found between SCCP concentrations and lipid content of the mollusks, whereas the lipid-normalized SCCP concentrations were negatively linear-related to the trophic levels (TL), which implied that SCCPs did not show biomagnification in mollusks in this region.

Free chlorine inactivation of fungi in drinking water sources.

PubMed

Pereira, V J; Marques, R; Marques, M; Benoliel, M J; Barreto Crespo, M T

2013-02-01

The effectiveness of free chlorine for the inactivation of fungi present in settled surface water was tested. In addition, free chlorine inactivation rate constants of Cladosporium tenuissimum, Cladosporium cladosporioides, Phoma glomerata, Aspergillus terreus, Aspergillus fumigatus, Penicillium griseofulvum, and Penicillium citrinum that were found to occur in different source waters were determined in different water matrices (laboratory grade water and settled water). The effect of using different disinfectant concentrations (1 and 3 mg/l), temperatures (21 and 4 °C), and pH levels (6 and 7) was addressed. The sensitivity degree of different fungi isolates to chlorine disinfection varied among different genera with some species showing a higher resistance to disinfection and others expected to be more prone to protection from inactivation by the water matrix components. When the disinfection efficiency measured in terms of the chlorine concentration and contact time (Ct) values needed to achieve 99% inactivation were compared with the Ct values reported as being able to achieve the same degree of inactivation of other microorganisms, fungi were found to be more resistant to chlorine inactivation than bacteria and viruses and less resistant than Cryptosporidium oocysts. Copyright © 2012 Elsevier Ltd. All rights reserved.

Free Chlorine and Monochloramine Application to Nitrifying Biofilm: Comparison of Biofilm Penetration, Activity, and Viability

EPA Science Inventory

Biofilm in drinking water systems is undesirable and effective biofilm control maintains public health. Free chlorine and monochloramine are commonly used as secondary drinking water disinfectants, but monochloramine is perceived to penetrate biofilm better than free chlorine. ...

Dechlorination by ultraviolet radiation: a suitable alternative to activated carbon in dialysis water systems?

PubMed

James, Ray

2009-12-01

Chlorine-based products are widely used in the water supply industry, and the potential for adverse effects in the haemodialysis setting is well documented. To date, the most commonly used method of chlorine removal has been granular activated carbon filters. An increasingly popular method of dechlorination is the use of high intensity, broad-spectrum UV systems to reduce both free chlorine and combined chlorine compounds (chloramines) into easily removed by-products. UV radiation has been successfully used in the pharmaceutical and food industries to destroy free chlorine and/or chloramines present in water, and kill all known spoilage microorganisms including bacteria, viruses, yeasts and moulds (and their spores). This nonchemical method can offer significant advantages and benefits compared to conventional dechlorination technologies currently employed in dialysis water systems. Whilst UV treatment at 254 nm wavelength has been routinely used for disinfection purposes in dialysis water systems, this paper considers whether UV radiation can be used as an alternative to more traditional methods of chlorine removal.

Potential Precursor Compounds for Chlorohydrocarbons Detected in Gale Crater, Mars, by the SAM Instrument Suite on the Curiosity Rover

NASA Technical Reports Server (NTRS)

Miller, Kristen E.; Eigenbrode, Jennifer L.; Freissinet, Caroline; Glavin, Daniel P.; Kotrc, Benjamin; Francois, Pascaline; Summons, Roger E.

2016-01-01

The detection of chlorinated organic compounds in near-surface sedimentary rocks by the Sample Analysis at Mars (SAM) instrument suite aboard the Mars Science Laboratory Curiosity rover represents an important step toward characterizing habitable environments on Mars. However, this discovery also raises questions about the identity and source of their precursor compounds and the processes by which they become chlorinated. Here we present the results of analog experiments, conducted under conditions similar to SAM gas chromatography-mass spectrometry analyses, in which we pyrolyzed potential precursor compounds in the presence of various Cl salts and Fe oxides that have been identified in Martian sediments. While chloromethanes could not be unambiguously identified, 1,2-dichloropropane (1,2-DCP), which is one of the chlorinated compounds identified in SAM data, is formed from the chlorination of aliphatic precursors. Additionally, propanol produced more 1,2-DCP than nonfunctionalized aliphatics such as propane or hexanes. Chlorinated benzenes ranging from chlorobenzene to hexachlorobenzene were identified in experiments with benzene carboxylic acids but not with benzene or toluene. Lastly, the distribution of chlorinated benzenes depended on both the substrate species and the nature and concentration of the Cl salt. Ca and Mg perchlorate, both of which release O2 in addition to Cl2 and HCl upon pyrolysis, formed less chlorobenzene relative to the sum of all chlorinated benzenes than in experiments with ferric chloride. FeCl3, a Lewis acid, catalyzes chlorination but does not aid combustion. Accordingly, both the precursor chemistry and sample mineralogy exert important controls on the distribution of chlorinated organics.

Transformation mechanism of benzophenone-4 in free chlorine promoted chlorination disinfection.

PubMed

Xiao, Ming; Wei, Dongbin; Yin, Junxia; Wei, Guohua; Du, Yuguo

2013-10-15

The UV-filter BP-4 (2-hydroxy-4-methoxybenzophenone-5-sulfonic acid) has been frequently observed in the environment, showing high potentials to invade drinking water, swimming water, or wastewater reclamation treatment systems. With the help of high performance liquid chromatography-high resolution mass spectrometry and nuclear magnetic resonance spectroscopy, 10 new products from free chlorine-promoted BP-4 disinfection have been disclosed and their possible transformation routes have been investigated. The first route is chlorine substitution of BP-4 and its transformation products, forming mono-, di-, and tri-chlorinated BP-4 analogs. The second is Baeyer-Villiger-Type oxidation, converting diphenyl ketone to phenyl ester derivatives. The third is ester hydrolysis, generating corresponding phenolic and benzoic products. The fourth is decarboxylation, replacing the carboxyl group by chloride in the benzoic-type intermediate. The fifth is desulfonation, degrading the sulfonic group through an alternative chlorine substitution on the benzene ring. Orthogonal experiments have been established to investigate the species transformed from BP-4 at different pH values and free available chlorine (FAC) dosages. The reaction pathways are strongly dependent on pH conditions, while an excessive amount of FAC eliminates BP-4 to the smaller molecules. The initial transformation of BP-4 in chlorination system follows pseudo-first-order kinetics, and its half-lives ranged from 7.48 s to 1.26 × 10(2) s. More importantly, we have observed that the FAC-treated BP-4 aqueous solution might increase the genotoxic potentials due to the generation of chlorinated disinfection by-products. Copyright © 2013 Elsevier Ltd. All rights reserved.

Catalysis of copper corrosion products on chlorine decay and HAA formation in simulated distribution systems.

PubMed

Zhang, Hong; Andrews, Susan A

2012-05-15

This study investigated the effect of copper corrosion products, including Cu(II), Cu(2)O, CuO and Cu(2)(OH)(2)CO(3), on chlorine degradation, HAA formation, and HAA speciation under controlled experimental conditions. Chlorine decay and HAA formation were significantly enhanced in the presence of copper with the extent of copper catalysis being affected by the solution pH and the concentration of copper corrosion products. Accelerated chlorine decay and increased HAA formation were observed at pH 8.6 in the presence of 1.0 mg/L Cu(II) compared with that observed at pH 6.6 and pH 7.6. Further investigation of chlorine decay in the presence of both Suwannee River NOM and Cu(II) indicated that an increased reactivity of NOM with dissolved and/or solid surface-associated Cu(II), rather than chlorine auto-decomposition, was a primary reason for the observed rapid chlorine decay. Copper corrosion solids [Cu(2)O, CuO, Cu(2)(OH)(2)CO(3)] exhibited catalytic effects on both chlorine decay and HAA formation. Contrary to the results observed when in the absence of copper corrosion products, DCAA formation was consistently predominant over other HAA species in the presence of copper corrosion products, especially at neutral and high pH. This study improves the understanding for water utilities and households regarding chlorine residuals and HAA concentrations in distribution systems, in particular once the water reaches domestic plumbing where copper is widely used. Copyright © 2012 Elsevier Ltd. All rights reserved.

Disinfection of bacteria attached to granular activated carbon.

PubMed Central

LeChevallier, M W; Hassenauer, T S; Camper, A K; McFeters, G A

1984-01-01

Heterotrophic plate count bacteria, coliform organisms, and pathogenic microorganisms attached to granular activated carbon particles were examined for their susceptibility to chlorine disinfection. When these bacteria were grown on carbon particles and then disinfected with 2.0 mg of chlorine per liter (1.4 to 1.6 mg of free chlorine residual per liter after 1 h) for 1 h, no significant decrease in viable counts was observed. Washed cells attached to the surface of granular activated carbon particles showed similar resistance to chlorine, but a progressive increase in sublethal injury was found. Observations made by scanning electron microscope indicated that granular activated carbon was colonized by bacteria which grow in cracks and crevices and are coated by an extracellular slime layer. These data suggest a possible mechanism by which treatment and disinfection barriers can be penetrated and pathogenic bacteria may enter drinking water supplies. Images PMID:6508306

Chronic Low Dose Chlorine Exposure Aggravates Allergic Inflammation and Airway Hyperresponsiveness and Activates Inflammasome Pathway

PubMed Central

Kim, Sae-Hoon; Park, Da-Eun; Lee, Hyun-Seung; Kang, Hye-Ryun; Cho, Sang-Heon

2014-01-01

Background Epidemiologic clinical studies suggested that chronic exposure to chlorine products is associated with development of asthma and aggravation of asthmatic symptoms. However, its underlying mechanism was not clearly understood. Studies were undertaken to define the effects and mechanisms of chronic low-dose chlorine exposure in the pathogenesis of airway inflammation and airway hyperresponsiveness (AHR). Methods Six week-old female BALB/c mice were sensitized and challenged with OVA in the presence and absence of chronic low dose chlorine exposure of naturally vaporized gas of 5% sodium hypochlorite solution. Airway inflammation and AHR were evaluated by bronchoalveolar lavage (BAL) cell recovery and non-invasive phlethysmography, respectively. Real-time qPCR, Western blot assay, and ELISA were used to evaluate the mRNA and protein expressions of cytokines and other inflammatory mediators. Human A549 and murine epithelial (A549 and MLE12) and macrophage (AMJ2-C11) cells were used to define the responses to low dose chlorine exposure in vitro. Results Chronic low dose chlorine exposure significantly augmented airway inflammation and AHR in OVA-sensitized and challenged mice. The expression of Th2 cytokines IL-4 and IL-5 and proinflammatory cytokine IL-1β and IL-33 were significantly increased in OVA/Cl group compared with OVA group. The chlorine exposure also activates the major molecules associated with inflammasome pathway in the macrophages with increased expression of epithelial alarmins IL-33 and TSLP in vitro. Conclusion Chronic low dose exposure of chlorine aggravates allergic Th2 inflammation and AHR potentially through activation of inflammasome danger signaling pathways. PMID:25202911

Persistent sub-lethal chlorine exposure augments temperature induced immunosuppression in Cyprinus carpio advanced fingerlings.

PubMed

Verma, A K; Pal, A K; Manush, S M; Das, T; Dalvi, R S; Chandrachoodan, P P; Ravi, P M; Apte, S K

2007-05-01

Apart from increased temperature, thermal effluents discharged through cooling systems of nuclear power plants may often contain chlorine (used against bio-fouling), which may affect the immune status of fish. Therefore, a 28-day trial was undertaken to delineate the effect of high temperature and a persistent sub-lethal chlorine exposure on immunomodulation in Cyprinus carpio advanced fingerlings. Fish were acclimated to four different temperatures (26, 31, 33 and 36 degrees C) and maintained for 30 days in two different groups. One group was exposed to persistent chlorine (0.1mgL(-1)) and was compared with their respective temperature control groups (without chlorine exposure). Expression of heat shock proteins (hsp 70) was tested in muscle after 28 days using Western blotting. Haematological parameters (erythrocyte count, leucocyte count, haemoglobin), serum parameters (total protein, albumin, globulin, A/G ratio) and respiratory burst activity were tested to assess immuno-competence of C. carpio in response to temperature and chlorine exposure. Results indicated that hsp 70 was induced at 36 degrees C in temperature control groups but not in their respective temperatures in the presence of chlorine. Haematological parameters such as haemoglobin, erythrocyte and leucocyte counts appeared depressed in chlorine treated groups as compared to their respective temperature control groups. Serum protein and globulin were affected due to chlorine exposure at different acclimation temperatures. A decrease in NBT activity was recorded in chlorine treated groups as compared to their respective temperature control groups. Overall results indicate that increasing acclimation temperatures alters the immune status of C. carpio advanced fingerlings and persistent sub-lethal exposure to chlorine augments this temperature induced immunosuppression.

Mutagenic activity associated with by-products of drinking water disinfection by chlorine, chlorine dioxide, ozone and UV-irradiation.

PubMed Central

Zoeteman, B C; Hrubec, J; de Greef, E; Kool, H J

1982-01-01

A retrospective epidemiological study in The Netherlands showed a statistical association between chlorination by-products in drinking water and cancer of the esophagus and stomach for males. A pilot-plant study with alternative disinfectants was carried out with stored water of the Rivers Rhine and Meuse. It was demonstrated that the increase of direct acting mutagens after treatment with chlorine dioxide is similar to the effect of chlorination. Ozonation of Rhine water reduced the mutagenic activity for Salmonella typhimurium TA 98 both with and without metabolic activation. UV alone hardly affects the mutagenicity of the stored river water for S. typh. TA 98. In all studies, practically no mutagenic activity for S. typh. TA 100 was found. Although remarkable changes in the concentration of individual organic compounds are reported, the identity of the mutagens detected is yet unclear. Compounds of possible interest due to their removal by ozonation are 1,3,3-trimethyloxindole, dicyclopentadiene and several alkylquinolines. Compounds which might be responsible for the increased mutagenicity after chlorination are two brominated acetonitriles and tri(2-chlorethyl) phosphate. Furthermore, the concentration procedure with adsorption on XAD resin and the subsequent elution step may have affected the results. It is proposed to focus further research more on the less volatile by-products of disinfection than on the trihalomethanes. PMID:7151762

IN-FLIGHT CAPTURE OF ELEMENTAL MERCURY BY A CHLORINE-IMPREGNATED ACTIVATED CARBON

EPA Science Inventory

The paper discusses the in-flight capture of elemental mercury (Hgo) by a chlorine (C1)-impregnated activated carbon. Efforts to develop sorbents for the control of Hg emissions have demonstrated that C1-impregnation of virgin activated carbons using dilute solutions of hydrogen ...

Large-eddy simulations of a solid-rocket booster jet

NASA Astrophysics Data System (ADS)

Paoli, Roberto; Poubeau, Adele; Cariolle, Daniel

2014-11-01

Emissions from solid-rocket boosters are responsible for a severe decrease in ozone concentration in the rocket plume during the first hours after a launch. The main source of ozone depletion is due to hydrogen chloride that is converted into chlorine in the high temperature regions of the jet (afterburning). The objective of this study is to evaluate the active chlorine concentration in the plume of a solid-rocket booster using large-eddy simulations. The gas is injected through the entire nozzle of the booster and a local time-stepping method based on coupling multi-instances of a fluid solver is used to extend the computational domain up to 600 nozzle exit diameters. The methodology is validated for a non-reactive case by analyzing the flow characteristics of supersonic co-flowing under expanded jets. Then, the chemistry of chlorine is studied offline using a complex chemistry solver and the LES data extracted from the mean trajectories of sample fluid particles. Finally, the online chemistry is analyzed by means of the multispecies version of the LES solver using a reduced chemistry scheme. The LES are able to capture the mixing of the exhaust with ambient air and the species concentrations, which is also useful to initialize atmospheric simulations on larger domains.

Volatile and organic compositions of sedimentary rocks in Yellowknife Bay, Gale crater, Mars.

PubMed

Ming, D W; Archer, P D; Glavin, D P; Eigenbrode, J L; Franz, H B; Sutter, B; Brunner, A E; Stern, J C; Freissinet, C; McAdam, A C; Mahaffy, P R; Cabane, M; Coll, P; Campbell, J L; Atreya, S K; Niles, P B; Bell, J F; Bish, D L; Brinckerhoff, W B; Buch, A; Conrad, P G; Des Marais, D J; Ehlmann, B L; Fairén, A G; Farley, K; Flesch, G J; Francois, P; Gellert, R; Grant, J A; Grotzinger, J P; Gupta, S; Herkenhoff, K E; Hurowitz, J A; Leshin, L A; Lewis, K W; McLennan, S M; Miller, K E; Moersch, J; Morris, R V; Navarro-González, R; Pavlov, A A; Perrett, G M; Pradler, I; Squyres, S W; Summons, R E; Steele, A; Stolper, E M; Sumner, D Y; Szopa, C; Teinturier, S; Trainer, M G; Treiman, A H; Vaniman, D T; Vasavada, A R; Webster, C R; Wray, J J; Yingst, R A

2014-01-24

H2O, CO2, SO2, O2, H2, H2S, HCl, chlorinated hydrocarbons, NO, and other trace gases were evolved during pyrolysis of two mudstone samples acquired by the Curiosity rover at Yellowknife Bay within Gale crater, Mars. H2O/OH-bearing phases included 2:1 phyllosilicate(s), bassanite, akaganeite, and amorphous materials. Thermal decomposition of carbonates and combustion of organic materials are candidate sources for the CO2. Concurrent evolution of O2 and chlorinated hydrocarbons suggests the presence of oxychlorine phase(s). Sulfides are likely sources for sulfur-bearing species. Higher abundances of chlorinated hydrocarbons in the mudstone compared with Rocknest windblown materials previously analyzed by Curiosity suggest that indigenous martian or meteoritic organic carbon sources may be preserved in the mudstone; however, the carbon source for the chlorinated hydrocarbons is not definitively of martian origin.

Validating the efficacy of peracetic acid mixture as an antimicrobial in poultry chillers.

PubMed

Bauermeister, Laura J; Bowers, Jordan W J; Townsend, Julie C; McKee, Shelly R

2008-06-01

Peracetic acid mixture (PAHP), which is a combination of peracetic acid and hydrogen peroxide, has been approved as an antimicrobial for use in poultry chillers. To validate its effectiveness, 85 ppm of PAHP was compared with the 30-ppm chlorine treatment in a commercial setting. In this trial, 100 carcasses were sampled for Salmonella and Campylobacter spp. prior to chilling and 100 carcasses were sampled after chilling. In all, 400 carcasses were sampled using 85 ppm of PAHP in the chiller and 400 carcasses were sampled using the chlorine treatment. PAHP at 85 ppm reduced Salmonella-positive carcasses by 92% exiting the chiller, whereas treatment with 30 ppm of chlorine reduced Salmonella by 57%. Additionally, PAHP reduced Campylobacter species-positive carcasses exiting the chiller by 43% while chlorine resulted in a 13% reduction. These results suggest that peracetic acid in combination with hydrogen peroxide may be an effective antimicrobial in poultry chiller applications.

Volatile and organic compositions of sedimentary rocks in Yellowknife Bay, Gale crater, Mars

USGS Publications Warehouse

Ming, D. W.; Archer, P.D.; Glavin, D.P.; Eigenbrode, J.L.; Franz, H.B.; Sutter, B.; Brunner, A.E.; Stern, J.C.; Freissinet, C.; McAdam, A.C.; Mahaffy, P.R.; Cabane, M.; Coll, P.; Campbell, J.L.; Atreya, S.K.; Niles, P.B.; Bell, J.F.; Bish, D.L.; Brinckerhoff, W.B.; Buch, A.; Conrad, P.G.; Des Marais, D.J.; Ehlmann, B.L.; Fairén, A.G.; Farley, K.; Flesch, G.J.; Francois, P.; Gellert, Ralf; Grant, J. A.; Grotzinger, J.P.; Gupta, S.; Herkenhoff, K. E.; Hurowitz, J.A.; Leshin, L.A.; Lewis, K.W.; McLennan, S.M.; Miller, Karl E.; Moersch, J.; Morris, R.V.; Navarro- González, R.; Pavlov, A.A.; Perrett, G.M.; Pradler, I.; Squyres, S. W.; Summons, Roger E.; Steele, A.; Stolper, E.M.; Sumner, D.Y.; Szopa, C.; Teinturier, S.; Trainer, M.G.; Treiman, A.H.; Vaniman, D.T.; Vasavada, A.R.; Webster, C.R.; Wray, J.J.; Yingst, R.A.

2014-01-01

H2O, CO2, SO2, O2, H2, H2S, HCl, chlorinated hydrocarbons, NO, and other trace gases were evolved during pyrolysis of two mudstone samples acquired by the Curiosity rover at Yellowknife Bay within Gale crater, Mars. H2O/OH-bearing phases included 2:1 phyllosilicate(s), bassanite, akaganeite, and amorphous materials. Thermal decomposition of carbonates and combustion of organic materials are candidate sources for the CO2. Concurrent evolution of O2 and chlorinated hydrocarbons suggests the presence of oxychlorine phase(s). Sulfides are likely sources for sulfur-bearing species. Higher abundances of chlorinated hydrocarbons in the mudstone compared with Rocknest windblown materials previously analyzed by Curiosity suggest that indigenous martian or meteoritic organic carbon sources may be preserved in the mudstone; however, the carbon source for the chlorinated hydrocarbons is not definitively of martian origin.

Characterization of the products formed by the reaction of trichlorocyanuric acid with 2-propanol.

PubMed

Sandercock, P Mark L; Barnett, Julie S

2009-11-01

We report a recent investigation into the death of a cat that was initially thought to involve intentionally burning the animal via the use of an ignitable liquid. The exposure of the animal to flame was ruled out. Instead, forensic investigation revealed the intentional mixing together of a common outdoor swimming pool chlorinator, trichlorocyanuric acid (TCCA), and 2-propanol (aka, isopropyl alcohol or rubbing alcohol). The reaction of these two chemicals resulted in the formation of cyanuric acid residue, hydrochloric acid, and the evolution of a significant volume of chlorine gas. Further alpha-chlorination side reactions also occurred between 2-propanol and TCCA to produce a variety of chlorinated 2-propanone species that were detected on the submitted evidence. The identification of the products of both the main reaction and the side reactions allowed the authors to determine what chemicals were originally mixed together by the culprit.

Reactivity of BrCl, Br₂, BrOCl, Br₂O, and HOBr toward dimethenamid in solutions of bromide + aqueous free chlorine.

PubMed

Sivey, John D; Arey, J Samuel; Tentscher, Peter R; Roberts, A Lynn

2013-02-05

HOBr, formed via oxidation of bromide by free available chlorine (FAC), is frequently assumed to be the sole species responsible for generating brominated disinfection byproducts (DBPs). Our studies reveal that BrCl, Br(2), BrOCl, and Br(2)O can also serve as brominating agents of the herbicide dimethenamid in solutions of bromide to which FAC was added. Conditions affecting bromine speciation (pH, total free bromine concentration ([HOBr](T)), [Cl(-)], and [FAC](o)) were systematically varied, and rates of dimethenamid bromination were measured. Reaction orders in [HOBr](T) ranged from 1.09 (±0.17) to 1.67 (±0.16), reaching a maximum near the pK(a) of HOBr. This complex dependence on [HOBr](T) implicates Br(2)O as an active brominating agent. That bromination rates increased with increasing [Cl(-)], [FAC](o) (at constant [HOBr](T)), and excess bromide (where [Br(-)](o)>[FAC](o)) implicate BrCl, BrOCl, and Br(2), respectively, as brominating agents. As equilibrium constants for the formation of Br(2)O and BrOCl (aq) have not been previously reported, we have calculated these values (and their gas-phase analogues) using benchmark-quality quantum chemical methods [CCSD(T) up to CCSDTQ calculations plus solvation effects]. The results allow us to compute bromine speciation and hence second-order rate constants. Intrinsic brominating reactivity increased in the order: HOBr ≪ Br(2)O < BrOCl ≈ Br(2) < BrCl. Our results indicate that species other than HOBr can influence bromination rates under conditions typical of drinking water and wastewater chlorination.

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

PubMed

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.

Genotoxic properties of haloacetonitriles: drinking water by-products of chlorine disinfection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daniel, F.B.; Schenck, K.M.; Mattox, J.K.

Chlorinated and brominated haloacetonitriles (HAN), known drinking water contaminants which form during chlorine disinfection, were investigated for genotoxic activity. The HAN produced DNA strand breaks in cultured human lymphoblastic (CCRF-CEM) cells, bound to the nucleophilic trapping agent 4-(p-nitrobenzyl)pyridine and formed a covalent bond to polyadenylic acid in a cell-free reaction system. Thus, we have demonstrated that these chemicals are genotoxic, which would indicate a potential for carcinogenic activity and for human health hazard.

Disinfection byproduct formation in drinking water sources: A case study of Yuqiao reservoir.

PubMed

Zhai, Hongyan; He, Xizhen; Zhang, Yan; Du, Tingting; Adeleye, Adeyemi S; Li, Yao

2017-08-01

This study investigated the potential formation of disinfection byproducts (DBPs) during chlorination and chloramination of 20 water samples collected from different points of Yuqiao reservoir in Tianjin, China. The concentrations of dissolved organic matter and ammonia decreased downstream the reservoir, while the specific UV absorbance (SUVA: the ratio of UV 254 to dissolved organic carbon) increased [from 0.67 L/(mg*m) upstream to 3.58 L/(mg*m) downstream]. The raw water quality played an important role in the formation of DBPs. During chlorination, haloacetic acids (HAAs) were the major DBPs formed in most of the water samples, followed by trihalomethanes (THMs). CHCl 3 and CHCl 2 Br were the major THM species, while trichloroacetic acid (TCAA) and dichloroacetic acid (DCAA) were the major HAA species. Chloramination, on the other hand, generally resulted in lower concentrations of THMs (CHCl 3 ), HAAs (TCAA and DCAA), and haloacetonitriles (HANs). All the species of DBPs formed had positive correlations with the SUVA values, and HANs had the highest one (R 2  = 0.8). The correlation coefficients between the analogous DBP yields and the SUVA values in chlorinated samples were close to those in chloraminated samples. Copyright © 2017 Elsevier Ltd. All rights reserved.

Legionella Contamination in Hot Water of Italian Hotels

PubMed Central

Borella, Paola; Montagna, Maria Teresa; Stampi, Serena; Stancanelli, Giovanna; Romano-Spica, Vincenzo; Triassi, Maria; Marchesi, Isabella; Bargellini, Annalisa; Tatò, Daniela; Napoli, Christian; Zanetti, Franca; Leoni, Erica; Moro, Matteo; Scaltriti, Stefania; Ribera D'Alcalà, Gabriella; Santarpia, Rosalba; Boccia, Stefania

2005-01-01

A cross-sectional multicenter survey of Italian hotels was conducted to investigate Legionella spp. contamination of hot water. Chemical parameters (hardness, free chlorine concentration, and trace element concentrations), water systems, and building characteristics were evaluated to study risk factors for colonization. The hot water systems of Italian hotels were strongly colonized by Legionella; 75% of the buildings examined and 60% of the water samples were contaminated, mainly at levels of ≥103 CFU liter−1, and Legionella pneumophila was the most frequently isolated species (87%). L. pneumophila serogroup 1 was isolated from 45.8% of the contaminated sites and from 32.5% of the hotels examined. When a multivariate logistic model was used, only hotel age was associated with contamination, but the risk factors differed depending on the contaminating species and serogroup. Soft water with higher chlorine levels and higher temperatures were associated with L. pneumophila serogroup 1 colonization, whereas the opposite was observed for serogroups 2 to 14. In conclusion, Italian hotels, particularly those located in old buildings, represent a major source of risk for Legionnaires' disease due to the high frequency of Legionella contamination, high germ concentration, and major L. pneumophila serogroup 1 colonization. The possible role of chlorine in favoring the survival of Legionella species is discussed. PMID:16204491

Legionella contamination in hot water of Italian hotels.

PubMed

Borella, Paola; Montagna, Maria Teresa; Stampi, Serena; Stancanelli, Giovanna; Romano-Spica, Vincenzo; Triassi, Maria; Marchesi, Isabella; Bargellini, Annalisa; Tatò, Daniela; Napoli, Christian; Zanetti, Franca; Leoni, Erica; Moro, Matteo; Scaltriti, Stefania; Ribera D'Alcalà, Gabriella; Santarpia, Rosalba; Boccia, Stefania

2005-10-01

A cross-sectional multicenter survey of Italian hotels was conducted to investigate Legionella spp. contamination of hot water. Chemical parameters (hardness, free chlorine concentration, and trace element concentrations), water systems, and building characteristics were evaluated to study risk factors for colonization. The hot water systems of Italian hotels were strongly colonized by Legionella; 75% of the buildings examined and 60% of the water samples were contaminated, mainly at levels of > or =10(3) CFU liter(-1), and Legionella pneumophila was the most frequently isolated species (87%). L. pneumophila serogroup 1 was isolated from 45.8% of the contaminated sites and from 32.5% of the hotels examined. When a multivariate logistic model was used, only hotel age was associated with contamination, but the risk factors differed depending on the contaminating species and serogroup. Soft water with higher chlorine levels and higher temperatures were associated with L. pneumophila serogroup 1 colonization, whereas the opposite was observed for serogroups 2 to 14. In conclusion, Italian hotels, particularly those located in old buildings, represent a major source of risk for Legionnaires' disease due to the high frequency of Legionella contamination, high germ concentration, and major L. pneumophila serogroup 1 colonization. The possible role of chlorine in favoring the survival of Legionella species is discussed.

Establishment of a Polychlorinated Biphenyl-Dechlorinating Microbial Consortium, Specific for Doubly Flanked Chlorines, in a Defined, Sediment-Free Medium

PubMed Central

Wu, Qingzhong; Sowers, Kevin R.; May, Harold D.

2000-01-01

Estuarine sediment from Charleston Harbor, South Carolina, was used as inoculum for the development of an anaerobic enrichment culture that specifically dechlorinates doubly flanked chlorines (i.e., chlorines bound to carbon that are flanked on both sides by other chlorine-carbon bonds) of polychlorinated biphenyls (PCBs). Dechlorination was restricted to the para chlorine in cultures enriched with 10 mM fumarate, 50 ppm (173 μM) 2,3,4,5-tetrachlorobiphenyl, and no sediment. Initially the rate of dechlorination decreased upon the removal of sediment from the medium. However, the dechlorinating activity was sustainable, and following sequential transfer in a defined, sediment-free estuarine medium, the activity increased to levels near that observed with sediment. The culture was nonmethanogenic, and molybdate, ampicillin, chloramphenicol, neomycin, and streptomycin inhibited dechlorination activity; bromoethanesulfonate and vancomycin did not. Addition of 17 PCB congeners indicated that the culture specifically removes double flanked chlorines, preferably in the para position, and does not attack ortho chlorines. This is the first microbial consortium shown to para or meta dechlorinate a PCB congener in a defined sediment-free medium. It is the second PCB-dechlorinating enrichment culture to be sustained in the absence of sediment, but its dechlorinating capabilities are entirely different from those of the other sediment-free PCB-dechlorinating culture, an ortho-dechlorinating consortium, and do not match any previously published Aroclor-dechlorinating patterns. PMID:10618202

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sobes, Vladimir; Scaglione, John M; Wagner, John C

Spent nuclear fuel (SNF) management practices in the United States rely on dry storage systems that include both canister- and cask-based systems. The United States Department of Energy Used Fuel Disposition Campaign is examining the feasibility of direct disposal of dual-purpose (storage and transportation) canisters (DPCs) in a geological repository. One of the major technical challenges for direct disposal is the ability to demonstrate the subcriticality of the DPCs loaded with SNF for the repository performance period (e.g., 10,000 years or more) as the DPCs may undergo degradation over time. Specifically, groundwater ingress into the DPC (i.e., flooding) could allowmore » the system to achieve criticality in scenarios where the neutron absorber plates in the DPC basket have degraded. However, as was shown by Banerjee et al., some aqueous species in the groundwater provide noticeable reactivity reduction for these systems. For certain amounts of particular aqueous species (e.g., chlorine, lithium) in the groundwater, subcriticality can be demonstrated even for DPCs with complete degradation of the neutron absorber plates or a degraded fuel basket configuration. It has been demonstrated that chlorine is the leading impurity, as indicated by significant neutron absorption in the water that is available in reasonable quantities for the deep geological repository media under consideration. This paper presents the results of an investigation of the available integral experiments worldwide that could be used to validate DPC disposal criticality evaluations, including credit for chlorine. Due to the small number of applicable critical configurations, validation through traditional trending analysis was not possible. The bias in the eigenvalue of the application systems due only to the chlorine was calculated using TSURFER analysis and found to be on the order of 100 percent mille (1 pcm = 10 -5 k eff). This study investigated the design of a series of critical configurations with varying amounts of chlorine to address validation gaps. Such integral experiments would support the crediting of the chlorine neutron-absorption properties in groundwater and the demonstration of subcriticality for DPCs in deep geologic repositories with sufficient chlorine availability.« less

Gasification Characteristics and Kinetics of Coke with Chlorine Addition

NASA Astrophysics Data System (ADS)

Wang, Cui; Zhang, Jianliang; Jiao, Kexin; Liu, Zhengjian; Chou, Kuochih

2017-10-01

The gasification process of metallurgical coke with 0, 1.122, 3.190, and 7.132 wt pct chlorine was investigated through thermogravimetric method from ambient temperature to 1593 K (1320 °C) in purified CO2 atmosphere. The variations in the temperature parameters that T i decreases gradually with increasing chlorine, T f and T max first decrease and then increase, but both in a downward trend indicated that the coke gasification process was catalyzed by the chlorine addition. Then the kinetic model of the chlorine-containing coke gasification was obtained through the advanced determination of the average apparent activation energy, the optimal reaction model, and the pre-exponential factor. The average apparent activation energies were 182.962, 118.525, 139.632, and 111.953 kJ/mol, respectively, which were in the same decreasing trend with the temperature parameters analyzed by the thermogravimetric method. It was also demonstrated that the coke gasification process was catalyzed by chlorine. The optimal kinetic model to describe the gasification process of chlorine-containing coke was the Šesták Berggren model using Málek's method, and the pre-exponential factors were 6.688 × 105, 2.786 × 103, 1.782 × 104, and 1.324 × 103 min-1, respectively. The predictions of chlorine-containing coke gasification from the Šesták Berggren model were well fitted with the experimental data.

Reaction kinetics and transformation of carbadox and structurally related compounds with aqueous chlorine.

PubMed

Shah, Amisha D; Kim, Jae-Hong; Huang, Ching-Hua

2006-12-01

The potential release of carbadox (CDX), a commonly used antibacterial agent in swine husbandry, into water systems is of a concern due to its carcinogenic and genotoxic effects. Until this study, the reactivity of carbadox (possessing quinoxaline N,N'-dioxide and hydrazone moieties) toward aqueous chlorine has yetto be investigated in depth. Chemical reactivity, reaction kinetics, and transformation pathways of carbadox and structurally related compounds with free chlorine under typical water treatment conditions were determined. This study found that only CDX and desoxycarbadox (DCDX), a main metabolite of CDX with no ring N-oxide groups, react rapidly with free chlorine while other structurally related compounds including olaquindox, quindoxin, quinoxaline N-oxide, quinoxaline, and quinoline N-oxide do not. The reaction kinetics of CDX and DCDX with chlorine are highly pH dependent (e.g., the apparent second-order rate constant, kapp, for CDX ranges from 51.8 to 3.15 x 10(4) M(-1)s(-1) at pH 4-11). The high reactivity of CDX and DCDX to chlorine involves deprotonation of their hydrazone N-H moieties where initial chlorine attack results in a reactive intermediate that is further attacked by nucleophiles in the matrix to yield non-chlorinated, hydroxylated, and larger molecular weight byproducts. All of the CDX's byproducts retain their biologically active N-oxide groups, suggesting that they may remain as active antibacterial agents.

Chloride and organic chlorine in forest soils: storage, residence times, and influence of ecological conditions.

PubMed

Redon, Paul-Olivier; Abdelouas, Abdesselam; Bastviken, David; Cecchini, Sébastien; Nicolas, Manuel; Thiry, Yves

2011-09-01

Recent studies have shown that extensive chlorination of natural organic matter significantly affects chlorine (Cl) residence time in soils. This natural biogeochemical process must be considered when developing the conceptual models used as the basis for safety assessments regarding the potential health impacts of 36-chlorine released from present and planned radioactive waste disposal facilities. In this study, we surveyed 51 French forested areas to determine the variability in chlorine speciation and storage in soils. Concentrations of total chlorine (Cl(tot)) and organic chlorine (Cl(org)) were determined in litterfall, forest floor and mineral soil samples. Cl(org) constituted 11-100% of Cl(tot), with the highest concentrations being found in the humus layer (34-689 mg Cl(org) kg(-1)). In terms of areal storage (53 - 400 kg Cl(org) ha(-1)) the mineral soil dominated due to its greater thickness (40 cm). Cl(org) concentrations and estimated retention of organochlorine in the humus layer were correlated with Cl input, total Cl concentration, organic carbon content, soil pH and the dominant tree species. Cl(org) concentration in mineral soil was not significantly influenced by the studied environmental factors, however increasing Cl:C ratios with depth could indicate selective preservation of chlorinated organic molecules. Litterfall contributions of Cl were significant but generally minor compared to other fluxes and stocks. Assuming steady-state conditions, known annual wet deposition and measured inventories in soil, the theoretical average residence time calculated for total chlorine (inorganic (Cl(in)) and organic) was 5-fold higher than that estimated for Cl(in) alone. Consideration of the Cl(org) pool is therefore clearly important in studies of overall Cl cycling in terrestrial ecosystems.

Palliative effects of H2 on SOFCs operating with carbon containing fuels

NASA Astrophysics Data System (ADS)

Reeping, Kyle W.; Bohn, Jessie M.; Walker, Robert A.

2017-12-01

Chlorine can accelerate degradation of solid oxide fuel cell (SOFC) Ni-based anodes operating on carbon containing fuels through several different mechanisms. However, supplementing the fuel with a small percentage of excess molecular hydrogen effectively masks the degradation to the catalytic activity of the Ni and carbon fuel cracking reaction reactions. Experiments described in this work explore the chemistry behind the "palliative" effect of hydrogen on SOFCs operating with chlorine-contaminated, carbon-containing fuels using a suite of independent, complementary techniques. Operando Raman spectroscopy is used to monitor carbon accumulation and, by inference, Ni catalytic activity while electrochemical techniques including electrochemical impedance spectroscopy and voltammetry are used to monitor overall cell performance. Briefly, hydrogen not only completely hides degradation observed with chlorine-contaminated carbon-containing fuels, but also actively removes adsorbed chlorine from the surface of the Ni, allowing for the methane cracking reaction to continue, albeit at a slower rate. When hydrogen is removed from the fuel stream the cell fails immediately due to chlorine occupation of methane/biogas reaction sites.

New Insight into Polar Stratospheric Cloud Processes from A-Train Observations

NASA Astrophysics Data System (ADS)

Pitts, M. C.; Poole, L. R.

2016-12-01

Polar stratospheric clouds (PSCs) play essential roles in the chemical depletion of stratospheric ozone at high latitudes. Heterogeneous reactions occurring on PSC particles, primarily supercooled ternary (H2SO4-H2O-HNO3) solution (STS) droplets, convert stable chlorine reservoir species to highly reactive ozone-destructive forms. Also, sedimentation and evaporation of large nitric acid trihydrate (NAT) particles irreversibly redistributes odd nitrogen and prolongs ozone depletion by slowing the reformation of stable chlorine reservoirs. Even after three decades of research, significant gaps in our understanding of PSC processes still exist, particularly concerning NAT nucleation and the extent to which chlorine is activated on cold background aerosol prior to PSC formation. These uncertainties limit our ability to represent PSCs accurately in global models and call into question predictions of ozone recovery in a changing climate. PSC observations from the A-Train satellite constellation have stimulated a number of new research activities that have both extended and challenged our knowledge of PSC processes and modeling capabilities. Specifically, the CALIOP (Cloud-Aerosol Lidar with Orthogonal Polarization) lidar on the CALIPSO (Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations) satellite is providing information on PSC morphology and composition in unprecedented detail, while the Microwave Limb Sounder (MLS) on the Aura satellite is providing nearly coincident measurements of gas-phase HNO3 and H2O, the major constituents of all PSC particles. The combined analyses of these datasets enable better PSC composition discrimination and provide valuable new insight into processes such as PSC-catalyzed chlorine activation and PSC particle growth kinetics. The more than ten years of CALIOP and MLS measurements have uniquely captured the primary aspects of the seasonal and multi-year variability of PSCs in the Arctic and Antarctic and are enabling the development of a state-of-the-art reference PSC data record and climatology which can be utilized to test current and future global models. In this paper, we will illustrate key features of this evolving PSC climatology and highlight recent significant findings with regard to PSC processes in the Arctic and Antarctic.

40 CFR 142.60 - Variances from the maximum contaminant level for total trihalomethanes.

Code of Federal Regulations, 2011 CFR

2011-07-01

... disinfectant or oxidant. (2) Use of chlorine dioxide as an alternate or supplemental disinfectant or oxidant... to reduce TTHM formation and, where necessary, substituting for the use of chlorine as a pre-oxidant chloramines, chlorine dioxide or potassium permanganate. (5) Use of powdered activated carbon for THM...

ASCORBIC ACID REDUCTION OF ACTIVE CHLORINE PRIOR TO DETERMINING AMES MUTAGENICITY OF CHLORINATED NATURAL ORGANIC MATTER (NOM)

EPA Science Inventory

Many potable water disinfection byproducts (DBPs) that result from the reaction of natural organic matter (NOM) with oxidizing chlorine are known or suspected to be carcinogenic and mutagenic. The Ames assay is routinely used to assess an overall level of mutagenicity for all com...

Reaction of bromine and chlorine with phenolic compounds and natural organic matter extracts--Electrophilic aromatic substitution and oxidation.

PubMed

Criquet, Justine; Rodriguez, Eva M; Allard, Sebastien; Wellauer, Sven; Salhi, Elisabeth; Joll, Cynthia A; von Gunten, Urs

2015-11-15

Phenolic compounds are known structural moieties of natural organic matter (NOM), and their reactivity is a key parameter for understanding the reactivity of NOM and the disinfection by-product formation during oxidative water treatment. In this study, species-specific and/or apparent second order rate constants and mechanisms for the reactions of bromine and chlorine have been determined for various phenolic compounds (phenol, resorcinol, catechol, hydroquinone, phloroglucinol, bisphenol A, p-hydroxybenzoic acid, gallic acid, hesperetin and tannic acid) and flavone. The reactivity of bromine with phenolic compounds is very high, with apparent second order rate constants at pH 7 in the range of 10(4) to 10(7) M(-1) s(-1). The highest value was recorded for the reaction between HOBr and the fully deprotonated resorcinol (k = 2.1 × 10(9) M(-1) s(-1)). The reactivity of phenolic compounds is enhanced by the activating character of the phenolic substituents, e.g. further hydroxyl groups. With the data set from this study, the ratio between the species-specific rate constants for the reactions of chlorine versus bromine with phenolic compounds was confirmed to be about 3000. Phenolic compounds react with bromine or chlorine either by oxidation (electron transfer, ET) or electrophilic aromatic substitution (EAS) processes. The dominant process mainly depends on the relative position of the hydroxyl substituents and the possibility of quinone formation. While phenol, p-hydroxybenzoic acid and bisphenol A undergo EAS, hydroquinone, catechol, gallic acid and tannic acid, with hydroxyl substituents in ortho or para positions, react with bromine by ET leading to quantitative formation of the corresponding quinones. Some compounds (e.g. phloroglucinol) show both partial oxidation and partial electrophilic aromatic substitution and the ratio observed for the pathways depends on the pH. For the reaction of six NOM extracts with bromine, electrophilic aromatic substitution accounted for only 20% of the reaction, and for one NOM extract (Pony Lake fulvic acid) it accounted for <10%. This shows that for natural organic matter samples, oxidation (ET) is far more important than bromine incorporation (EAS). Copyright © 2015 Elsevier Ltd. All rights reserved.

ACE-FTS and MIPAS observations of phosgene (COCl2) and comparisons with SLIMCAT chemical transport model calculations

NASA Astrophysics Data System (ADS)

Harrison, Jeremy; Chipperfield, Martyn; Moore, David; Boone, Christopher; Bernath, Peter; Hossaini, Ryan

2017-04-01

The majority of chlorine in the atmosphere has arisen from anthropogenic emissions of 'organic' species such as chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). Due to their long lifetimes, many of these species reach the stratosphere where they break down, liberating chlorine which catalyses the destruction of ozone. The principal degradation products of Cl-containing organic species are carbonyl chloride (phosgene, COCl2), carbonyl chloride fluoride (COClF), and hydrogen chloride (HCl). Of these, phosgene is probably the most notorious, having been used as a chemical weapon in World War I. In the lower stratosphere, where the phosgene mixing ratios peak, the principal sources are the photolysis of carbon tetrachloride (CCl4) and, to a lesser extent, methyl chloroform (CH3CCl3). Smaller contributions arise from very short-lived substances such as CH2Cl2, CHCl3 and C2Cl4. Due to the success of the Montreal Protocol in phasing out the use of CCl4 and CH3CCl3, the abundance of phosgene continues to fall. Observing and understanding phosgene in the stratosphere helps us better understand the chlorine budget, and particularly the atmospheric removal of CCl4, which has attracted particular interest recently on account of the inconsistency between observations of its abundance and estimated sources and sinks. This work presents global distributions and trends of COCl2 using data from two satellite limb instruments: the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS), and the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS). The ACE-FTS instrument, on board the SCISAT satellite, has been recording solar occultation spectra through the Earth's atmosphere since 2004 and continues to take measurements with only minor loss in performance. ACE-FTS time series are available for a range of chlorine 'source' gases, including CCl3F (CFC-11), CCl2F2 (CFC-12), CHF2Cl (HCFC-22) and CCl4, and the chlorine 'product' gases COCl2, COClF and HCl. The MIPAS instrument, onboard ENVISAT (ENVIronmental SATellite), recorded atmospheric limb emissions spectra between 2002 and 2012, with time series available for the key Cl-containing species except HCl. ACE-FTS and MIPAS phosgene observations are compared with the output of SLIMCAT, a state-of-the-art offline three-dimensional chemical transport model (CTM), which contains a detailed treatment of stratospheric chemistry, including the major species in the Ox, NOy, HOx, Fy, Cly, and Bry chemical families.

TRPA1 is a major oxidant sensor in murine airway sensory neurons

PubMed Central

Bessac, Bret F.; Sivula, Michael; von Hehn, Christian A.; Escalera, Jasmine; Cohn, Lauren; Jordt, Sven-Eric

2008-01-01

Sensory neurons in the airways are finely tuned to respond to reactive chemicals threatening airway function and integrity. Nasal trigeminal nerve endings are particularly sensitive to oxidants formed in polluted air and during oxidative stress as well as to chlorine, which is frequently released in industrial and domestic accidents. Oxidant activation of airway neurons induces respiratory depression, nasal obstruction, sneezing, cough, and pain. While normally protective, chemosensory airway reflexes can provoke severe complications in patients affected by inflammatory airway conditions like rhinitis and asthma. Here, we showed that both hypochlorite, the oxidizing mediator of chlorine, and hydrogen peroxide, a reactive oxygen species, activated Ca2+ influx and membrane currents in an oxidant-sensitive subpopulation of chemosensory neurons. These responses were absent in neurons from mice lacking TRPA1, an ion channel of the transient receptor potential (TRP) gene family. TRPA1 channels were strongly activated by hypochlorite and hydrogen peroxide in primary sensory neurons and heterologous cells. In tests of respiratory function, Trpa1–/– mice displayed profound deficiencies in hypochlorite- and hydrogen peroxide–induced respiratory depression as well as decreased oxidant-induced pain behavior. Our results indicate that TRPA1 is an oxidant sensor in sensory neurons, initiating neuronal excitation and subsequent physiological responses in vitro and in vivo. PMID:18398506

Chlorinated Phospholipids and Fatty Acids: (Patho)physiological Relevance, Potential Toxicity, and Analysis of Lipid Chlorohydrins

PubMed Central

2016-01-01

Chlorinated phospholipids are formed by the reaction of hypochlorous acid (HOCl), generated by the enzyme myeloperoxidase under inflammatory conditions, and the unsaturated fatty acyl residues or the head group. In the first case the generated chlorohydrins are both proinflammatory and cytotoxic, thus having a significant impact on the structures of biomembranes. The latter case leads to chloramines, the properties of which are by far less well understood. Since HOCl is also widely used as a disinfecting and antibacterial agent in medicinal, industrial, and domestic applications, it may represent an additional source of danger in the case of abuse or mishandling. This review discusses the reaction behavior of in vivo generated HOCl and biomolecules like DNA, proteins, and carbohydrates but will focus on phospholipids. Not only the beneficial and pathological (toxic) effects of chlorinated lipids but also the importance of these chlorinated species is discussed. Some selected cleavage products of (chlorinated) phospholipids and plasmalogens such as lysophospholipids, (chlorinated) free fatty acids and α-chloro fatty aldehydes, which are all well known to massively contribute to inflammatory diseases associated with oxidative stress, will be also discussed. Finally, common analytical methods to study these compounds will be reviewed with focus on mass spectrometric techniques. PMID:28090245

Fast and Simple Analytical Method for Direct Determination of Total Chlorine Content in Polyglycerol by ICP-MS.

PubMed

Jakóbik-Kolon, Agata; Milewski, Andrzej; Dydo, Piotr; Witczak, Magdalena; Bok-Badura, Joanna

2018-02-23

The fast and simple method for total chlorine determination in polyglycerols using low resolution inductively coupled plasma mass spectrometry (ICP-MS) without the need for additional equipment and time-consuming sample decomposition was evaluated. Linear calibration curve for 35 Cl isotope in the concentration range 20-800 µg/L was observed. Limits of detection and quantification equaled to 15 µg/L and 44 µg/L, respectively. This corresponds to possibility of detection 3 µg/g and determination 9 µg/g of chlorine in polyglycerol using studied conditions (0.5% matrix-polyglycerol samples diluted or dissolved with water to an overall concentration of 0.5%). Matrix effects as well as the effect of chlorine origin have been evaluated. The presence of 0.5% (m/m) of matrix species similar to polyglycerol (polyethylene glycol-PEG) did not influence the chlorine determination for PEGs with average molecular weights (MW) up to 2000 Da. Good precision and accuracy of the chlorine content determination was achieved regardless on its origin (inorganic/organic). High analyte recovery level and low relative standard deviation values were observed for real polyglycerol samples spiked with chloride. Additionally, the Combustion Ion Chromatography System was used as a reference method. The results confirmed high accuracy and precision of the tested method.

International Symposium On the Ecological Effects of Arctic Airborne Contaminants, held in Reykjavik, Iceland on October 4 - 8, 1993. Abstracts

DTIC Science & Technology

1993-10-08

fluctuations occur, there appears to be a general increase in concentration of the lighter congener groups (two, three, and four chlorines) toward the...traditional diet in communities across the NWT. Caribou were collected from four herds in the first year of a study to examine levels of organo- chlorine...organochlorine pesticides, and PCBs. Results of variability studies comparing concentrations of target analytes in four species (Cetraria cucullata

Arctic chlorine activation and ozone depletion: Comparison of chemistry transport models with satellite observations.

NASA Astrophysics Data System (ADS)

Grooß, J.-U.; Wegner, T.; Müller, R.; Chipperfield, M. P.; Feng, W.; Santee, M. L.

2009-04-01

The accurate simulation of Arctic stratospheric ozone depletion has been an issue for two decades. However, there are still notable quantitative discrepancies between the models and observations. We show results from the SLIMCAT and CLaMS 3D chemistry-transport models that differ in some aspects of simulated chlorine activation and descent in the polar vortex. Consequently, the estimates of accumulated ozone depletion in the polar vortex for these two models in cold Arctic winters still largely disagree. As shown recently by Santee et al. (JGR, 2008) using MLS and ACE data, the extent of chlorine activation for the cold Arctic winter of 2004/2005 within the basic SLIMCAT model is overestimated with the likely consequence of too much simulated ozone depletion. In contrast, the CLaMS simulation for the same winter shows too little chlorine activation compared to observations, and therefore likely too little loss. For SLIMCAT the version used by Santee et al. has been updated to replace the equilibrium treatment of NAT PSCs with a Lagrangian microphysical scheme. This leads to smaller regions of NAT particles and less denitrification, in better agreement with observations. The impact of this on the modeled extent of chlorine activation will be discussed. For CLaMS we have changed the parameterization of heterogeneous reactions on liquid aerosols from Carslaw et al. to that of Shi et al. (2001), with which chlorine activation on liquid aerosol becomes more efficient. In turn, the simulated chlorine activation agrees better with the observations. The impact of these model changes on chlorine activation and ozone loss will be assessed and remaining model-observation discrepancies will be discussed in terms of different model formulations. We will also show the impact of recent lab measurements of Cl2O2 absorption cross sections by von Hobe et al. (2009) on the simulated ozone depletion. References: von Hobe, M., F. Stroh, H. Beckers, T. Benter, and H. Willner, The UV/Vis absorption spectrum of matrix isolated dichlorine peroxide, ClOOCl, Phys. Chem. Chem. Phys. , doi:10.1039/B814373K, 2009. Santee M. L., I. A. MacKenzie, G. L. Manney, M. P. Chipperfield, P. F. Bernath, K. A. Walker, C. D. Boone, L. Froidevaux, N. J. Livesey, J. W. Waters, A study of stratospheric chlorine partitioning based on new satellite measurements and modeling, J. Geophys. Res., 113, D12307, doi:10.1029/2007JD009057, 2008. Shi, Q., J. Jayne, C. Kolb, D. Worsnop, and P. Davidovits, Kinetic model for reaction of ClONO2 with H2O and HCl and HOCl with HCl in sulfuric acid solutions, J. Geophys. Res., 106, 24259-24274, 2001.

Chlorinated Hydrocarbon Degradation in Plants: Mechanisms and Enhancement of Phytoremediation of Groundwater Contamination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strand, Stuart E.

2002-06-01

Several varieties of transgenic poplar containing cytochrome P-450 2E1 have been constructed and are undergoing tests. Strategies for improving public acceptance and safety of transgenic poplar for chlorinated hydrocarbon phytoremediation are being developed. We have discovered a unique rhizobium species that lives within the stems of poplar and we are investigating whether this bacterium contributes nitrogen fixed from the air to the plant and whether this endophyte could be used to introduce genes into poplar. Studies of the production of chloride ion from TCE have shown that our present P-450 constructs did not produce chloride more rapidly than wild typemore » plants. Follow-up studies will determine if there are other rate limiting downstream steps in TCE metabolism in plants. Studies of the metabolism of carbon tetrachloride in poplar cells have provided evidence that the native plant metabolism is due to the activity of oxidative enzymes similar to the mammalian cytochrome P-450 2E1.« less

Wastewater injection, aquifer biogeochemical reactions, and resultant groundwater N fluxes to coastal waters: Kā'anapali, Maui, Hawai'i.

PubMed

Fackrell, Joseph K; Glenn, Craig R; Popp, Brian N; Whittier, Robert B; Dulai, Henrietta

2016-09-15

We utilize N and C species concentration data along with δ(15)N values of NO3(-) and δ(13)C values of dissolved inorganic C to evaluate the stoichiometry of biogeochemical reactions (mineralization, nitrification, anammox, and denitrification) occurring within a subsurface wastewater plume that originates as treated wastewater injection and enters the coastal waters of Maui as submarine groundwater discharge. Additionally, we compare wastewater effluent time-series data, injection rates, and treatment history with submarine spring discharge time-series data. We find that heterotrophic denitrification is the primary mechanism of N loss within the groundwater plume and that chlorination for pathogen disinfection suppresses microbial activity in the aquifer responsible for N loss, resulting in increased coastal ocean N loading. Replacement of chlorination with UV disinfection may restore biogeochemical reactions responsible for N loss within the aquifer and return N-attenuating conditions in the effluent plume, reducing N loading to coastal waters. Copyright © 2016 Elsevier Ltd. All rights reserved.

Disinfection by-products and microbial contamination in the treatment of pool water with granular activated carbon.

PubMed

Uhl, W; Hartmann, C

2005-01-01

For swimming pools, it is generally agreed that free chlorine levels have to be maintained to guarantee adequate disinfection. Recommended free chlorine levels can vary between 0.3 and 0.6 mg/L in Germany and up to 3 mg/L in other countries. Bathers introduce considerable amounts of organic matter, mainly in the form of such as urine and sweat, into the pool water. As a consequence, disinfection byproducts (DBPs) are formed. Regulations in Germany recommend levels of combined chlorine of less than 0.2 mg/L and levels of trihalomethanes (THMs) of less than 20 microg/L. Haloacetic acids (HAAs), haloacetonitriles (HANs), chloropicrin and chloral hydrate are also detected in considerable amounts. However, these compounds are not regulated yet. Swimming pool staff and swimmers, especially athletes, are primarily exposed to these byproducts by inhalation and/or dermal uptake. In Germany, new regulations for swimming pool water treatment generally require the use of activated carbon. In this project, three different types of granular activated carbon (GAC) (one standard GAC, two catalytic GACs) are compared for their long time behaviour in pool water treatment. In a pilot plant operated with real swimming pool water, production and removal of disinfection byproducts (THMs, HAAs, AOXs), of biodegradable substances (AOC), of bacteria (Pseudomonas aeruginosa, Legionella, coliforms, HPC) as well as the removal of chlorine and chloramines are monitored as function of GAC bed depth. Combined chlorine penetrates deeper in the filter bed than free chlorine does. However, both, free and combined chlorine removal efficiencies decrease over the time of filter operation. The decreases of removal efficiencies are also observed for parameters such as dissolved organic carbon, spectral absorption coefficient, adsorbable organic carbon and most of the disinfection byproducts. However, THMs, especially chloroform are produced in the filter bed. The GAC beds were contaminated microbially, especially with P. aeruginosa. The contamination was not removable by backwashing with chlorine concentrations up to 2 mg/l free chlorine.

Tyrosine 192 in apolipoprotein A-I is the major site of nitration and chlorination by myeloperoxidase, but only chlorination markedly impairs ABCA1-dependent cholesterol transport.

PubMed

Shao, Baohai; Bergt, Constanze; Fu, Xiaoyun; Green, Pattie; Voss, John C; Oda, Michael N; Oram, John F; Heinecke, Jay W

2005-02-18

High density lipoprotein (HDL) isolated from human atherosclerotic lesions and the blood of patients with established coronary artery disease contains elevated levels of 3-nitrotyrosine and 3-chlorotyrosine. Myeloperoxidase (MPO) is the only known source of 3-chlorotyrosine in humans, indicating that MPO oxidizes HDL in vivo. In the current studies, we used tandem mass spectrometry to identify the major sites of tyrosine oxidation when lipid-free apolipoprotein A-I (apoA-I), the major protein of HDL, was exposed to MPO or peroxynitrite (ONOO(-)). Tyrosine 192 was the predominant site of both nitration and chlorination by MPO and was also the major site of nitration by ONOO(-). Electron paramagnetic spin resonance studies of spin-labeled apoA-I revealed that residue 192 was located in an unusually hydrophilic environment. Moreover, the environment of residue 192 became much more hydrophobic when apoA-I was incorporated into discoidal HDL, and Tyr(192) of HDL-associated apoA-I was a poor substrate for nitration by both myeloperoxidase and ONOO(-), suggesting that solvent accessibility accounted in part for the reactivity of Tyr(192). The ability of lipid-free apoA-I to facilitate ATP-binding cassette transporter A1 cholesterol transport was greatly reduced after chlorination by MPO. Loss of activity occurred in concert with chlorination of Tyr(192). Both ONOO(-) and MPO nitrated Tyr(192) in high yield, but unlike chlorination, nitration minimally affected the ability of apoA-I to promote cholesterol efflux from cells. Our results indicate that Tyr(192) is the predominant site of nitration and chlorination when MPO or ONOO(-) oxidizes lipid-free apoA-I but that only chlorination markedly reduces the cholesterol efflux activity of apoA-I. This impaired biological activity of chlorinated apoA-I suggests that MPO-mediated oxidation of HDL might contribute to the link between inflammation and cardiovascular disease.

Theoretical studies on the structural and spectra properties of two C74 fullerenes and the chlorinated species C74Cl10

NASA Astrophysics Data System (ADS)

Zheng, Mei; Song, Xitong; Li, Xiaoqi; Qi, Jiayuan

2018-07-01

The geometrical/electronic structures, X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy of two especially C74 fullerenes (D3h-C74 and C1-C74) and the chlorinated species C1-C74Cl10, which are newly isolated in the experiment, have been calculated by means of the density functional theory (DFT) method. Effective changes in the electronic structure and simulated X-ray spectra have been observed after chlorination. Strong isomer dependence has been found in both spectra, thus the 'fingerprints' in the spectra can be employed as a tool to identify the isomers. The ultraviolet-visible (UV-vis) absorption spectrum of C1-C74Cl10 has been performed by using the time-dependent DFT method. The generated UV-vis spectrum coincides with the previous experimental counterpart. The results of this work can provide useful information especially for isomer identification and further study on fullerenes by means of the aforementioned spectroscopy techniques.

Chlorination of humic materials: Byproduct formation and chemical interpretations

USGS Publications Warehouse

Reckhow, D.A.; Singer, P.C.; Malcolm, R.L.

1990-01-01

Ten aquatic humic and fulvic acids were isolated and studied with respect to their reaction with chlorine. Yields of TOX, chloroform, trichloroacetic acid, dichloroacetic acid, dichloroacetonitrile, and 1,1,1-trichloropropanone were measured at pH 7 and 12. Humic acids produced higher concentrations than their corresponding fulvic acids of all byproducts except 1,1,1-trichloropropanone. Chlorine consumption and byproduct formation were related to fundamental chemical characteristics of the humic materials. A statistical model was proposed for activated aromatic content based on 13C NMR and base titration data. The values estimated from this model were found to be well correlated with chlorine consumption. Specific byproduct formation was related to UV absorbance, nitrogen content, or the activated aromatic content. ?? 1990 American Chemical Society.

The recovery of gold from refractory ores by the use of carbon-in-chlorine leaching

NASA Astrophysics Data System (ADS)

Greaves, John N.; Palmer, Glenn R.; White, William W.

1990-09-01

Recently, the U.S. Bureau of Mines examined the recovery of gold by chlorination of refractory carbonaceous and sulfidic ores, comparing various treatment methods in which a ground ore pulp is contacted with chlorine gas and activated carbon is added to the pulp for a carbon-in-chlorine leach (CICL). The objective of this research was to demonstrate the basic feasibility of CICL technology. Results showed that the organic carbon deactivating environment of CICL lowers, but does not eliminate, the adsorption of gold on activated carbon. In this environment, the refractory ore is altered, and gold is extracted and then recovered on activated carbon. With highly carbonaceous ores, CICL achieved a higher recovery than with primarily sulfidic refractory ores. Basic cyanide amenability testing of two carbonaceous ores achieved recoveries of only 5.5% and 46%. With CICL treatment, recoveries on carbon were 90% and 92%.

THE RESPONSE OF SOME HEALTH PHYSICS INSTRUMENTS TO SODIUM-24 AND CHLORINE- 38 ACTIVITIES IN POLYTHENE MANPHANTOMS AND THE HUMAN BODY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peabody, C.O.

1963-12-01

Measurements were made of the response of five commonly used health physics instruments when held near polythene man-phantoms filled with aqueous solutions containing sodium-24 and chlorine-38. The ratios of the wholebody chlorine-38 and sodium-24 activities are calculated for various periods of accidental human irradiation by neutrons. These ratios and the phantom results are used to estimate the response of the five instruments when held near the human body at various times after irradiation. Relative contributions of the chlorine-38 and sodium-24 to the instrument indications are listed. The tabulated data enable the instrument readings to be converted to wholebody sodium- 24more » activity at the time of irradiation. This may be used as a quick estimate of the degree of neutron irradiation. (auth)« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jordan, A.; Harnisch, J.; Borchers, R.

Previous investigations reported on the volcanic production of halocarbons including chlorofluorocarbons (CFCs). It has been suggested that this natural source could account for a significant atmospheric CFC background concentration, but no quantitative assessment of its source strength has yet been presented. The synthetic mechanism for their volcanic formation has neither been clarified. Fumarole and lava gas samples from four volcanoes (Kuju, Satsuma Iwojima, Mt. Etna, Vulcano) have been studied using gas chromatography/ion trap-mass spectrometry. More than 300 organic substances were detected, among which 5 fluorinated, 100 chlorinated, 25 brominated, and 4 iodinated compounds have been identified. The most abundant organohalogenmore » species were chlorinated methanes, unsaturated C{sub 2}-chlorohydrocarbons, and chlorobenzene, suggesting a synthetic course that includes the thermolytic formation of acetylene from hydrothermal methane, condensation reactions, and synchronous catalytic halogenation in the presence of highly activated surfaces of cooling magma or juvenile ash. The only CFC compound found was CFCl{sub 3} (CFC-11), which was detected in some samples at concentrations of up to 1 ppbv. A conservative estimate of the upper limit of global CFC emissions by volcanoes clearly shows that this source is negligible as compared to the atmospheric burden by anthropogenic activities.« less

Influence of drinking water treatments on chlorine dioxide consumption and chlorite/chlorate formation.

PubMed

Sorlini, Sabrina; Gialdini, Francesca; Biasibetti, Michela; Collivignarelli, Carlo

2014-05-01

Disinfection is the last treatment stage of a Drinking Water Treatment Plant (DWTP) and is carried out to maintain a residual concentration of disinfectant in the water distribution system. Chlorine dioxide (ClO2) is a widely used chemical employed for this purpose. The aim of this work was to evaluate the influence of several treatments on chlorine dioxide consumption and on chlorite and chlorate formation in the final oxidation/disinfection stage. A number of tests was performed at laboratory scale employing water samples collected from the DWTP of Cremona (Italy). The following processes were studied: oxidation with potassium permanganate, chlorine dioxide and sodium hypochlorite, coagulation/flocculation with ferric chloride and aluminum sulfate, filtration and adsorption onto activated carbon. The results showed that the chlorine dioxide demand is high if sodium hypochlorite or potassium permanganate are employed in pre-oxidation. On the other hand, chlorine dioxide leads to the highest production of chlorite and chlorate. The coagulation/flocculation process after pre-oxidation shows that chlorine dioxide demand decreases if potassium permanganate is employed as an oxidant, both with ferric chloride and aluminum sulfate. Therefore, the combination of these processes leads to a lower production of chlorite and chlorate. Aluminum sulfate is preferable in terms of the chlorine dioxide demand reduction and minimization of the chlorite and chlorate formation. Activated carbon is the most effective solution as it reduced the chlorine dioxide consumption by about 50% and the DBP formation by about 20-40%. Copyright © 2014 Elsevier Ltd. All rights reserved.

Vacuum-based surface modification of organic and metallic substrates

NASA Astrophysics Data System (ADS)

Torres, Jessica

Surface physico-chemical properties play an important role in the development and performance of materials in different applications. Consequently, understanding the chemical and physical processes involved during surface modification strategies is of great scientific and technological importance. This dissertation presents results from the surface modification of polymers, organic films and metallic substrates with reactive species, with the intent of simulating important modification processes and elucidating surface property changes of materials under different environments. The reactions of thermally evaporated copper and titanium with halogenated polytetrafluoroethylene (PTFE) and polyvinyl chloride (PVC) are used to contrast the interaction of metals with polymers. Results indicate that reactive metallization is thermodynamically favored when the metal-halogen bond strength is greater than the carbon-halogen bond strength. X-ray post-metallization treatment results in an increase in metal-halide bond formation due to the production of volatile halogen species in the polymer that react with the metallic overlayer. The reactions of atomic oxygen (AO) and atomic chlorine with polyethylene (PE) and self-assembled monolayers (SAMs) films were followed to ascertain the role of radical species during plasma-induced polymer surface modification. The reactions of AO with X-ray modified SAMs are initially the dominated by the incorporation of new oxygen containing functionality at the vacuum/film interface, leading to the production of volatile carbon containing species such as CO2 that erodes the hydrocarbon film. The reaction of atomic chlorine species with hydrocarbon SAMs, reveals that chlorination introduces C-Cl and C-Cl2 functionalities without erosion. A comparison of the reactions of AO and atomic chlorine with PE reveal a maximum incorporation of the corresponding C-O and C-Cl functionalities at the polymer surface. A novel method to prepare phosphorous-containing polymer surfaces through ion implantation of trimethyl phosphine onto PE is presented. Air exposure of the resulting P-implanted PE leads to the surface selective oxidation of phosphorous moieties. P-containing hydrocarbon films are used to model the surface chemical changes of P-containing polymers exposed to AO. Results indicate that oxidized phosphorous species protect the film from AO-induced erosion. The low temperature (<150 K) oxidation of nitrided iron surfaces exposed to oxygen reveal the formation of iron oxynitride (FexNyO z, nitrosonium ions (NO+) as well as nitrite/nitrito and nitrate type species. The production of nitrite/nitrito and nitrate species is taken as evidence for the existence of oxygen insertion chemistry into the iron nitride lattice under these low temperature oxidation conditions. Upon annealing the oxidized iron nitride surface, nitrogen desorbs exclusively as nitric oxide (NO).

Regioselective electrochemical reduction of 2,4-dichlorobiphenyl - Distinct standard reduction potentials for carbon-chlorine bonds using convolution potential sweep voltammetry

NASA Astrophysics Data System (ADS)

Muthukrishnan, A.; Sangaranarayanan, M. V.; Boyarskiy, V. P.; Boyarskaya, I. A.

2010-04-01

The reductive cleavage of carbon-chlorine bonds in 2,4-dichlorobiphenyl (PCB-7) is investigated using the convolution potential sweep voltammetry and quantum chemical calculations. The potential dependence of the logarithmic rate constant is non-linear which indicates the validity of Marcus-Hush theory of quadratic activation-driving force relationship. The ortho-chlorine of the 2,4-dichlorobiphenyl gets reduced first as inferred from the quantum chemical calculations and bulk electrolysis. The standard reduction potentials pertaining to the ortho-chlorine of 2,4-dichlorobiphenyl and that corresponding to para chlorine of the 4-chlorobiphenyl have been estimated.

Natural chlorine and fluorine in the atmosphere, water and precipitation

NASA Technical Reports Server (NTRS)

Friend, James P.

1990-01-01

The geochemical cycles of chlorine and fluorine are surveyed and summarized as framework for the understanding of the global natural abundances of these species in the atmosphere, water, and precipitation. In the cycles the fluxes into and out of the atmosphere can be balanced within the limits of our knowledge of the natural sources and sinks. Sea salt from the ocean surfaces represent the predominant portion of the source of chlorine. It is also an important source of atmospheric fluorine, but volcanoes are likely to be more important fluorine sources. Dry deposition of sea salt returns about 85 percent of the salt released there. Precipitation removes the remainder. Most of the sea salt materials are considered to be cyclic, moving through sea spray over the oceans and either directly back to the oceans or deposited dry and in precipitation on land, whence it runs off into rivers and streams and returns to the oceans. Most of the natural chlorine in the atmosphere is in the form of particulate chloride ion with lesser amounts as gaseous inorganic chloride and methyl chloride vapor. Fluorine is emitted from volcanoes primarily as HF. It is possible that HF may be released directly form the ocean surface but this has not been confirmed by observation. HCl and most likely HF gases are released into the atmosphere by sea salt aerosols. The mechanism for the release is likely to be the provision of protons from the so-called excess sulfate and HNO3. Sea salt aerosol contains fluorine as F(-), MgF(+), CaF(+), and NaF. The concentrations of the various species of chlorine and fluorine that characterize primarily natural, unpolluted atmospheres are summarized in tables and are discussed in relation to their fluxes through the geochemical cycle.

What’s in the Pool? A Comprehensive Identification of Disinfection By-products and Assessment of Mutagenicity of Chlorinated and Brominated Swimming Pool Water

PubMed Central

Richardson, Susan D.; DeMarini, David M.; Kogevinas, Manolis; Fernandez, Pilar; Marco, Esther; Lourencetti, Carolina; Ballesté, Clara; Heederik, Dick; Meliefste, Kees; McKague, A. Bruce; Marcos, Ricard; Font-Ribera, Laia; Grimalt, Joan O.; Villanueva, Cristina M.

2010-01-01

Background Swimming pool disinfectants and disinfection by-products (DBPs) have been linked to human health effects, including asthma and bladder cancer, but no studies have provided a comprehensive identification of DBPs in the water and related that to mutagenicity. Objectives We performed a comprehensive identification of DBPs and disinfectant species in waters from public swimming pools in Barcelona, Catalonia, Spain, that disinfect with either chlorine or bromine and we determined the mutagenicity of the waters to compare with the analytical results. Methods We used gas chromatography/mass spectrometry (GC/MS) to measure trihalomethanes in water, GC with electron capture detection for air, low- and high-resolution GC/MS to comprehensively identify DBPs, photometry to measure disinfectant species (free chlorine, monochloroamine, dichloramine, and trichloramine) in the waters, and an ion chromatography method to measure trichloramine in air. We assessed mutagenicity with the Salmonella mutagenicity assay. Results We identified > 100 DBPs, including many nitrogen-containing DBPs that were likely formed from nitrogen-containing precursors from human inputs, such as urine, sweat, and skin cells. Many DBPs were new and have not been reported previously in either swimming pool or drinking waters. Bromoform levels were greater in brominated than in chlorinated pool waters, but we also identified many brominated DBPs in the chlorinated waters. The pool waters were mutagenic at levels similar to that of drinking water (~ 1,200 revertants/L-equivalents in strain TA100–S9 mix). Conclusions This study identified many new DBPs not identified previously in swimming pool or drinking water and found that swimming pool waters are as mutagenic as typical drinking waters. PMID:20833605

Optimizing the Activation of Chlorin e6 Utilizing Upconversion Energy Transfer

NASA Astrophysics Data System (ADS)

Avalos, Julio C.; Pedraza, Francisco J.; Sardar, Dhiraj K.

2015-03-01

Current cancer therapy techniques, such as chemotherapy and radiation therapy, possess several drawbacks including lack of selectivity resulting in harmful side effects. Photodynamic therapy (PDT) is one of the fastest emerging techniques due to its many advantages, including the use of nonionizing radiation, targeted delivery, and controlled doses. In PDT, photosensitizers (PSs) are activated inside targeted cells to produce irreversible damage inducing cell death. Since most PSs operate in the visible range, it is difficult to activate them due to the high attenuation of soft tissue. Upconverting nanoparticles (UCNP) are able to absorb in the NIR region, where light is less attenuated, and emit in the visible range, resulting in deeper tissue penetration. UCNPs are able to assist with the activation of the PS by energy transfer when the PS is conjugated onto the UCNP. Chlorin e6 (Ce6) is a commonly used PSs due to its ability to release reactive oxygen species (ROS), which is one of the main processes utilized in PDT. The UCNP studied contain a combination of rare earth doped ions including Erbium, Thulium, and Holmium precisely doped into the host nanocrystal to improve upconversion emission and energy transfer. The work presented will focus on exploring the factors that affect the activation of Ce6. The results will include the enhancement of Ce6 activation and ROS release when conjugated onto a rare earth-doped UCNP. This research was funded by NSF-PREM Grant No. DMR -0934218 and RISE Grant No. GM 060655.

Mutagenic activity of disinfection by-products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cognet, L.; Courtois, Y.; Mallevialle, J.

1986-11-01

Data on raw water quality, disinfection treatment practices, and the resulting mutagenic properties of the treated water were compiled from pilot- and full-scale treatment experiments to evaluate that parameter which might produce variability in the results of a mutagenic study. Analysis of the data and comparison of treatment practices indicated that the measured mutagenic activity is strongly related to the characteristics of the organic matter in the raw water, the methodology used to sample and detect mutagens, the scale of the study both in terms of treatment flow and period of study, and the point at which and the conditionsmore » under which oxidants are added during treatment. Conclusions regarding disinfection systems in full-scale water treatment plants include the following: When raw water is pretreated and high concentrations of organics are present in the raw water, both ozonation and chlorination increased mutagenic activity. However, no significant difference in mutagenicity was found between the two oxidants. Both in the case of a nitrified groundwater and a clarified surface water, the mutagenic activity of the water after ozonation was related to its mutagenic activity before ozonation. With ozonation, mutagenic activity decreased after granular activated carbon (GAC) filtration. Thus, when GAC filtration follows ozone disinfection, early addition of oxidants may not be deleterious to the finished water quality. When chlorine or chlorine dioxide is added after GAC filtration, chlorine dioxide was found to produce a less mutagenic water than chlorine. Although these conclusions suggest means of controlling mutagenic activity during treatment, it must be stressed that the measurement of mutagenicity is a presumptive index of contamination level.« less

Determination of levels of polychlorinated biphenyl in transformers oil from some selected transformers in parts of the Greater Accra Region of Ghana.

PubMed

Buah-Kwofie, Archibold; Yeboah, Philip O; Pwamang, John

2011-01-01

Although polychlorinated biphenyls have never been manufactured in Ghana, it has been used extensively as dielectric fluid in electric transformers and capacitors. However, very little is known of its health and environmental impacts by both managers of these transformers and capacitors and also the general public. This work therefore seeks to explore INAA as a possible alternative to screening transformer oils for PCBs by determining the total chlorine content. The total chlorine content of transformer oil samples from Ghana that tested positive and some randomly selected samples that tested negative from screening using CLOR-N-OIL test kits, have had their total chlorine estimated. INAA using the Research Reactor located at the Ghana Atomic Energy Commission was used to estimate the total chlorine content of the oil samples. Neutron Activation and gamma ray spectroscopy using HPGe detector coupled to MAESTRO 32 software was used to determine the total chlorine content by integrating the peak area of the spectrum into a simplified program that was developed from the activation equation. Instrumental Neutron Activation Analysis was able to validate the result obtained from the test kits screening with accuracy 7.5%. The minimum total chlorine content of the positive samples determined by NAA was 71.34 μg g⁻¹. Copyright © 2010 Elsevier Ltd. All rights reserved.

Method and apparatus for rebalancing a redox flow cell system

NASA Technical Reports Server (NTRS)

Gahn, Randall F. (Inventor)

1986-01-01

A rebalance cell is provided for a REDOX electrochemical system of the type having anode and cathode fluids which are aqueous HCl solutions with two metal species in each. The rebalance cell has a cathode compartment and a chlorine compartment separated by an ion permeable membrane. By applying an electrical potential to the rebalance cell while circulating cathode fluid through the cathode compartment and while circulating an identical fluid through the chlorine compartment, any significant imbalance of the REDOX system is prevented.

Method and apparatus for rebalancing a REDOX flow cell system

NASA Technical Reports Server (NTRS)

Gahn, R. F. (Inventor)

1985-01-01

A rebalance cell is provided for a REDOX electrochemical system of the type with anode and cathode fluids which are aqueous HC1 solutions with two metal species in each. The rebalance cell has a cathode compartment and a chlorine compartment separated by an ion permeable membrane. By applying an electrical potential to the rebalance cell while circulating cathode fluid through the cathode compartment and while circulating an identical fluid through the chlorine compartment, any significant imbalance of the REDOX system is prevented.

SENSITIVITY OF THREE ENCEPHALITOZOON SPECIES TO CHLORINE AND CHLORAMINE TREATMENT AS DETECTED BY AN IN-VITRO MICROWELL PLATE ASSAY (POSTER PRESENTATION)

EPA Science Inventory

Microsporidia are obligate intracellular parasites that form environmentally resistant, infectious spores. These parasites are ubiquitous in the environment, infecting members of almost every class of verebrates and invertebrates. At least 14 microsporidian species that infect th...

ESTIMATION OF MICROBIAL REDUCTIVE TRANSFORMATION RATES FOR CHLORINATED BENZENES AND PHENOLS USING A QUANTITATIVE STRUCTURE-ACTIVITY RELATIONSHIP APPROACH

EPA Science Inventory

A set of literature data was used to derive several quantitative structure-activity relationships (QSARs) to predict the rate constants for the microbial reductive dehalogenation of chlorinated aromatics. Dechlorination rate constants for 25 chloroaromatics were corrected for th...

Impact of Photosensitizers Activation on Intracellular Trafficking and Viscosity

PubMed Central

Aubertin, Kelly; Bonneau, Stéphanie; Silva, Amanda K. A.; Bacri, Jean-Claude; Gallet, François; Wilhelm, Claire

2013-01-01

The intracellular microenvironment is essential for the efficiency of photo-induced therapies, as short-lived reactive oxygen species generated must diffuse through their intracellular surrounding medium to reach their cellular target. Here, by combining measurements of local cytoplasmic dissipation and active trafficking, we found that photosensitizers activation induced small changes in surrounding viscosity but a massive decrease in diffusion. These effects are the signature of a return to thermodynamic equilibrium of the system after photo-activation and correlated with depolymerization of the microtubule network, as shown in a reconstituted system. These mechanical measurements were performed with two intracellular photosensitizing chlorins having similar quantum yield of singlet oxygen production but different intracellular localizations (cytoplasmic for mTHPC, endosomal for TPCS2a). These two agents demonstrated different intracellular impact. PMID:24386423

Distribution, identification, and quantification of residues after treatment of ready-to-eat salami with 36Cl-labeled or nonlabeled chlorine dioxide gas

USDA-ARS?s Scientific Manuscript database

Chlorine dioxide gas actively eliminates a variety of food-borne pathogens and rot organisms, including Listeria monocytogenes on food and food preparation surfaces. However the disposition and fate of chlorine dioxide gas on ready-to-eat meat products has not been previously described. When ready-t...

Chlorine Diffusion in Uranium Dioxide: Thermal Effects versus Radiation Enhanced Effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pipon, Yves; Moncoffre, Nathalie; Bererd, Nicolas

2007-07-01

Chlorine is present as an impurity in the UO{sub 2} nuclear fuel. {sup 35}Cl is activated into {sup 36}Cl by thermal neutron capture. In case of interim storage or deep geological disposal of the spent fuel, this isotope is known to be able to contribute significantly to the instant release fraction because of its mobile behavior and its long half life (around 300000 years). It is therefore important to understand its migration behavior within the fuel rod. During reactor operation, chlorine diffusion can be due to thermally activated processes or can be favoured by irradiation defects induced by fission fragmentsmore » or alpha decay. In order to decouple both phenomena, we performed two distinct experiments to study the effects of thermal annealing on the behaviour of chlorine on one hand and the effects of the irradiation with fission products on the other hand. During in reactor processes, part of the {sup 36}Cl may be displaced from its original position, due to recoil or to collisions with fission products. In order to study the behavior of the displaced chlorine, {sup 37}Cl has been implanted into sintered depleted UO{sub 2} pellets (mean grain size around 18 {mu}m). The spatial distribution of the implanted and pristine chlorine has been analyzed by SIMS before and after treatment. Thermal annealing of {sup 37}Cl implanted UO{sub 2} pellets (implantation fluence of 10{sup 13} ions.cm{sup -2}) show that it is mobile from temperatures as low as 1273 K (E{sub a}=4.3 eV). The irradiation with fission products (Iodine, E=63.5 MeV) performed at 300 and 510 K, shows that the diffusion of chlorine is enhanced and that a thermally activated contribution is preserved (E{sub a}=0.1 eV). The diffusion coefficients measured at 1473 K and under fission product irradiation at 510 K are similar (D = 3.10{sup -14} cm{sup 2}.s{sup -1}). Considering in first approximation that the diffusion length L can be expressed as a function of the diffusion coefficient D and time t by : L=(Dt)1/2, the diffusion distance after 3 years is L=17 {mu}m. It results that there is a great probability for the chlorine contained in the UO{sub 2} grains to have reached the grain boundaries after 3 years, in the core of the fuel rod as well as at its periphery. Moreover, diffusion and concentration of chlorine at grain boundaries has been evidenced using SIMS mapping. Our results indicate therefore, that, during reactor operation and after, the majority of {sup 36}Cl is likely to have moved to grain boundaries, rim and gap. This fraction might then significantly contribute to the rapid or instant release of chlorine. This could have important consequences for safety assessment. During reactor operation, chlorine ({sup 35}Cl), an impurity of the nuclear fuel, is activated into {sup 36}Cl, a long lived mobile isotope. Because of its long half life and its mobility, this isotope may contribute significantly to the instant release fraction under disposal conditions. Thermal annealing of Cl implanted UO{sub 2} sintered pellets show that it is mobile from temperatures as low as 1273 K (E{sub a} = 4.3 eV). Chlorine diffusion induced by irradiation with fission products preserves a thermally activated contribution. The radiation induced defects significantly enhance chlorine migration. (authors)« less

Effect of pH, application technique, and chlorine-to-nitrogen ratio on disinfectant activity of inorganic chloramines with pure culture bacteria.

PubMed Central

Ward, N R; Wolfe, R L; Olson, B H

1984-01-01

The influence of pH, application technique, and chlorine-to-nitrogen weight ratio on the bactericidal activity of inorganic chloramine compounds was determined with stock and environmental strains of Escherichia coli, Salmonella spp., Pseudomonas aeruginosa, Klebsiella pneumoniae, and Enterobacter cloacae. The rate of inactivation increased from 1.5 to 2 times as the chlorine-to-nitrogen weight ratio was adjusted from 2:1 to 5:1, 5 to 6 times as the pH was decreased from 8 to 6, and 5 to 6 times as the concentration was increased from 1 to 5 mg/liter. Separate additions of free chlorine and ammonia (concurrent addition and preammoniation) into seeded water at or below pH 7.5 resulted in killing comparable to that observed with free chlorine (99% inactivation in less than 20 s). At pH 8, inactivation by separate additions was considerably slower and was comparable to that by prereacted chloramine compounds (99% inactivation in 25 to 26 min). Determination of the effectiveness of inorganic chloramine compounds as primary disinfectants for drinking water must consider the method of application, pH and concentrations of chlorine and ammonia. PMID:6437328

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

NASA Astrophysics Data System (ADS)

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 ± 0.5 mg/g. For the two commercial activated carbons, removal efficiencies were 11.4 ± 0.2 mg/g. The column experiment also showed positive results; no breakthrough has been observed after 1L of chlorine solution has passed through a column packed with 4 g of biochar made from the pyrolysis of grape seeds. Toxicity tests were also performed with the chlorine solution before and after passing through this column. The toxicity of the solution decreased after passing through the column packed with biochar suggesting that no toxic compounds are formed during the removal of chlorine by the biochar. The overall idea of this study is the sustainable use of the solid by-products of a food industry or producer to treat water or treated wastewater in order to enhance its quality and lower its toxicity. American Water Works Association (AWWA) 1990 Water quality and treatment, a handbook of community water supplies, Fourth edition.

Decontamination of PCBs-containing soil using subcritical water extraction process.

PubMed

Islam, Mohammad Nazrul; Park, Jeong-Hun; Shin, Moon-Su; Park, Ha-Seung

2014-08-01

Polychlorinated biphenyls (PCBs) are one of the excision compounds listed at the Stockholm convention in 2001. Although their use has been heavily restricted, PCBs can be found in some specific site-contaminated soils. Either removal or destruction is required prior to disposal. The subcritical water extraction (SCWE) of organic hazardous compounds from contaminated soils is a promising technique for hazardous waste contaminated-site cleanup. In this study, the removal of PCBs by the SCWE process was investigated. The effects of temperature and treatment time on removal efficiency have been determined. In the SCWE experiments, a removal percentage of 99.7% was obtained after 1h of treatment at 250°C. The mass removal efficiency of low-chlorinated species was higher than high-chlorinated congeners at lower temperatures, but it was oppositely observed at higher temperatures because the lower chlorinated congeners are formed by dechlorination of higher chlorinated congeners. Gas chromatography/mass spectrometry analysis confirmed that the PCBs underwent partial degradation. Several degradation products including mono- and di-chlorinated biphenyls, oxygen-containing aromatic compounds, and small-size hydrocarbons were identified in the effluent water, which were not initially present in the contaminated soil. Copyright © 2014 Elsevier Ltd. All rights reserved.

Hydroalumination of a chlorotrialkynylsilane: spontaneous stepwise 1,3-dyotropic rearrangement via an intermediate silyl cation.

PubMed

Uhl, Werner; Bohnemann, Jörg; Layh, Marcus; Würthwein, Ernst-Ulrich

2014-07-07

A new functionalised alkynylsilane, Cl-Si(CC-CMe3 )3 (3), was obtained by a facile multistep synthesis. Treatment of 3 with equimolar quantities of the hydrides H-M(CMe3 )2 (M=Al, Ga) gave the mixed alkenyl-di(alkynyl)silanes, in which the chlorine atom adopts a bridging position between the aluminium and silicon atoms. Dual hydrogallation of 3 resulted in the formation of a di(alkenyl)-alkynylsilane containing two gallium atoms, one of which is coordinated to the chlorine atom, and the second is bonded to the α-carbon atom of the remaining alkynyl group. A tert-butylsilane was unexpectedly formed by a unique 1,3-dyotropic chlorine-tert-butyl exchange for the corresponding dialuminium compound. One aluminium atom is bonded to a tert-butyl group, a terminal chlorine atom and the α-carbon atom of the ethynyl moiety; the second is coordinatively unsaturated, with two terminal tert-butyl substituents. High-level quantum-chemical calculations favour a stepwise dyotropic rearrangement with an intermediate cationic silicon species over a simultaneous tert-butyl-chlorine migration via a five-coordinate silicon atom in the transition state. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Superior bactericidal activity of N-bromine compounds compared to their N-chlorine analogues can be reversed under protein load.

PubMed

Gottardi, W; Klotz, S; Nagl, M

2014-06-01

To investigate and compare the bactericidal activity (BA) of active bromine and chlorine compounds in the absence and presence of protein load. Quantitative killing tests against Escherichia coli and Staphylococcus aureus were performed both in the absence and in the presence of peptone with pairs of isosteric active chlorine and bromine compounds: hypochlorous and hypobromous acid (HOCl and HOBr), dichloro- and dibromoisocyanuric acid, chlorantine and bromantine (1,3-dibromo- and 1,3 dichloro-5,5-dimethylhydantoine), chloramine T and bromamine T (N-chloro- and N-bromo-4-methylbenzenesulphonamide sodium), and N-chloro- and N-bromotaurine sodium. To classify the bactericidal activities on a quantitative basis, an empirical coefficient named specific bactericidal activity (SBA), founded on the parameters of killing curves, was defined: SBA= mean log reductions/(mean exposure times x concentration) [mmol 1(-1) min (-1)]. In the absence of peptone, tests with washed micro-organisms revealed a throughout higher BA of bromine compounds with only slight differences between single substances. This was in contrast to chlorine compounds, whose killing times differed by a factor of more than four decimal powers. As a consequence, also the isosteric pairs showed according differences. In the presence of peptone, however, bromine compounds showed an increased loss of BA, which partly caused a reversal of efficacy within isosteric pairs. In medical practice, weakly oxidizing active chlorine compounds like chloramines have the highest potential as topical anti-infectives in the presence of proteinaceous material (mucous membranes, open wounds). Active bromine compounds, on the other hand, have their chance at insensitive body regions with low organic matter, for example skin surfaces. The expected protein load is one of the most important parameters for selection of a suited active halogen compound. © 2014 The Society for Applied Microbiology.

Degradation of lipid regulators by the UV/chlorine process: Radical mechanisms, chlorine oxide radical (ClO•)-mediated transformation pathways and toxicity changes.

PubMed

Kong, Xiujuan; Wu, Zihao; Ren, Ziran; Guo, Kaiheng; Hou, Shaodong; Hua, Zhechao; Li, Xuchun; Fang, Jingyun

2018-06-15

Degradation of three lipid regulators, i.e., gemfibrozil, bezafibrate and clofibric acid, by a UV/chlorine treatment was systematically investigated. The chlorine oxide radical (ClO • ) played an important role in the degradation of gemfibrozil and bezafibrate with second-order rate constants of 4.2 (±0.3) × 10 8  M -1  s -1 and 3.6 (±0.1) × 10 7  M -1  s -1 , respectively, whereas UV photolysis and the hydroxyl radical (HO • ) mainly contributed to the degradation of clofibric acid. The first-order rate constants (k') for the degradation of gemfibrozil and bezafibrate increased linearly with increasing chlorine dosage, primarily due to the linear increase in the ClO • concentration. The k' values for gemfibrozil, bezafibrate, and clofibric acid degradation decreased with increasing pH from 5.0 to 8.4; however, the contribution of the reactive chlorine species (RCS) increased. Degradation of gemfibrozil and bezafibrate was enhanced in the presence of Br - , whereas it was inhibited in the presence of natural organic matter (NOM). The presence of ammonia at a chlorine: ammonia molar ratio of 1:1 resulted in decreases in the k' values for gemfibrozil and bezafibrate of 69.7% and 7%, respectively, but led to an increase in that for clofibric acid of 61.8%. Degradation of gemfibrozil by ClO • was initiated by hydroxylation and chlorine substitution on the benzene ring. Then, subsequent hydroxylation, bond cleavage and chlorination reactions led to the formation of more stable products. Three chlorinated intermediates were identified during ClO • oxidation process. Formation of the chlorinated disinfection by-products chloral hydrate and 1,1,1-trichloropropanone was enhanced relative to that of other by-products. The acute toxicity of gemfibrozil to Vibrio fischeri increased significantly when subjected to direct UV photolysis, whereas it decreased when oxidized by ClO • . This study is the first to report the transformation pathway of a micropollutant by ClO • . Copyright © 2018 Elsevier Ltd. All rights reserved.

Characterization of low molecular weight dissolved natural organic matter along the treatment trait of a waterworks using Fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Zhang, Haifeng; Zhang, Yahe; Shi, Quan; Ren, Shuoyi; Yu, Jianwei; Ji, Feng; Luo, Wenbin; Yang, Min

2012-10-15

Dissolved natural organic matter (DOM), particularly the low molecular weight DOM, can affect the performance of water treatment processes and serve as a main precursor of disinfection by-products (DBPs) during chlorination. In this study, electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) was used to characterize the low molecular weight DOM along the treatment trait of a conventional drinking water treatment plant. The ESI FT-ICR MS data showed that various C, H, O-only class species were the major components in the source water. According to the van Krevelen diagram analysis, lignin- and tannin-like compounds were the most abundant components. Within an isobaric group, the DOM molecules with a high degree of oxidation (high O/C value) were preferentially removed during coagulation, while those with low degree of oxidation were found to be more reactive toward chlorine. In addition, 357 one-chlorine containing products and 199 two-chlorine containing products formed during chlorination were detected in the chlorination effluent sample at a high confidence level. The chlorinated products can be arranged into series, suggesting that they were originated from C, H, O-only precursor compounds, which were in series related by the replacement of CH(4) against oxygen. For the first time, this study explored the behavior of low molecular weight DOM along a drinking water treatment trait on the molecular level, and revealed the presence of abundant unknown chlorinated products, which are probably rich in carboxylic and phenolic groups, in drinking water. Copyright © 2012 Elsevier Ltd. All rights reserved.

Kinetics of aqueous chlorination of some pharmaceuticals and their elimination from water matrices.

PubMed

Acero, Juan L; Benitez, F Javier; Real, Francisco J; Roldan, Gloria

2010-07-01

Apparent rate constants for the reactions of four selected pharmaceutical compounds (metoprolol, naproxen, amoxicillin, and phenacetin) with chlorine in ultra-pure (UP) water were determined as a function of the pH. It was found that amoxicillin (in the whole pH range 3-12), and naproxen (in the low pH range 2-4) presented high reaction rates, while naproxen (in the pH range 5-9), and phenacetin and metoprolol (in the pH range 2.5-12 for phenacetin, and 3-10 for metoprolol) followed intermediate and slow reaction rates. A mechanism is proposed for the chlorination reaction, which allowed the evaluation of the intrinsic rate constants for the elementary reactions of the ionized and un-ionized species of each selected pharmaceutical with chlorine. An excellent agreement is obtained between experimental and calculated rate constants by this mechanism.The elimination of these substances in several waters (a groundwater, a surface water from a public reservoir, and two effluents from municipal wastewater treatment plants) was also investigated at neutral pH. The efficiency of the chlorination process with respect to the pharmaceuticals elimination and the formation THMs was also established. It is generally observed that the increasing presence of organic and inorganic matter in the water matrices demand more oxidant agent (chlorine), and therefore, less chlorine is available for the oxidation of these compounds. Finally, half-life times and oxidant exposures (CT) required for the removal of 99% of the four pharmaceuticals are also evaluated. These parameters are useful for the establishment of safety chlorine doses in oxidation or disinfection stages of pharmaceuticals in treatment plants.

Relationship of dietary iodide and drinking water disinfectants to thyroid function in experimental animals.

PubMed Central

Revis, N W; McCauley, P; Holdsworth, G

1986-01-01

The importance of dietary iodide on the reported hypothyroid effect of drinking water disinfectants on thyroid function was investigated. Previous studies have also showed differences in the relative sensitivity of pigeons and rabbits to chlorinated water. Pigeons and rabbits were exposed for 3 months to diets containing high (950 ppb) or low (300 ppb) levels of iodide and to drinking water containing two levels of chlorine. Results showed that the high-iodide diet prevented the hypothyroid effect observed in pigeons given the low-iodide diet and chlorinated drinking water. Similar trends were observed in rabbits exposed to the same treatment; however, significant hypothyroid effects were not observed in this animal model. The factor associated with the observed effect of dietary iodide on the chlorine-induced change in thyroid function is unknown, as is the relative sensitivity of rabbits and pigeons to the effect of chlorine. Several factors may explain the importance of dietary iodide and the relative sensitivity of these species. For example, the iodine formed by the known reaction of chlorine with iodide could result in a decrease in the plasma level of iodide because of the relative absorption rates of iodide and iodine in the intestinal tract, and the various types and concentrations of chloroorganics (metabolites) formed in the diet following the exposure of various dietary constituents to chlorine could affect the thyroid function. The former factor was investigated in the present studies. Results do not confirm a consistent, significant reduction in the plasma level of iodide in rabbits and pigeons exposed to chlorinated water and the low-iodide diet. The latter factor is being investigated. PMID:3816728

[Comparative evaluation of health hazards associated with industrial chemicals and their derivates forming during water chlorination].

PubMed

Zholdakova, Z I; Poliakova, E E; Lebedev, A T

2006-01-01

Many industrial chemicals found in waste waters are able to form organochlorine by-products during water disinfection. The transformation of seven model compounds, cyclohexene, n-butanol, diphenylmethane, acetophenone, aniline, 1-methylnaphthalene, and phenylxylylethane during a reaction with active chlorine was studied. Aqueous chlorine and sodium hypochlorite were used as chlorinating agents. The products of the reaction were analyzed by means of chromatomass-spectrometry. A schematic model of diphenylmethane transformation was proposed. Comparative evaluation of hazards associated with the model chemicals and their derivates confirmed that chlorination products can be more toxic and dangerous than the initial compounds, and may possess mutagenic and cancerigenic properties.

Boron-doped diamond electrooxidation of ethyl paraben: The effect of electrolyte on by-products distribution and mechanisms.

PubMed

Frontistis, Zacharias; Antonopoulou, Maria; Yazirdagi, Melis; Kilinc, Zeynep; Konstantinou, Ioannis; Katsaounis, Alexandros; Mantzavinos, Dionissios

2017-06-15

Ethyl paraben (EP), a representative emerging pollutant of the parabens family, was subject to electrochemical oxidation over a boron-doped diamond (BDD) anode. Experiments were carried out in a single-compartment cell at 10-70 mA cm -2 current density, 200-600 μg L -1 EP concentration, initial solution pH 3-9 and 0.1 M electrolyte concentration. The degradation rate is favored at increased current densities and in the presence of NaCl as the supporting electrolyte, while the pH effect is inconsiderable. For instance, the first order rate constant for the degradation of 200 μg L -1 EP at 30 mA cm -2 was 0.25, 0.1 and 0.07 min -1 with NaCl, Na 2 SO 4 and HClO 4 , respectively. Degradation in secondary treated wastewater was faster than in pure water presumably due to the action of chloride ions present in the effluent. Liquid chromatography time-of-flight mass spectrometry (LC-TOF-MS) was employed to determine major transformation by-products (TBPs). The route of EP degradation with Na 2 SO 4 involves hydroxylation and demethylation reactions, signifying the role of electrogenerated hydroxyl radicals in the process. Twenty one TBPs were identified with NaCl as the electrolyte, including several chlorinated and non-chlorinated dimers and trimers; these findings suggest that indirect oxidation mediated by chlorine radicals and other chlorine active species also takes place. In this view, the role of the supporting electrolyte is crucial since it can influence both reaction kinetics and pathways. Copyright © 2016 Elsevier Ltd. All rights reserved.

Repairing oxidized proteins in the bacterial envelope using respiratory chain electrons.

PubMed

Gennaris, Alexandra; Ezraty, Benjamin; Henry, Camille; Agrebi, Rym; Vergnes, Alexandra; Oheix, Emmanuel; Bos, Julia; Leverrier, Pauline; Espinosa, Leon; Szewczyk, Joanna; Vertommen, Didier; Iranzo, Olga; Collet, Jean-François; Barras, Frédéric

2015-12-17

The reactive species of oxygen and chlorine damage cellular components, potentially leading to cell death. In proteins, the sulfur-containing amino acid methionine is converted to methionine sulfoxide, which can cause a loss of biological activity. To rescue proteins with methionine sulfoxide residues, living cells express methionine sulfoxide reductases (Msrs) in most subcellular compartments, including the cytosol, mitochondria and chloroplasts. Here we report the identification of an enzymatic system, MsrPQ, repairing proteins containing methionine sulfoxide in the bacterial cell envelope, a compartment particularly exposed to the reactive species of oxygen and chlorine generated by the host defence mechanisms. MsrP, a molybdo-enzyme, and MsrQ, a haem-binding membrane protein, are widely conserved throughout Gram-negative bacteria, including major human pathogens. MsrPQ synthesis is induced by hypochlorous acid, a powerful antimicrobial released by neutrophils. Consistently, MsrPQ is essential for the maintenance of envelope integrity under bleach stress, rescuing a wide series of structurally unrelated periplasmic proteins from methionine oxidation, including the primary periplasmic chaperone SurA. For this activity, MsrPQ uses electrons from the respiratory chain, which represents a novel mechanism to import reducing equivalents into the bacterial cell envelope. A remarkable feature of MsrPQ is its capacity to reduce both rectus (R-) and sinister (S-) diastereoisomers of methionine sulfoxide, making this oxidoreductase complex functionally different from previously identified Msrs. The discovery that a large class of bacteria contain a single, non-stereospecific enzymatic complex fully protecting methionine residues from oxidation should prompt a search for similar systems in eukaryotic subcellular oxidizing compartments, including the endoplasmic reticulum.

FIGAERO ToF CIMS measurements of chlorine photochemical activation by nitryl chloride chemistry at a semi-rural site in Beijing

NASA Astrophysics Data System (ADS)

Le Breton, Michael; Hallquist, Åsa M.; Kant Pathak, Ravi; Simpson, David; Wang, Yujue; Zheng, Jing; Yang, Yudong; Shang, Dongjie; Wang, Haichao; Lu, Keding; Guo, Song; Hu, Min; Hallquist, Mattias

2017-04-01

Severe pollution events across China pose a major threat to air quality and climate through the direct emission of pollutants, but also via the production of photochemically induced secondary pollutants. Nitryl chloride (ClNO2), produced from heterogeneous reactions of dinitrogen pentoxide (N2O5) and aerosols containing chloride, is photolysed rapidly in sunlight and activates chlorine. Subsequent daytime oxidation via the chlorine atom can proceed orders of magnitude faster than that of the hydroxyl radical and therefore significantly perturb radical budgets and concentrations of ozone and secondary pollutants. Knowledge of the formation pathways, abundance and fate of these secondary pollutants, which can depend on ClNO2 abundance, is not fully understood but is necessary to support abatement strategies which will efficiently account for both primary and secondary pollutants. A Time of Flight Chemical Ionisation Mass Spectrometer (ToF CIMS) utilising the Filter Inlet for Gases and AEROsols (FIGAERO) was deployed in Changping, Beijing, during June and July, 2016 as part of an intercollaborative project to assess the photochemical smog in China. Concentrations of ClNO2 regularly exceeded 500 ppt throughout the campaign and reached a maximum concentration of 2.8 ppb, whereas relatively low N2O5 concentrations were observed, indicating a rapid heterogeneous production of ClNO2. Correlation of particulate chloride and carbon monoxide during the campaign suggests an anthropogenic chlorine source, also supported by high daytime Cl2 concentrations. Observations of ClNO2 desorptions using the FIGAERO suggest a possible unaccounted particulate reservoir of active chlorine in highly polluted regions. The persistence of ClNO2 several hours passed sunrise significantly increases the atomic chlorine production rate throughout the day further perturbing standard daytime oxidation processes. Simultaneous ToF CIMS measurements of Cl2, ClNO2, HCl, HOCl, OClO and ClONO2 were implemented into steady state calculations using the Master Chemical Mechanism (MCM) to assess how the daytime activation of chlorine competes with OH as a dominant oxidant in this heavily polluted region. The reactions of atomic chlorine with VOCs are traced and assessed via the gas and particle phase measurements of chlorinated VOCs and supporting Proton Transfer Reaction Mass Spectrometer (PTR MS) VOC measurements. This provides the first high frequency measurements of unique tracers for chlorine atom chemistry, several of which are represented in the MCM, in both the gas and particle phase and enable the detailed assessment of their diurnal variation and importance for photochemical smog formation.

The effect of pH and chloride concentration on the stability and antimicrobial activity of chlorine-based sanitizers.

PubMed

Waters, Brian W; Hung, Yen-Con

2014-04-01

Chlorinated water and electrolyzed oxidizing (EO) water solutions were made to compare the free chlorine stability and microbicidal efficacy of chlorine-containing solutions with different properties. Reduction of Escherichia coli O157:H7 was greatest in fresh samples (approximately 9.0 log CFU/mL reduction). Chlorine loss in "aged" samples (samples left in open bottles) was greatest (approximately 40 mg/L free chlorine loss in 24 h) in low pH (approximately 2.5) and high chloride (Cl(-) ) concentrations (greater than 150 mg/L). Reduction of E. coli O157:H7 was also negatively impacted (<1.0 log CFU/mL reduction) in aged samples with a low pH and high Cl(-) . Higher pH values (approximately 6.0) did not appear to have a significant effect on free chlorine loss or numbers of surviving microbial cells when fresh and aged samples were compared. This study found chloride levels in the chlorinated and EO water solutions had a reduced effect on both free chlorine stability and its microbicidal efficacy in the low pH solutions. Greater concentrations of chloride in pH 2.5 samples resulted in decreased free chlorine stability and lower microbicidal efficacy. © 2014 Institute of Food Technologists®

Separation of chlorinated diastereomers of decarboxy-betacyanins in myeloperoxidase catalyzed chlorinated Beta vulgaris L. extract.

PubMed

Wybraniec, Sławomir; Starzak, Karolina; Szneler, Edward; Pietrzkowski, Zbigniew

2016-11-15

A comparative chromatographic evaluation of chlorinated decarboxylated betanins and betanidins generated under activity of hypochlorous acid exerted upon these highly antioxidative potent decarboxylated pigments derived from natural sources was performed by LC-DAD-ESI-MS/MS. Comparison of the chromatographic profiles of the chlorinated pigments revealed two different directions of retention changes in relation to the corresponding substrates. Chlorination of all betacyanins that are decarboxylated at carbon C-17 results in an increase of their retention times. In contrast, all other pigments (the non-decarboxylated betacyanins as well as 2-decarboxy- and 15-decarboxy-derivatives) exhibit lower retention after chlorination. During further chromatographic experiments based upon chemical transformation of the related pigments (decarboxylation and deglucosylation), the compounds' structures were confirmed. The elaborated method for determination of chlorinated pigments enabled analysis of a chlorinated red beet root extract that was submitted to the MPO/H 2 O 2 /Cl - system acting under inflammation-like conditions (pH 5). This indicates a promising possibility for measurement of these chlorinated pigments as indicators of specific inflammatory states wherein betacyanins and decarboxylated betacyanins act as hypochlorite scavengers. Copyright © 2016 Elsevier B.V. All rights reserved.

Oxychlorine Species on Mars: The Gale Crater Story

NASA Technical Reports Server (NTRS)

Archer, P. D., Jr.; Ming, D. W.; Sutter, B.; Morris, R. V.; Clark, B. C.; Mahaffy, P. H.; Wray, J. J.; Fairen, A. G.; Gellert, R.; Yen, A. S.;

Environmental behaviour of short-chain chlorinated paraffins in aquatic and terrestrial ecosystems of Ny-Ålesund and London Island, Svalbard, in the Arctic.

PubMed

Li, Huijuan; Fu, Jianjie; Pan, Wenxiao; Wang, Pu; Li, Yingming; Zhang, Qinghua; Wang, Yawei; Zhang, Aiqian; Liang, Yong; Jiang, Guibin

2017-07-15

The environmental behaviour of short-chain chlorinated paraffins (SCCPs) was investigated in both aquatic and terrestrial ecosystems in the Arctic. The mean concentrations of SCCPs in the aquatic and terrestrial samples were 178.9ng/g dry weight (dw) and 157.2ng/g dw, respectively. Short carbon chain (C 10 ) and less-chlorinated (Cl 6 ) congener groups were predominant in the Arctic samples, accounting for 48.6% and 34.8% of the total SCCPs, respectively. The enrichment of lighter SCCP congener groups (i.e., fewer chlorine atoms with shorter carbon chain lengths) indicated that the fractionation process occurred during long-range transport. The biomagnification factor (BMF) was 0.46 from gammarid to cod, which indicated that the SCCPs did not biomagnify between these two species. The soil-vegetation bioaccumulation factor (BAF) of SCCPs was 29.9, and C 13 and Cl 7, 8 congener groups tended to accumulate in the terrestrial vegetation. Regression analysis (BAFs=10.9×#C+5.6×#Cl-125.2, R=0.53, P<0.01) showed that the number of carbon and chlorine atoms influenced the bioaccumulative behaviour of SCCPs and suggested that the number of carbon atoms had a greater influence on the BAFs of SCCPs in the terrestrial ecosystem than did the number of chlorine atoms. Copyright © 2017 Elsevier B.V. All rights reserved.

Degradation of methadone by the sunlight/FC process: Kinetics, radical species participation and influence of the water matrix.

PubMed

Hsieh, Ming-Chi; Panchangam, Sri Chandana; Lai, Webber Wei-Po; Lin, Angela Yu-Chen

2018-06-12

Free chlorine sunlight photolysis (sunlight/FC) markedly enhances the degradation rate of methadone, a synthetic opioid used medically, over that obtained using sunlight alone. The pseudo-first-order rate constants of methadone degradation under acidic conditions ([methadone] = 0.2 μM, [free chlorine] = 4 μM, and pH = 4) for sunlight/FC and sunlight photolysis are 7.0 ± 1.1 × 10 -2  min -1 and 1.4 ± 0.2 × 10 -2  min -1 , respectively. The improved methadone degradation can be attributed to the production of HO and reactive chlorine species (RCS) during sunlight/FC photolysis. HO and RCS predominantly accounted for degradation during sunlight/FC photolysis under acidic and neutral conditions, while direct photolysis was the major contributor towards methadone degradation in alkaline conditions. The initial pH (pH 4-11) and free chlorine concentration (1-6 μM) significantly influenced the overall degradation efficiency of methadone. The presence of HCO 3 - , Cl - and dissolved organic matters, which may competitively react with HO and RCS, retard the degradation of methadone in synthetic wastewater. Consequently, a 50% lower methadone degradation rate was observed when deionized (DI) water was replaced with tap water. These results emphasize the need to consider different water matrices when applying sunlight/FC photolysis for water treatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Chlorine isn't Just for Swimming Pools Anymore... Chlorination of Organic Compounds in the Arctic

NASA Astrophysics Data System (ADS)

Han, A.; Raab, T. K.

2013-12-01

The cycling of chlorine between its organic and inorganic forms is known to occur in forest soils, but little is known about the generality of this mechanism, which soil components chlorine attaches to, and at what rate chlorination occurs. The study uses peat-rich tundra soils from Barrow, Alaska varying in age since formation of 50 yrs - 5500 yrs BP, and seeks to measure the rate at which organic molecules are chlorinated and to understand what changes those molecules undergo once chlorinated. Soil abundance of chlorine and bromine was estimated in soils of varying age using X-ray fluorescence, and org-Cl levels were measured using pyro-hydrolysis [Table 1]. We considered activity of the enzyme Chloroperoxidase, and data was gathered using absorbance scans of the organic molecule monochlorodimedone to determine whether it had been chlorinated and if so, at what rate. Additional information was gathered from the chlorination of small organic components of the macromolecule lignin, whose constituent molecules make up a large portion of humic materials critical to soil health, through emission scans and fluorescence scans. The results showed that the enzyme chloroperoxidase, which is found in nature and is associated with fungi or bacteria, attaches a chlorine atom to monochlorodimedone and that similar enzymes found in Arctic soils act on it, as well as the lignin model subunits cinnamaldehyde ((2E)-3-phenylprop-2-enal) and naringenin-7-rhamnoglucoside. The results may provide more information on chlorination rates in the Arctic and may contribute to an understanding of how and at what rate chlorine changes form in nature, and answer questions about ozone deterioration or anthropogenic chlorine impact(s) on the environment.Average Halogen Abundance in Arctic Soils xrf=Energy Dispersive X-Ray Fluorescencepyro= TOX Pyro-Hydrolysis

Inactivation, reactivation and regrowth of indigenous bacteria in reclaimed water after chlorine disinfection of a municipal wastewater treatment plant.

PubMed

Li, Dan; Zeng, Siyu; Gu, April Z; He, Miao; Shi, Hanchang

2013-07-01

Disinfection of reclaimed water prior to reuse is important to prevent the transmission of pathogens. Chlorine is a widely utilized disinfectant and as such is a leading contender for disinfection of reclaimed water. To understand the risks of chlorination resulting from the potential selection of pathogenic bacteria, the inactivation, reactivation and regrowth rates of indigenous bacteria were investigated in reclaimed water after chlorine disinfection. Inactivation of total coliforms, Enterococcus and Salmonella showed linear correlations, with constants of 0.1384, 0.1624 and 0.057 L/(mg.min) and R2 of 0.7617, 0.8316 and 0.845, respectively. However, inactivation of total viable cells by measurement of metabolic activity typically showed a linear correlation at lower chlorine dose (0-22 (mg-min)/L), and a trailing region with chlorine dose increasing from 22 to 69 (mg.min)/L. Reactivation and regrowth of bacteria were most likely to occur after exposure to lower chlorine doses, and extents of reactivation decreased gradually with increasing chlorine dose. In contrast to total coliforms and Enterococcus, Salmonella had a high level of regrowth and reactivation, and still had 2% regrowth even after chlorination of 69 (mg.min)/L and 24 hr storage. The bacterial compositions were also significantly altered by chlorination and storage of reclaimed water, and the ratio of Salmonella was significantly increased from 0.001% to 0.045% after chlorination of 69 (mg.min)/L and 24 hr storage. These trends indicated that chlorination contributes to the selection of chlorine-resistant pathogenic bacteria, and regrowth of pathogenic bacteria after chlorination in reclaimed water with a long retention time could threaten public health security during wastewater reuse.

A kinetics investigation of several reactions involving chlorine containing compounds

NASA Technical Reports Server (NTRS)

Davis, D. D.

1978-01-01

The technique of flash photolysis-resonance fluorescence was utilized to study nine reactions of stratospheric importance. The tropospheric degradation reactions of seven halogenated hydrocarbons were studied to assess their possible influx into the stratosphere. There are reactions of either Cl, OH, or O(3P) species with hydrogenated species, O3 or chlorinated compounds. Apart from the kinetic measurements, the quantum yield for the production of O(1D) from O3 in the crucial wavelength region of 293 to 316.5 nm was studied by utilizing a narrow wavelength laser as the photolysis source. The product formation was monitored by measuring the fluorescence of NO2 formed through O(1D) reaction with N2O followed by NO reaction with O3 to give NO2.

The role of microbial low-molecular-weight autoregulatory factors (alkylhydroxybenzenes) in resistance of microorganisms to radiation

NASA Astrophysics Data System (ADS)

El-Registan, G. I.; Mulyukin, A. L.; Nikolaev, Yu. A.; Stepanenko, I. Yu.; Shanenko, E. A.; Strakhovskaya, M. G.; Revina, A. A.

Low-molecular-weight cell-to-cell communication factors are produced by various pro- and eukaryotes and involved in autoregulation of the growth and development of microbial cultures. As for some bacterial and yeast species, these factors were identified as isomers and homologs of alkylhydroxybenzenes (AHBs). Depending on the concentration, they participate in controlling the transition to stationary phase, entering the resting state, and stress resistance of vegetative cells to gamma-irradiation, photooxidation (singlet oxygen), heat shock. Chemical analogs of microbial AHBs protected microbial cultures from stressful situations and prolonged starvation and exerted (1) the stabilizing activity toward biomacromolecules and supermolecular structures (cell membranes) and (2) the ability to scavenge active oxygen species. The stabilizing effect of AHBs as chemical chaperones resulted from their complex formation with protected macromolecules due to intermolecular hydrogen bonds, hydrophobic and electrostatic interactions and was demonstrated on models of individual enzymes (trypsin, amylase, etc.). The action of AHBs as active oxygen species scavengers was related to their oxidative conversion to water-insoluble polymeric products. Particularly, AHBs protected the yeast from the action of (a) active oxygen species formed during gamma-irradiation (50 krad, 196 rad/sec) or (b) singlet oxygen generated in cells photosensitized by chlorin e6 (10 mkg/L). It is important that microbial AHBs were not species-specific and defended cultured animal cells (ras-transformed fibroblasts) from the action of organic toxicants. The use of AHBs as protectants and adaptogens will be discussed as well as perspectives of further investigations.

Removal of sulfamethoxazole, ibuprofen and nitrobenzene by UV and UV/chlorine processes: A comparative evaluation of 275 nm LED-UV and 254 nm LP-UV.

PubMed

Kwon, Minhwan; Yoon, Yeojoon; Kim, Seonbaek; Jung, Youmi; Hwang, Tae-Mun; Kang, Joon-Wun

2018-10-01

The aim of this study is to evaluate the micropollutant removal capacity of a 275 nm light-emitting diode (LED)-UV/chlorine system. The sulfamethoxazole, ibuprofen, and nitrobenzene removal efficiencies of this system were compared with those of a conventional 254 nm low-pressure (LP)-UV system as a function of the UV dose. In a direct photolysis system, the photon reactivity of sulfamethoxazole is higher than that of nitrobenzene and ibuprofen at both wavelengths. The molar absorption coefficients and quantum yields of each micropollutant were as follows: sulfamethoxazole (ε SMX, 275 nm protonated  = 17,527 M -1  cm -1 , Φ SMX, 275 nm protonated  = 0.239, ε SMX, 275 nm deprotonated  = 8430 M -1  cm -1 , and Φ SMX, 275 nm deprotonated  = 0.026), nitrobenzene (ε NB, 275 nm  = 7176 M -1  cm -1 and Φ NB, 275 nm  = 0.057), and ibuprofen (ε NB, 275 nm  = 200 M -1  cm -1 and Φ IBF, 275 nm  = 0.067). The photon reactivity of chlorine species, i.e., HOCl and OCl-, were determined at 275 nm (ε HOCl, 275 nm  = 28 M -1  cm -1 , Φ HOCl, 275 nm  = 1.97, ε OCl-, 275 nm  = 245 M -1  cm -1 , and Φ OCl-, 275 nm  = 0.8), which indicate that the decomposition rate of OCl - is higher and that of HOCl is lower by 275 nm photolysis than that by 254 nm photolysis (ε HOCl, 254 nm  = 60 M -1  cm -1 , Φ HOCl, 254 nm  = 1.46, ε OCl-, 254 nm  = 58 M -1  cm -1 , and Φ OCl-, 254 nm  = 1.11). In the UV/chlorine system, the removal rates of ibuprofen and nitrobenzene were increased by the formation of OH and reactive chlorine species. The 275-nm LED-UV/chlorine system has higher radical yields at pH 7 and 8 than the 254 nm LP-UV/chlorine system. Copyright © 2018 Elsevier B.V. All rights reserved.

Wildlife toxicology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kendall, R.J.

1982-08-01

Wildlife toxicology may be defined as the study of the effects of environmental contaminants on wildlife species, as related to their wellbeing, general health, and reproduction. Results of studies with pesticides, heavy metals, and chlorinated hydrocarbons are examined. Integrated field and laboratory studies using selected model species might lead to ways of quantifying the adverse effects of chemical contaminants. (KRM)

General Theories of Chemical Disinfection and Sterilization of Sludge--Part 3.

ERIC Educational Resources Information Center

Wang, Mu Hao; And Others

1978-01-01

A general discussion of sewage sterilization methods, including techniques using pH, Chlorine, Chlorine Dioxide, Ozone, Iodine and Bromine, metal ions, and cationic surface active agents is presented. (MDR)

Transformation of methylparaben during water chlorination: Effects of bromide and dissolved organic matter on reaction kinetics and transformation pathways.

PubMed

Yoom, Hoonsik; Shin, Jaedon; Ra, Jiwoon; Son, Heejong; Ryu, Dongchoon; Kim, Changwon; Lee, Yunho

2018-09-01

The reaction kinetics, products, and pathways of methylparaben (MeP) during water chlorination with and without bromide (Br - ) were investigated to better understand the fate of parabens in chlorinated waters. During the chlorination of MeP-spiked waters without Br - , MeP was transformed into mono-Cl-MeP and di-Cl-MeP with apparent second-order rate constants (k app ) of 64M -1 s -1 and 243M -1 s -1 at pH7, respectively, while further chlorination of di-Cl-MeP was relatively slower (k app =1.3M -1 s -1 at pH7). With increasing Br - concentration, brominated MePs, such as mono-Br-MeP, Br-Cl-MeP, and di-Br-MeP, became major transformation products. The di-halogenated MePs (di-Cl-MeP, Br,Cl-MeP, and di-Br-MeP) showed relatively low reactivity to chlorine at pH7 (k app =1.3-4.6M -1 s -1 ) and bromine (k app =32-71M -1 s -1 ), which explains the observed high stability of di-halogenated MePs in chlorinated waters. With increasing pH from 7 to 8.5, the transformation of di-halogenated MePs was further slowed due to the decreasing reactivity of di-MePs to chlorine. The formation of the di-halogenated MePs and their further transformation become considerably faster at Br - concentrations higher than 0.5μM (40μg/L). Nonetheless, the accelerating effect of Br - diminishes in the presence of dissolved organic matter (DOM) extract (Suwannee River humic acid (SRHA)) due to a more rapid consumption of bromine by DOM than chlorine. The effect of Br - on the fate of MeP was less in the tested real water matrices, possibly due to a more rapid bromine consumption by the real water DOM compared to SRHA. A kinetic model was developed based on the determined species-specific second-order rate constants for chlorination/bromination of MeP and its chlorinated and brominated MePs and the transformation pathway information, which could reasonably simulate the transformation of MePs during the chlorination of water in the presence of Br - and selected DOM. Copyright © 2017 Elsevier B.V. All rights reserved.

Short-chain chlorinated paraffins in terrestrial bird species inhabiting an e-waste recycling site in South China.

PubMed

Luo, Xiao-Jun; Sun, Yu-Xin; Wu, Jiang-Ping; Chen, She-Jun; Mai, Bi-Xian

2015-03-01

Short-chain chlorinated paraffins (SCCPs) are under review by the Stockholm Convention on Persistent Organic Pollutants. Currently, limited data are available about SCCPs in terrestrial organisms. In the present study, SCCP concentration in the muscles of seven terrestrial bird species (n = 38) inhabiting an e-waste recycling area in South China was determined. This concentration varied from 620 to 17,000 ng/g lipid. Resident birds accumulated significantly higher SCCP concentrations than migratory birds (p < 0.01). Trophic magnification was observed for migratory bird species but not for resident, which was attributed to high heterogeneity of SCCP in e-waste area. Two different homologue group patterns were observed in avian samples. The first pattern was found in five bird species dominated by C10 and C11 congeners, while the second was found in the remains, which show rather equal abundance of homologue groups. This may be caused by two sources of SCCPs (local and e-waste) in the study area. Copyright © 2014 Elsevier Ltd. All rights reserved.

Induction of prophage lambda by chlorinated organics: Detection of some single-species/single-site carcinogens

DOE Office of Scientific and Technical Information (OSTI.GOV)

DeMarini, D.M.; Brooks, H.G.

1992-01-01

Twenty-eight chlorinated organic compounds were evaluated for their ability to induce DNA damage using the Microscreen prophage-induction assay in Escherichia coli. Comparison of the performance characteristics of the prophage-induction and Salmonella assays to rodent carcinogenicity assays showed that the prophage-induction assay had a somewhat higher specificity than did the Salmonella assay (70% vs. 50%); sensitivity, concordance, and positive and negative predictivity were similar for the two microbial assays. The Microscreen prophage-induction assay failed to detect eight carcinogens, perhaps due to toxicity or other unknown factors; five of these eight carcinogens were detected by the Salmonella assay. However, the prophage-induction assaymore » did detect six carcinogens that were not detected by the Salmonella assay, and five of these were single-species, single-site carcinogens, mostly mouse liver carcinogens. Some of these carcinogens, such as the chloroethanes, produce free radicals, which may be the basis for their carcinogenicity and ability to induce prophage. The prophage-induction (or other SOS) assay may be useful in identifying some genotoxic chlorinated carcinogens that induce DNA damage that do not revert the standard Salmonella tester strains.« less

Depletion of ozone and reservoir species of chlorine and nitrogen oxide in the lower Antarctic polar vortex measured from aircraft

NASA Astrophysics Data System (ADS)

Jurkat, T.; Voigt, C.; Kaufmann, S.; Grooß, J.-U.; Ziereis, H.; Dörnbrack, A.; Hoor, P.; Bozem, H.; Engel, A.; Bönisch, H.; Keber, T.; Hüneke, T.; Pfeilsticker, K.; Zahn, A.; Walker, K. A.; Boone, C. D.; Bernath, P. F.; Schlager, H.

2017-06-01

Novel airborne in situ measurements of inorganic chlorine, nitrogen oxide species, and ozone were performed inside the lower Antarctic polar vortex and at its edge in September 2012. We focus on one flight during the Transport and Composition of the LMS/Earth System Model Validation (TACTS/ESMVal) campaign with the German research aircraft HALO (High-Altitude LOng range research aircraft), reaching latitudes of 65°S and potential temperatures up to 405 K. Using the early winter correlations of reactive trace gases with N2O from the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS), we find high depletion of chlorine reservoir gases up to ˜40% (0.8 ppbv) at 12 km to 14 km altitude in the vortex and 0.4 ppbv at the edge in subsided stratospheric air with mean ages up to 4.5 years. We observe denitrification of up to 4 ppbv, while ozone was depleted by 1.2 ppmv at potential temperatures as low as 380 K. The advanced instrumentation aboard HALO enables high-resolution measurements with implications for the oxidation capacity of the lowermost stratosphere.

Hybrid simulations of positively and negatively charged pickup ions and cyclotron wave generation at Europa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Desai, Ravindra T.; Cowee, Misa; Wei, Hanying

In the vicinity of Europa, Galileo observed bursty Alfvén-cyclotron wave power at the gyrofrequencies of a number of species including K +, math formula, Na +, and Cl +, indicating the localised pickup of these species. Additional evidence for the presence of Chlorine was the occurrence of both left-hand (LH) and right-hand (RH) polarised transverse wave power near the Cl + gyrofrequency, thought to be due to the pickup of both Cl + and the easily formed Chlorine anion, Cl –. To test this hypothesis we use one-dimensional hybrid (kinetic ion, massless fluid electron) simulations for both positive and negativemore » pickup ions and self-consistently reproduce the growth of both LH and RH Alfvén-cyclotron waves in agreement with linear theory. We show how the simultaneous generation of LH and RH waves can result in non-gyrotropic ion distributions and increased wave amplitudes, and how even trace quantities of negative pickup ions are able to generate an observable RH signal. Here, through comparing simulated and observed wave amplitudes, we are able to place the first constraints on the densities of Chlorine pickup ions in localised regions at Europa.« less

Hybrid simulations of positively and negatively charged pickup ions and cyclotron wave generation at Europa

DOE PAGES

Desai, Ravindra T.; Cowee, Misa; Wei, Hanying; ...

2017-09-19

In the vicinity of Europa, Galileo observed bursty Alfvén-cyclotron wave power at the gyrofrequencies of a number of species including K +, math formula, Na +, and Cl +, indicating the localised pickup of these species. Additional evidence for the presence of Chlorine was the occurrence of both left-hand (LH) and right-hand (RH) polarised transverse wave power near the Cl + gyrofrequency, thought to be due to the pickup of both Cl + and the easily formed Chlorine anion, Cl –. To test this hypothesis we use one-dimensional hybrid (kinetic ion, massless fluid electron) simulations for both positive and negativemore » pickup ions and self-consistently reproduce the growth of both LH and RH Alfvén-cyclotron waves in agreement with linear theory. We show how the simultaneous generation of LH and RH waves can result in non-gyrotropic ion distributions and increased wave amplitudes, and how even trace quantities of negative pickup ions are able to generate an observable RH signal. Here, through comparing simulated and observed wave amplitudes, we are able to place the first constraints on the densities of Chlorine pickup ions in localised regions at Europa.« less

Hybrid Simulations of Positively and Negatively Charged Pickup Ions and Cyclotron Wave Generation at Europa.

PubMed

Desai, R T; Cowee, M M; Wei, H; Fu, X; Gary, S P; Volwerk, M; Coates, A J

2017-10-01

In the vicinity of Europa, Galileo observed bursty Alfvén-cyclotron wave power at the gyrofrequencies of a number of species including K + , O 2+, Na + , and Cl + , indicating the localized pickup of these species. Additional evidence for the presence of chlorine was the occurrence of both left-hand (LH) and right-hand (RH) polarized transverse wave power near the Cl + gyrofrequency, thought to be due to the pickup of both Cl + and the easily formed chlorine anion, Cl - . To test this hypothesis, we use one-dimensional hybrid (kinetic ion, massless fluid electron) simulations for both positive and negative pickup ions and self-consistently reproduce the growth of both LH and RH Alfvén-cyclotron waves in agreement with linear theory. We show how the simultaneous generation of LH and RH waves can result in nongyrotropic ion distributions and increased wave amplitudes, and how even trace quantities of negative pickup ions are able to generate an observable RH signal. Through comparing simulated and observed wave amplitudes, we are able to place the first constraints on the densities of Chlorine pickup ions in localized regions at Europa.

Chemical fate and changes in mutagenic activity of antibiotics nitrofurazone and furazolidone during aqueous chlorination.

PubMed

Nakamura, Hitomi; Kawakami, Tsuyoshi; Niino, Tatsuhiro; Takahashi, Yasuo; Onodera, Sukeo

2008-12-01

Reactions of nitrofuran antibiotics (nitrofurazone (NFZ) and frazolidone (FZD)) with hypochlorite in aqueous solution were investigated under the conditions that simulate wastewater disinfection. The chlorination byproducts were determined by high performance liquid chromatography. At the levels of 5 microM, NFZ reacted rapidly with free chlorine in neutral pH (7.0), while the FZD-hypochlorite reaction was reasonably slow under the same pH. Nevertheless, the strong mutagenic parents disappeared completely after the hypochlorite reactions, and the chlorination byproducts were observed to exert a weak mutagenic effect on Salmonella typhimurium TA100 without S9-mix. The extent of the reactions depended on the chlorine dose, solution pH and compound structures.

Nocturnal chlorine radical reservoir species at noon during CalNex-LA 2010

NASA Astrophysics Data System (ADS)

Mielke, L. H.; Griffith, S. M.; Hansen, R. F.; Dusanter, S.; Stevens, P. S.; Flynn, J. H.; Grossberg, N.; Lefer, B. L.; Veres, P. R.; Roberts, J. M.; Gilman, J. B.; Kuster, W. C.; Young, C. J.; Washenfelder, R. A.; Cochran, A. K.; Osthoff, H. D.

2011-12-01

While the role of the hydroxyl radical (OH) in the oxidation of volatile organic compounds (VOCs) is relatively well understood and recognized, less attention has been paid to Cl as an oxidant even though Cl is more reactive towards VOCs than OH. In the troposphere, mixing ratios of chlorine atoms are quite low (103 - 105 atoms cm-3), making them difficult to quantify directly in the atmosphere. The presence of chlorine atoms has been inferred only indirectly using hydrocarbon ratios, but this approach works well only in very remote environments. In polluted coastal urban areas such as Los Angeles, modeling studies have indicated that Cl radical initiated chemistry can have a significant impact on ozone formation. Here, chlorine atoms are produced by reaction of OH with hydrochloric acid and by photolysis of photolabile chlorine containing species, such as the nocturnally formed nitryl chloride (ClNO2) and molecular chlorine (Cl2). In this presentation, measurements of ClNO2 and Cl2 mixing ratios using chemical ionization mass spectrometry (CIMS) at the Calnex-LA campaign ground site between May 15, and June 15, 2010 are presented with a focus on their daytime abundances and photolysis to produce Cl atoms. Photolysis of ClNO2 in the morning (7 am to 10 am) produced Cl atoms at a median rate of 6.1×105 atoms cm-3 s-1. Daytime ClNO2 was observed with a median mixing ratio of 14 parts-per-trillion by volume (pptv). Assuming a steady state between ClNO2 photolysis and its formation via the reaction of Cl atom with NO2, we calculate a median Cl atom concentration of up to 1×105 atoms cm-3, approximately 3% of that of OH, which was quantified by laser induced fluorescence. Implications of Cl on the oxidation of VOCs in the Los Angeles area will be discussed. For example, methane is oxidized by Cl at a relative rate of up to half that of OH under the conditions outlined above.

[Formation mechanism and chemical safety of nonintentional chemical substances present in chlorinated drinking water and wastewater].

PubMed

Onodera, Sukeo

2010-09-01

This paper reviews the formation mechanism and chemical safety of nonintentional chemical substances (NICS) present in chlorine-treated water containing organic contaminants. Undesirable compounds, i.e., NICS, may be formed under certain conditions when chlorine reacts with organic matter. The rate and extent of chlorine consumption with organics are strongly dependent on their chemical structures, particularly whether double bonds or sulfur and nitrogen atoms occur in the molecules. Organothiophosphorus pesticides (P=S type) are easily oxidized to their phosphorus compounds (P=O type) in chlorinated water containing HOCl as little as 0.5 mg/l, resulting in an increase in cholinesterase-inhibitory activity. Chlorination of phenols in water also produces a series of highly chlorinated compounds, including chlorophenols, chloroquinones, chlorinated carboxylic acids, and polychlorinated phenoxyphenols (PCPPs). In some of these chloroquinones, 2,6-dichloroalkylsemiquinones exhibit a strong mutagenic response as do positive controls used in the Ames test. 2-phenoxyphenols in these PCPPs are particularly interesting, as they are present in the chlorine-treated phenol solution and they are also precursors (predioxins) of the highly toxic chlorinated dioxins. Polynuclear aromatic hydrocarbons (PAHs) were found to undergo chemical changes due to hypochlorite reactions to give chloro-substituted PAHs, oxygenated (quinones) and hydroxylated (phenols) compounds, but they exhibit a lower mutagenic response. In addition, field work was performed in river water and drinking water to obtain information on chemical distribution and their safety, and the results are compared with those obtained in the model chlorination experiments.

Comparative antimicrobial activity, in vitro and in vivo, of soft N-chloramine systems and chlorhexidine.

PubMed Central

Selk, S H; Pogány, S A; Higuchi, T

1982-01-01

Antimicrobial activity of the following four new N-chloramine compounds was evaluated: two chlorinated simple amino acids, a chlorinated half-ester of succinic acid, and a chlorinated half-ester of glutaric acid. For comparison, the known bactericidal agents 3-chloro-4,4-dimethyl-2-oxazolidinone and chlorhexidine were evaluated by the same procedure. The contact germicidal efficiency screen was used to examine the in vitro bactericidal activity of all six compounds in the absence and presence of 5% horse serum or 5% Triton X-100. The four new compounds were found to have greater germicidal activity than the other compounds tested and to exhibit low toxicity and skin irritation values. The in vivo bactericidal activity was evaluated in two studies. In the occlusion test, three of the four new compounds plus chlorhexidine diacetate were tested. The N-chloramines were significantly superior to chlorhexidine in preventing the expansion of the normal flora under occlusion. In the scrub test, a gloved-hand wash method was used to compare the antimicrobial effect of a 1% solution of the chlorinated half-ester of succinic acid in triacetin with that of a commercial germicidal hand wash containing 4% chlorhexidine gluconate. The two preparations exhibited essentially the same hand-degerming activity. PMID:6805433

Chlorine inactivation of Tubifex tubifex in drinking water and the synergistic effect of sequential inactivation with UV irradiation and chlorine.

PubMed

Nie, Xiao-Bao; Li, Zhi-Hong; Long, Yuan-Nan; He, Pan-Pan; Xu, Chao

2017-06-01

The inactivation of Tubifex tubifex is important to prevent contamination of drinking water. Chlorine is a widely-used disinfectant and the key factor in the inactivation of T. tubifex. This study investigated the inactivation kinetics of chlorine on T. tubifex and the synergistic effect of the sequential use of chlorine and UV irradiation. The experimental results indicated that the Ct (concentration × time reaction ) concept could be used to evaluate the inactivation kinetics of T. tubifex with chlorine, thus allowing for the use of a simpler Ct approach for the assessment of T. tubifex chlorine inactivation requirements. The inactivation kinetics of T. tubifex by chlorine was found to be well-fitted to a delayed pseudo first-order Chick-Watson expression. Sequential experiments revealed that UV irradiation and chlorine worked synergistically to effectively inactivate T. tubifex as a result of the decreased activation energy, E a , induced by primary UV irradiation. Furthermore, the inactivation effectiveness of T. tubifex by chlorine was found to be affected by several drinking water quality parameters including pH, turbidity, and chemical oxygen demand with potassium permanganate (COD Mn ) concentration. High pH exhibited pronounced inactivation effectiveness and the decrease in turbidity and COD Mn concentrations contributed to the inactivation of T. tubifex. Copyright © 2017 Elsevier Ltd. All rights reserved.

Chlorinated Water Modulates the Development of Colorectal Tumors with Chromosomal Instability and Gut Microbiota in Apc-Deficient Mice

PubMed Central

Sasada, Tatsunari; Hinoi, Takao; Saito, Yasufumi; Adachi, Tomohiro; Takakura, Yuji; Kawaguchi, Yasuo; Sotomaru, Yusuke; Sentani, Kazuhiro; Oue, Naohide; Yasui, Wataru; Ohdan, Hideki

2015-01-01

The gastrointestinal tract is continuously exposed to a variety of chemicals and commensal bacteria. Recent studies have shown that changes in gut microbial populations caused by chlorine or other chemicals in the drinking water influence the development of human colorectal cancer, although the mechanism of tumorigenesis in the gut epithelium is obfuscated by the diversity of microflora and complexity of the tumor microenvironment. In this regard, mouse models that recapitulate human colorectal cancer are an invaluable tool. In this study, we used two conditional adenomatous polyposis coli (Apc) knockout mouse models to investigate the effect of chlorinated water on tumorigenesis in the digestive tract. Mice with colon-specific carcinoma—caused by either chromosomal (CDX2P 9.5-NLS Cre;Apc+/flox, abbreviated to CPC;Apc) or microsatellite (CDX2P9.5-G19Cre;Apcflox/flox and CDX2P9.5-G22Cre;Apcflox/flox) instability, respectively—were administered chlorinated (10.0 mg/L chlorine) or tap (0.7 mg/L chlorine) water and evaluated for colon polyp formation. In CPC;Apc mice given chlorinated drinking water, tumors tended to develop in the colon, whereas in those that drank tap water, tumors were mostly observed in the small intestine. There was no difference in the rate of tumor formation of CDX2P9.5-G19Cre;Apcflox/flox and CDX2P9.5-G22Cre;Apcflox/flox mice consuming chlorinated as compared to tap water, suggesting that microsatellite instability in the Apc gene does not significantly affect tumorigenesis. Chlorinated water altered the enteric environment by reducing the fecal populations of the obligatory anaerobes Clostridium perfringens and C. difficile, as well as species belonging to the Atopobium cluster, including Enterobacteriaceae and Staphylococcus sp., which was associated with colon tumorigenesis in CPC;Apc mice. These results suggest that differences in tumorigenesis among CPC;Apc mice consuming chlorinated versus tap water may be due to differences in gastrointestinal commensal populations. PMID:26186212

Chlorinated Water Modulates the Development of Colorectal Tumors with Chromosomal Instability and Gut Microbiota in Apc-Deficient Mice.

PubMed

Sasada, Tatsunari; Hinoi, Takao; Saito, Yasufumi; Adachi, Tomohiro; Takakura, Yuji; Kawaguchi, Yasuo; Sotomaru, Yusuke; Sentani, Kazuhiro; Oue, Naohide; Yasui, Wataru; Ohdan, Hideki

2015-01-01

The gastrointestinal tract is continuously exposed to a variety of chemicals and commensal bacteria. Recent studies have shown that changes in gut microbial populations caused by chlorine or other chemicals in the drinking water influence the development of human colorectal cancer, although the mechanism of tumorigenesis in the gut epithelium is obfuscated by the diversity of microflora and complexity of the tumor microenvironment. In this regard, mouse models that recapitulate human colorectal cancer are an invaluable tool. In this study, we used two conditional adenomatous polyposis coli (Apc) knockout mouse models to investigate the effect of chlorinated water on tumorigenesis in the digestive tract. Mice with colon-specific carcinoma--caused by either chromosomal (CDX2P 9.5-NLS Cre;Apc(+/flox), abbreviated to CPC;Apc) or microsatellite (CDX2P9.5-G19Cre;Apc(flox/flox) and CDX2P9.5-G22Cre;Apc(flox/flox)) instability, respectively--were administered chlorinated (10.0 mg/L chlorine) or tap (0.7 mg/L chlorine) water and evaluated for colon polyp formation. In CPC;Apc mice given chlorinated drinking water, tumors tended to develop in the colon, whereas in those that drank tap water, tumors were mostly observed in the small intestine. There was no difference in the rate of tumor formation of CDX2P9.5-G19Cre;Apc(flox/flox) and CDX2P9.5-G22Cre;Apc(flox/flox) mice consuming chlorinated as compared to tap water, suggesting that microsatellite instability in the Apc gene does not significantly affect tumorigenesis. Chlorinated water altered the enteric environment by reducing the fecal populations of the obligatory anaerobes Clostridium perfringens and C. difficile, as well as species belonging to the Atopobium cluster, including Enterobacteriaceae and Staphylococcus sp., which was associated with colon tumorigenesis in CPC;Apc mice. These results suggest that differences in tumorigenesis among CPC;Apc mice consuming chlorinated versus tap water may be due to differences in gastrointestinal commensal populations.

Influence of Plants on Chlorine Cycling in Terrestrial Environments

NASA Astrophysics Data System (ADS)

Montelius, Malin; Thiry, Yves; Marang, Laura; Ranger, Jacques; Cornelis, Jean-Thomas; Svensson, Teresia; Bastviken, David

2016-04-01

Chlorine (Cl), one of the 20 most abundant elements on Earth, is crucial for life as a regulator of cellular ionic strength and an essential co-factor in photosynthesis. Chlorinated organic compounds (Clorg) molecules are surprisingly abundant in soils, in fact many studies during the last decades show that Clorg typically account for more than 60% of the total soil Cl pool in boreal and temperate forest soils and frequently exceed chloride (Cl-) levels. The natural and primarily biotic formation of this Clorg pool has been confirmed experimentally but the detailed content of the Clorg pool and the reasons for its high abundance remains puzzling and there is a lack of Cl budgets for different ecosystems. Recently, the radioisotope 36Cl has caused concerns because of presence in radioactive waste, a long half-life (301 000 years), potential high mobility, and limited knowledge about Cl residence times, speciation and uptake by organisms in terrestrial environments. The chlorination of organic molecules may influence the pool of available Cl- to organisms and thereby the Cl cycling dynamics. This will prolong residence times of total Cl in the soil-vegetation system, which affects exposure times in radioactive 36Cl isotope risk assessments. We tested to what extent the dominating tree species influences the overall terrestrial Cl cycling and the balance between Cl- and Clorg. Total Cl and Clorg were measured in different tree compartments and soil horizons in the Breuil experimental forest, Bourgogne, established in 1976 and located at Breuil-Chenue in Eastern France. The results from this field experiment show how the dominating tree species affected Cl cycling and accumulation over a time period of 30 years. Cl uptake by trees as well as content of both total Cl and Clorg in soil humus was much higher in experimental plots with coniferous forests compared to deciduous forests. The amounts of Clorg found in plant tissue indicate significant Clorg production inside trees in addition to substantial soil production of Clorg. A large and tree species dependent "luxury" Cl uptake, rapidly released through the leaves and returned to the soil as throughfall, was indicated for some tree species. The physiology of dominating tree species, along with tree-related soil microbial communities, thus appears more important for the local Cl levels and cycling than atmospheric Cl deposition.

The stability of chlorinated, brominated, and iodinated haloacetamides in drinking water.

PubMed

Ding, Shunke; Chu, Wenhai; Krasner, Stuart W; Yu, Yun; Fang, Chao; Xu, Bin; Gao, Naiyun

2018-06-13

Haloacetamides (HAMs), a group of nitrogenous disinfection byproducts (N-DBPs), can decompose to form corresponding intermediate products and other DBPs. The stability of ten different HAMs, including two chlorinated, five brominated, and three iodinated species was investigated with and without the presence of chlorine, chloramines, and reactive solutes such as quenching agents. The HAM basic hydrolysis and chlorination kinetics were well described by a second-order kinetics model, including first-order in HAM and hydroxide and first-order in HAM and hypochlorite, respectively, whereas the HAM neutral hydrolysis kinetic was first-order in HAM. Furthermore, HAMs decompose instantaneously when exposed to hypochlorite, which was almost two and nine orders of magnitude faster than HAM basic and neutral hydrolysis, respectively. In general, HAM hydrolysis and chlorination rates both increased with increasing pH and the number of halogens substituted on the methyl group. Moreover, chlorinated HAMs are more unstable than their brominated analogs, followed by the iodinated ones, due to the decrease in the electron-withdrawing inductive effect from chlorine to iodine atom. During hydrolysis, HAMs mainly directly decompose into the corresponding haloacetic acids (HAAs) via a nucleophilic reaction between the carbonyl carbon and hydroxide. For HAM chlorination reactions, hypochlorite reacts with HAMs to form the N-chloro-HAMs (N-Cl-HAMs) via Cl + transfer from chlorine to the amide nitrogen. N-Cl-HAMs can further degrade to form HAAs via hypochlorous acid addition. In contrast, the reactions between chloramines and HAMs were found to be insignificant. Additionally, four common quenching agents, including sodium sulfite, sodium thiosulfate, ascorbic acid, and ammonium chloride, were demonstrated to expedite HAM degradation, whereas ammonium chloride was the least influential among the four. Taft linear free energy relationships were established for both HAM hydrolysis and chlorination reactions, based on which the hydrolysis and chlorination rate constants for three monohaloacetamides were estimated. The hydrolysis and chlorination rates of 13 HAMs decreased in the following order: TCAM > BDCAM > DBCAM > TBAM > DCAM > BCAM > DBAM > CIAM > BIAM > DIAM > MCAM > MBAM > MIAM (where C = chloro, B = bromo, I = iodo, T = tri, D = di, M = mono). Lastly, using the HAM kinetic model established in this study, HAM half-lifes in drinking water distribution systems can be predicted on the basis of pH and residual chlorine concentration. Copyright © 2018 Elsevier Ltd. All rights reserved.

Fingerprints of endogenous process on Europa through linear spectral modeling of ground-based observations (ESO/VLT/SINFONI)

NASA Astrophysics Data System (ADS)

Ligier, Nicolas; Carter, John; Poulet, François; Langevin, Yves; Dumas, Christophe; Gourgeot, Florian

2016-04-01

Jupiter's moon Europa harbors a very young surface dated, based on cratering rates, to 10-50 M.y (Zahnle et al. 1998, Pappalardo et al. 1999). This young age implies rapid surface recycling and reprocessing, partially engendered by a global salty subsurface liquid ocean that could result in tectonic activity (Schmidt et al. 2011, Kattenhorn et al. 2014) and active plumes (Roth et al. 2014). The surface of Europa should contain important clues about the composition of this sub-surface briny ocean and about the potential presence of material of exobiological interest in it, thus reinforcing Europa as a major target of interest for upcoming space missions such as the ESA L-class mission JUICE. To perform the investigation of the composition of the surface of Europa, a global mapping campaign of the satellite was performed between October 2011 and January 2012 with the integral field spectrograph SINFONI on the Very Large Telescope (VLT) in Chile. The high spectral binning of this instrument (0.5 nm) is suitable to detect any narrow mineral signature in the wavelength range 1.45-2.45 μm. The spatially resolved spectra we obtained over five epochs nearly cover the entire surface of Europa with a pixel scale of 12.5 by 25 m.a.s (~35 by 70 km on Europa's surface), thus permitting a global scale study. Until recently, a large majority of studies only proposed sulfate salts along with sulfuric acid hydrate and water-ice to be present on Europa's surface. However, recent works based on Europa's surface coloration in the visible wavelength range and NIR spectral analysis support the hypothesis of the predominance of chlorine salts instead of sulfate salts (Hand & Carlson 2015, Fischer et al. 2015). Our linear spectral modeling supports this new hypothesis insofar as the use of Mg-bearing chlorines improved the fits whatever the region. As expected, the distribution of sulfuric acid hydrate is correlated to the Iogenic sulfur ion implantation flux distribution (Hendrix et al. 2011, Dalton et al. 2013). However, the distribution of chlorine species is inconsistent with this process and together with abundance maps of different sizes of crystalline water-ice grain exhibits clear spatial inhomogeneities in their distribution, hence suggesting an endogenous origin for these species. Abundance maps will be presented and the question of the distribution and the formation of these species will be addressed.

Detection, formation and occurrence of 13 new polar phenolic chlorinated and brominated disinfection byproducts in drinking water.

PubMed

Pan, Yang; Wang, Ying; Li, Aimin; Xu, Bin; Xian, Qiming; Shuang, Chendong; Shi, Peng; Zhou, Qing

2017-04-01

Recently, 13 new polar phenolic chlorinated and brominated disinfection byproducts (Cl- and Br-DBPs) were identified and quantified in simulated chlorinated drinking water by adopting product ion scan, precursor ion scan, and multiple reaction monitoring (MRM) analyses using ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry (UPLC/ESI-tqMS). The 13 new DBPs have been drawing increasing concern not only because they possess significantly higher growth inhibition, developmental toxicity, and chronic cytotoxicity than commonly known aliphatic DBPs, but also because they act as intermediate DBPs that can decompose to form the U.S. EPA regulated DBPs. In this study, through MS parameter optimization of the UPLC/ESI-tqMS MRM analysis, the instrument detection and quantitation limits of the 13 new DBPs were substantially lowered to 0.42-6.44 and 1.35-16.51 μg/L, respectively. The total levels of the 13 new DBPs formed in chlorination were much higher than those formed in chloramination within a contact time of 3 d. In chlorination, the 13 new DBPs formed quickly and decomposed rapidly, and their total concentration kept on decreasing with contact time. In chloramination, the levels of the dominant species (i.e., trihalo-phenols) firstly increased and then decreased with contact time, whereas the levels of the other new DBPs were relatively low and kept on increasing with contact time. An increasing of pH from 6.0 to 9.0 decreased the formation of the 13 new DBPs by 57.8% and 62.3% in chlorination and chloramination, respectively. Gallic acid was found to be present in various simulated and real source water samples and was demonstrated to be a precursor of the 13 new DBPs with elucidated formation pathways. Furthermore, 12 of the 13 new DBPs were detected in 16 tap water samples obtained from major cities in East China, at total levels from 9.5 to 329.8 ng/L. The concentrations of the new DBPs were higher in samples with source waters containing higher bromide levels. Ozone-activated carbon treatment prior to disinfection might reduce the formation of the new DBPs since it was effective in precursor reduction. Copyright © 2017 Elsevier Ltd. All rights reserved.

Myeloperoxidase: a target for new drug development?

PubMed Central

Malle, E; Furtmüller, P G; Sattler, W; Obinger, C

2007-01-01

Myeloperoxidase (MPO), a member of the haem peroxidase-cyclooxygenase superfamily, is abundantly expressed in neutrophils and to a lesser extent in monocytes and certain type of macrophages. MPO participates in innate immune defence mechanism through formation of microbicidal reactive oxidants and diffusible radical species. A unique activity of MPO is its ability to use chloride as a cosubstrate with hydrogen peroxide to generate chlorinating oxidants such as hypochlorous acid, a potent antimicrobial agent. However, evidence has emerged that MPO-derived oxidants contribute to tissue damage and the initiation and propagation of acute and chronic vascular inflammatory disease. The fact that circulating levels of MPO have been shown to predict risks for major adverse cardiac events and that levels of MPO-derived chlorinated compounds are specific biomarkers for disease progression, has attracted considerable interest in the development of therapeutically useful MPO inhibitors. Today, detailed information on the structure of ferric MPO and its complexes with low- and high-spin ligands is available. This, together with a thorough understanding of reaction mechanisms including redox properties of intermediates, enables a rationale attempt in developing specific MPO inhibitors that still maintain MPO activity during host defence and bacterial killing but interfere with pathophysiologically persistent activation of MPO. The various approaches to inhibit enzyme activity of MPO and to ameliorate adverse effects of MPO-derived oxidants will be discussed. Emphasis will be put on mechanism-based inhibitors and high-throughput screening of compounds as well as the discussion of physiologically useful HOCl scavengers. PMID:17592500

The occurrence of chlorine in serpentine minerals

USGS Publications Warehouse

Miura, Y.; Rucklidge, J.; Nord, G.L.

1981-01-01

Partially serpentinized dunites containing small amounts of Chlorine (< 0.5%) from Dumont, Quebec, and Horoman, Hokkaido, Japan, and one containing less than 0.05% Chlorine from Higashi-Akaishi-Yama, Ehime, Japan have been examined using the electron probe microanalyzer and scanning transmission electron microscope with X-ray analytical capabilities. Chlorine was found together with Si, Mg, Ca and Fe in the serpentine minerals of the Dumont and Hokkaido dunites but not in the Ehime dunite. Chlorine is found associated only with the most finely crystalline facies of the serpentine (grain size less than 10 nm). The Ehime dunite contained no such fine grained serpentine, and was thus effectively chlorine-free, as are the coarser grained serpentines of the other samples. The finegrained chlorine-bearing serpentine also has a much higher concentration of Fe, and can contain smaller amounts of Ca, Ni and Mn than the coarse-grained variety as well as minute awaruite (FeNi3) grains. This fine-grained serpentine probably represents an early stage in the transformation of olivine to serpentine, with chlorine from hydrothermal solutions assisting the necessary chemical changes. The Cl increases the reaction rate by lowering the activation barrier to reaction by the introduction of reaction steps. ?? 1981 Springer-Verlag.

Conventional Treatment Options for HABs Impacted Waters

EPA Science Inventory

This presentation discusses (1) the removal of cyanobacterial cells through coagulation, flocculation, sedimentation and filtration, (2) the control of cyanobacterial toxins by powdered activated carbon, (3) the control of cyanobacterial toxins by chlorine, UV, ozone, chlorine di...

[Chlorine coatings on skin surfaces. II. Parameters influencing the coating strength].

PubMed

Gottardi, W; Karl, A

1991-05-01

Although active chlorine compounds have been used for more than 140 years (Semmelweis, 1848) as a skin disinfectant the phenomenon of the "chlorine covers" not earlier than 1988 has been described for the first time (Hyg. + Med. 13 (1988) 157). It deals with a chemical alteration of the uppermost skin layer which comes apparent in an oxydizing action against aqueous iodide. Its origin is chlorine covalently bound in the form of N-Cl functions to the protein matrix of the horny skin. Since the chlorine covers exhibit a persistant disinfecting activity which might be important for practice, the factors influencing their strength have been established. The most important are: the kind of the chlorine system, the concentration (oxydation capacity), pH, temperature and the volume of the used solution, the time of action, the application technique and the state of the skin. Variations of the latter can be observed at different skin areas of one and the same person as well as at the same areas of different persons, and result in differences of the cover strength up to 100%. The stability on dry skin is very good, showing a decomposition rate of approximately 1.2% per hour. However on skin surfaces moistened by sweat (e.g. hands covered by surgeons gloves) the chlorine cover is disingrated much more faster (decomposition rate: 40-50% per hour). Washing with soap as well as the action of alcohols cause virtually no decrease in the cover strength, while wetting by solutions of reducing agents (e.g. thiosulfate, cysteine, iodide) provokes a fast decomposition suitable for removing the chlorine covers.(ABSTRACT TRUNCATED AT 250 WORDS)

Using digital flow cytometry to assess the degradation of three cyanobacteria species after oxidation processes.

PubMed

Wert, Eric C; Dong, Mei Mei; Rosario-Ortiz, Fernando L

2013-07-01

Depending on drinking water treatment conditions, oxidation processes may result in the degradation of cyanobacteria cells causing the release of toxic metabolites (microcystin), odorous metabolites (MIB, geosmin), or disinfection byproduct precursors. In this study, a digital flow cytometer (FlowCAM(®)) in combination with chlorophyll-a analysis was used to evaluate the ability of ozone, chlorine, chlorine dioxide, and chloramine to damage or lyse cyanobacteria cells added to Colorado River water. Microcystis aeruginosa (MA), Oscillatoria sp. (OSC) and Lyngbya sp. (LYN) were selected for the study due to their occurrence in surface water supplies, metabolite production, and morphology. Results showed that cell damage was observed without complete lysis or fragmentation of the cell membrane under many of the conditions tested. During ozone and chlorine experiments, the unicellular MA was more susceptible to oxidation than the filamentous OSC and LYN. Rate constants were developed based on the loss of chlorophyll-a and oxidant exposure, which showed the oxidants degraded MA, OSC, and LYN according to the order of ozone > chlorine ~ chlorine dioxide > chloramine. Digital and binary images taken by the digital flow cytometer provided qualitative insight regarding cell damage. When applying this information, drinking water utilities can better understand the risk of cell damage or lysis during oxidation processes. Copyright © 2013 Elsevier Ltd. All rights reserved.

Health Impacts of Environmental Mycobacteria†

PubMed Central

Primm, Todd P.; Lucero, Christie A.; Falkinham, Joseph O.

2004-01-01

Environmental mycobacteria are emerging pathogens causing opportunistic infections in humans and animals. The health impacts of human-mycobacterial interactions are complex and likely much broader than currently recognized. Environmental mycobacteria preferentially survive chlorination in municipal water, using it as a vector to infect humans. Widespread chlorination of water has likely selected more resistant environmental mycobacteria species and potentially explains the shift from M. scrofulaceum to M. avium as a cause of cervical lymphadenitis in children. Thus, human activities have affected mycobacterial ecology. While the slow growth and hydrophobicity of environmental mycobacteria appear to be disadvantages, the unique cell wall architecture also grants high biocide and antibiotic resistance, while hydrophobicity facilitates nutrient acquisition, biofilm formation, and spread by aerosolization. The remarkable stress tolerance of environmental mycobacteria is the major reason they are human pathogens. Environmental mycobacteria invade protozoans, exhibiting parasitic and symbiotic relationships. The molecular mechanisms of mycobacterial intracellular pathogenesis in animals likely evolved from similar mechanisms facilitating survival in protozoans. In addition to outright infection, environmental mycobacteria may also play a role in chronic bowl diseases, allergies, immunity to other pulmonary infections, and the efficacy of bacillus Calmette-Guerin vaccination. PMID:14726457

In Vitro and In Vivo Demonstration of Human-Ovarian-Cancer Necrosis through a Water-Soluble and Near-Infrared-Absorbing Chlorin.

PubMed

Marydasan, Betsy; Madhuri, Bollapalli; Cherukommu, Shirisha; Jose, Jedy; Viji, Mambattakkara; Karunakaran, Suneesh C; Chandrashekar, Tavarekere K; Rao, Kunchala Sridhar; Rao, Ch Mohan; Ramaiah, Danaboyina

2018-06-14

With the objective of developing efficient sensitizers for therapeutic applications, we synthesized a water-soluble 5,10,15,20-tetrakis(3,4-dihydroxyphenyl)chlorin (TDC) and investigated its in vitro and in vivo biological efficacy, comparing it with the commercially available sensitizers. TDC showed high water solubility (6-fold) when compared with that of Foscan and exhibited excellent triplet-excited-state (84%) and singlet-oxygen (80%) yields. In vitro photobiological investigations in human-ovarian-cancer cell lines SKOV-3 showed high photocytotoxicity, negligible dark toxicity, rapid cellular uptake, and specific localization of TDC in neoplastic cells as assessed by flow-cytometric cell-cycle and propidium iodide staining analysis. The photodynamic effects of TDC include confirmed reactive-oxygen-species-induced mitochondrial damage leading to necrosis in SKOV-3 cell lines. The in vivo photodynamic activity in nude-mouse models demonstrated abrogation of tumor growth without any detectable pathology in the skin, liver, spleen, or kidney, thereby demonstrating TDC application as an efficient and safe photosensitizer.

Health impacts of environmental mycobacteria.

PubMed

Primm, Todd P; Lucero, Christie A; Falkinham, Joseph O

2004-01-01

Environmental mycobacteria are emerging pathogens causing opportunistic infections in humans and animals. The health impacts of human-mycobacterial interactions are complex and likely much broader than currently recognized. Environmental mycobacteria preferentially survive chlorination in municipal water, using it as a vector to infect humans. Widespread chlorination of water has likely selected more resistant environmental mycobacteria species and potentially explains the shift from M. scrofulaceum to M. avium as a cause of cervical lymphadenitis in children. Thus, human activities have affected mycobacterial ecology. While the slow growth and hydrophobicity of environmental mycobacteria appear to be disadvantages, the unique cell wall architecture also grants high biocide and antibiotic resistance, while hydrophobicity facilitates nutrient acquisition, biofilm formation, and spread by aerosolization. The remarkable stress tolerance of environmental mycobacteria is the major reason they are human pathogens. Environmental mycobacteria invade protozoans, exhibiting parasitic and symbiotic relationships. The molecular mechanisms of mycobacterial intracellular pathogenesis in animals likely evolved from similar mechanisms facilitating survival in protozoans. In addition to outright infection, environmental mycobacteria may also play a role in chronic bowl diseases, allergies, immunity to other pulmonary infections, and the efficacy of bacillus Calmette-Guerin vaccination.

Evaluating fluorescence spectroscopy as a tool to characterize cyanobacteria intracellular organic matter upon simulated release and oxidation in natural water.

PubMed

Korak, Julie A; Wert, Eric C; Rosario-Ortiz, Fernando L

2015-01-01

Intracellular organic matter (IOM) from cyanobacteria may be released into natural waters following cell death in aquatic ecosystems and during oxidation processes in drinking water treatment plants. Fluorescence spectroscopy was evaluated to identify the presence of IOM from three cyanobacteria species during simulated release into natural water and following oxidation processes (i.e. ozone, free chlorine, chloramine, chlorine dioxide). Peak picking and the fluorescence index (FI) were explored to determine which IOM components (e.g., pigments) provide unique and persistent fluorescence signatures with minimal interferences from the background dissolved organic matter (DOM) found in Colorado River water (CRW). When IOM was added to ultrapure water, the fluorescence signature of the three cyanobacteria species showed similarities to each other. Each IOM exhibited a strong protein-like fluorescence and fluorescence at Ex 370 nm and Em 460 nm (FDOM), where commercial fluorescence sensors monitor. All species also had strong phycobiliprotein fluorescence (i.e. phycocyanin or phycoerythrin) in the higher excitation range (500-650 nm). All three IOM isolates had FI values greater than 2. When IOM was added to CRW, phycobiliprotein fluorescence was quenched through interactions between IOM and CRW-DOM. Mixing IOM and CRW demonstrated that protein-like and FDOM intensity responses were not a simple superposition of the starting material intensities, indicating that interactions between IOM and CRW-DOM fluorescing moieties were important. Fluorescence intensity in all regions decreased with exposure to ozone, free chlorine, and chlorine dioxide, but the FI still indicated compositional differences compared to CRW-DOM. The phycobiliproteins in IOM are not promising as a surrogate for IOM release, because their fluorescence intensity is quenched by interactions with DOM and decreased during oxidation processes. Increases in both FDOM intensity and FI are viable qualitative indicators of IOM release in natural waters and following oxidation and may provide a more robust real-time indication of the presence of IOM than conventional dissolved organic carbon or UV absorbance measurements.

Studies on toxicity of OTEC plant components on Eucalanus sp. from the Gulf of Mexico. Annual report, October 1980-September 1981

DOE Office of Scientific and Technical Information (OSTI.GOV)

Venkataramiah, A.; Lakshmi, G.J.; Best, C.

1981-10-01

These bioassays were undertaken as a part of the environmental impact studies of the pollutants from the Ocean Thermal Energy Conversion (OTEC) plants. Ammonia and chlorine were selected as toxicants. Eucalanus pileatus and E. elongatus were used as experimental animals because of their importance in the food cycle of the commercial fisheries. A considerable amount of time was devoted to become familiar with the culturing procedures of the Eucalanus sp. and to adapt those procedures to laboratory needs. Algae cultures were developed with Rhizosolenia alata and Thalassiosira fluviatilis for use as food for the copepods. Collection and maintenance techniques formore » E. pileatus and E. elongatus were developed. Culturing operations were successful through the F/sub 1/ generation for E. pileatus. A mini-flow-through seawater bioassay system was designed and built for these studies. The system can also be used for running the bioassays with small organisms, embryos and larvae of fish, etc. In the chronic exposure the survival rates in the sublethal concentrations did not change significantly from the acute ammonia and chlorine bioassays. However, in the incipient lethal concentrations of ammonia and chlorine the survival rates decreased gradually. It was concluded that oceanic species like sargassum shrimp (Latreutes fucorum), filefish (Monocanthus hispidus) and copepods Eucalanus sp. were apparently more sensitive to toxicants than the mullet (Mugil cephalus) collected in inshore waters. Within the same species the tolerance to toxicity increased significantly with increasing size (age). Among the oceanic forms, sargassum shrimp appeared to be the hardiest of all species with filefish being most sensitive to ammonia. In chlorine sargassum shrimp exhibited a much greater tolerance toward ammonia than the copepods. The tolerance limits of small mullet (0.3 and 0.4g), which evidently were fresh arrivals from offshore, responded similarly to both toxicants as sargassum shrimp.« less

Effects of thermal treatment on halogenated disinfection by-products in drinking water.

PubMed

Wu, W W; Benjamin, M M; Korshin, G V

2001-10-01

The influence of heating or boiling on the formation and behavior of disinfection by-products (DBPs) was investigated in DBP-spiked reagent water, municipal tap water, and synthetic water containing chlorinated aquatic humic substances. Thermal cleavage of larger halogenated species leads to both formation of smaller chlorinated molecules (including THMs and HAAs) and dechlorination of organics. In parallel with their formation from larger molecules, THMs can be volatilized, and this latter process dominates the change in their concentration when water is boiled. HAAs are not volatile, but they can be destroyed by chemical reactions at elevated temperatures, with the net effect being loss of trihalogenated HAAs and either formation or loss of less chlorinated HAAs. Although other identifiable DBPs can be generated at slightly elevated temperatures, in most cases their concentrations decline dramatically when the solution is heated.

Monte Carlo analysis of uncertainty propagation in a stratospheric model. 2: Uncertainties due to reaction rates

NASA Technical Reports Server (NTRS)

Stolarski, R. S.; Butler, D. M.; Rundel, R. D.

1977-01-01

A concise stratospheric model was used in a Monte-Carlo analysis of the propagation of reaction rate uncertainties through the calculation of an ozone perturbation due to the addition of chlorine. Two thousand Monte-Carlo cases were run with 55 reaction rates being varied. Excellent convergence was obtained in the output distributions because the model is sensitive to the uncertainties in only about 10 reactions. For a 1 ppby chlorine perturbation added to a 1.5 ppby chlorine background, the resultant 1 sigma uncertainty on the ozone perturbation is a factor of 1.69 on the high side and 1.80 on the low side. The corresponding 2 sigma factors are 2.86 and 3.23. Results are also given for the uncertainties, due to reaction rates, in the ambient concentrations of stratospheric species.

LOWLY CHLORINATED DIBENZODIOXINS AS TEQ INDICATORS. A COMBINED APPROACH USING SPECTROSCOPIC MEASUREMENTS WITH DLR JET-REMPI AND STATISTICAL CORRELATIONS WITH WASTE COMBUSTOR EMISSIONS

EPA Science Inventory

Continuous monitoring of trace gas species in incineration processes can serve two purposes: (i) monitoring precursors of polychlorinated dibenzodioxin and polychlorinated dibenzofuran (PCDD/F) or other indicator species in the raw gas will enable use of their on-line signals for...

Short-, Medium-, and Long-Chain Chlorinated Paraffins in Wildlife from Paddy Fields in the Yangtze River Delta.

PubMed

Du, Xinyu; Yuan, Bo; Zhou, Yihui; Benskin, Jonathan P; Qiu, Yanling; Yin, Ge; Zhao, Jianfu

2018-02-06

Short-chain chlorinated paraffins (SCCPs) were added to Annex A of the Stockholm Convention on Persistent Organic Pollutants in April, 2017. As a consequence of this regulation, increasing production and usage of alternatives, such as medium- and long-chain chlorinated paraffins (MCCPs and LCCPs, respectively), is expected. Little is known about the environmental fate and behavior of MCCPs and LCCPs. In the present study, SCCPs, MCCPs, and LCCPs were analyzed in nine wildlife species from paddy fields in the Yangtze River Delta, China, using atmospheric pressure chemical ionization-quadrupole time-of-flight mass spectrometry. SCCPs, MCCPs, and LCCPs were detected in all samples at concentrations ranging from <91-43 000, 96-33 000, and 14-10 000 ng/g lipid, respectively. Most species contained primarily MCCPs (on average 44%), with the exception of collared scops owl and common cuckoo, in which SCCPs (43%) accumulated to a significantly (i.e., p < 0.05) greater extent than MCCPs (40%). Cl 6 groups were dominant in most species except for yellow weasel and short-tailed mamushi, which contained primarily Cl 7 groups. Principal components analysis, together with CP concentrations and carbon stable isotope analysis showed that habitat and feeding habits were key factors driving CP accumulation and congener group patterns in wildlife. This is the first report of LCCP exposure in wildlife and highlights the need for data on risks associated with CP usage.

Short-chain chlorinated paraffins (SCCPs) in a freshwater food web from Dianshan Lake: Occurrence level, congener pattern and trophic transfer.

PubMed

Zhou, Yihui; Yin, Ge; Du, Xinyu; Xu, Maoying; Qiu, Yanling; Ahlqvist, Patrik; Chen, Qiaofeng; Zhao, Jianfu

2018-02-15

Short-chain chlorinated paraffins (SCCPs) are new group of persistent organic pollutants (POPs) listed in the Stockholm Convention. The Yangtze River Delta is among the industrially most developed areas in China, supporting a large production and consumption of chlorinated paraffins (CPs). Despite this, there is very limited data on the environmental exposure of SCCPs from the region. This study analyzed SCCPs in 14 wild aquatic organisms from Dianshan Lake, Shanghai, China. The concentrations of total SCCPs ranged from 10 to 1300μgg -1 lipid weight, with significantly higher levels (p<0.05) in benthic (benthic fish and invertebrates) than in non-benthic species (pelagic and mesopelagic fish). The abundance of C 10 congeners was much higher in the benthic species compared to in the non-benthic species. The calculated trophic magnification factors (TMFs) of SCCP congeners varied from 1.19 (C 10 H 12 Cl 10 ) to 1.57 (C 13 H 20 Cl 8 ). The TMFs were significantly correlated (p<0.01) with carbon-chain length in a positive linear relationship and with Log K ow in a parabolic curve relationship. Considering the high concentrations of SCCPs in wild aquatic organisms and the trophic magnification observed in the freshwater food web, further studies should be undertaken to assess the environmental fate of SCCPs and the public health risk in the Yangtze River Delta. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Chlorination of bisphenol A: non-targeted screening for the identification of transformation products and assessment of estrogenicity in generated water.

PubMed

Bourgin, Marc; Bichon, Emmanuelle; Antignac, Jean-Philippe; Monteau, Fabrice; Leroy, Gaëla; Barritaud, Lauriane; Chachignon, Mathilde; Ingrand, Valérie; Roche, Pascal; Le Bizec, Bruno

2013-11-01

Besides the performance of water treatments on the removal of micropollutants, concern about the generation of potential biologically active transformation products has been growing. Thus, the detection and structural elucidation of micropollutants transformation products have turned out to be major issues to evaluate comprehensively the efficiency of the processes implemented for drinking water treatment. However, most of existing water treatment studies are carried out at the bench scale with high concentrations and simplified conditions and thus do not reflect realistic conditions. Conversely, this study describes a non-targeted profiling approach borrowed from metabolomic science, using liquid chromatography coupled to high-resolution mass spectrometry, in order to reveal potential chlorination products of bisphenol A (BPA) in real water samples spiked at 50μgL(-1). Targeted measurements first evidenced a fast removal of BPA (>99%) by chlorination with sodium hypochlorite (0.8mgL(-1)) within 10min. Then, the developed differential global profiling approach enabled to reveal 21 chlorination products of BPA. Among them, 17 were brominated compounds, described for the first time, demonstrating the potential interest of this innovative methodology applied to environmental sciences. In parallel to the significant removal of BPA, the estrogenic activity of water samples, evaluated by ER-CALUX assay, was found to significantly decrease after 10min of chlorination. These results confirm that chlorination is effective at removing BPA in drinking water and they may indicate that the generated compounds have significantly lower estrogenic activity. Copyright © 2013 Elsevier Ltd. All rights reserved.

Approaches for the Analysis of Chlorinated Lipids

PubMed Central

Wang, Wen-yi; Albert, Carolyn J.; Ford, David A.

2013-01-01

Leukocytes are key cellular mediators of human diseases through their role in inflammation. Identifying unique molecules produced by leukocytes may provide new biomarkers and mechanistic insights into the role of leukocytes in disease. Chlorinated lipids are generated as a result of myeloperoxidase-containing leukocyte-derived hypochlorous acid targeting the vinyl ether bond of plasmalogens. The initial product of this reaction is α-chlorofatty aldehyde. α -Chlorofatty aldehyde is both oxidized to α-chlorofatty acid and reduced to α-chlorofatty alcohol by cellular metabolism. This review focuses on the separation techniques and quantitative analysis for these chlorinated lipids. For α-chlorofatty acid the negative charge of carboxylic acids is exploited to detect the chlorinated lipid species of these acids by electrospray ionization mass spectrometry in the negative ion mode. In contrast, α-chlorofatty aldehyde and α-chlorofatty alcohol are converted to pentafluorobenzyl oxime and pentafluorobenzoyl ester derivatives, which are detected by negative ion-chemical ionization mass spectrometry. These two detection methods coupled with the use of stable isotope internal standards and either liquid chromatography or gas chromatography provide highly sensitive analytical approaches to measure these novel lipids. PMID:24056259

Release of sulfur and chlorine during cofiring RDF and coal in an internally circulating fluidized bed

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiaolin Wei; Yang Wang; Dianfu Liu

2009-03-15

An internally circulating fluidized bed (ICFB) was applied to investigate the behavior of chlorine and sulfur during cofiring RDF and coal. The pollutant emissions in the flue gas were measured by Fourier transform infrared (FTIR) spectrometry (Gasmet DX-3000). In the tests, the concentrations of the species CO, CO{sub 2}, HCl, and SO{sub 2} were measured online. Results indicated when cofiring RDF and char, due to the higher content of chlorine in RDF, the formation of HCl significantly increases. The concentration of SO{sub 2} is relatively low because alkaline metal in the fuel ash can absorb SO{sub 2}. The concentration ofmore » CO emission during firing pure RDF is relatively higher and fluctuates sharply. With the CaO addition, the sulfur absorption by calcium quickly increases, and the desulfurization ratio is bigger than the dechlorination ratio. The chemical equilibrium method is applied to predict the behavior of chlorine. Results show that gaseous HCl emission increases with increasing RDF fraction, and gaseous KCl and NaCl formation might occur. 35 refs., 18 figs., 2 tabs.« less

WATER INGESTION DURING SWIMMING ACTIVITIES IN A POOL: A PILOT STUDY

EPA Science Inventory

Chloroisocyanurates are commonly added to outdoor swimming pools to stabilize chlorine disinfectants. The chloroisocyanurates decompose slowly to release chlorine and cyanuric acid. Studies conducted to determine if the chloroisocyanurates might be toxic to swimmers showed that...

Degradation of sulfamethoxazole using ozone and chlorine dioxide - Compound-specific stable isotope analysis, transformation product analysis and mechanistic aspects.

PubMed

Willach, Sarah; Lutze, Holger V; Eckey, Kevin; Löppenberg, Katja; Lüling, Michelle; Terhalle, Jens; Wolbert, Jens-Benjamin; Jochmann, Maik A; Karst, Uwe; Schmidt, Torsten C

2017-10-01

The sulfonamide antibiotic sulfamethoxazole (SMX) is a widely detected micropollutant in surface and groundwaters. Oxidative treatment with e.g. ozone or chlorine dioxide is regularly applied for disinfection purposes at the same time exhibiting a high potential for removal of micropollutants. Especially for nitrogen containing compounds such as SMX, the related reaction mechanisms are largely unknown. In this study, we systematically investigated reaction stoichiometry, product formation and reaction mechanisms in reactions of SMX with ozone and chlorine dioxide. To this end, the neutral and anionic SMX species, which may occur at typical pH-values of water treatment were studied. Two moles of chlorine dioxide and approximately three moles of ozone were consumed per mole SMX degraded. Oxidation of SMX with ozone and chlorine dioxide leads in both cases to six major transformation products (TPs) as revealed by high-resolution mass spectrometry (HRMS). Tentatively formulated TP structures from other studies could partly be confirmed by compound-specific stable isotope analysis (CSIA). However, for one TP, a hydroxylated SMX, it was not possible by HRMS alone to identify whether hydroxylation occurred at the aromatic ring, as suggested in literature before, or at the anilinic nitrogen. By means of CSIA and an analytical standard it was possible to identify sulfamethoxazole hydroxylamine unequivocally as one of the TPs of the reaction of SMX with ozone as well as with chlorine dioxide. H-abstraction and electron transfer at the anilinic nitrogen are suggested as likely initial reactions of ozone and chlorine dioxide, respectively, leading to its formation. Oxidation of anionic SMX with ozone did not show any significant isotopic fractionation whereas the other reactions studied resulted in a significant carbon isotope fractionation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effects of conventional ozonation and electro-peroxone pretreatment of surface water on disinfection by-product formation during subsequent chlorination.

PubMed

Mao, Yuqin; Guo, Di; Yao, Weikun; Wang, Xiaomao; Yang, Hongwei; Xie, Yuefeng F; Komarneni, Sridhar; Yu, Gang; Wang, Yujue

2018-03-01

The electro-peroxone (E-peroxone) process is an emerging ozone-based electrochemical advanced oxidation process that combines conventional ozonation with in-situ cathodic hydrogen peroxide (H 2 O 2 ) production for oxidative water treatment. In this study, the effects of the E-peroxone pretreatment on disinfection by-product (DBP) formation from chlorination of a synthetic surface water were investigated and compared to conventional ozonation. Results show that due to the enhanced transformation of ozone (O 3 ) to hydroxyl radicals (OH) by electro-generated H 2 O 2 , the E-peroxone process considerably enhanced dissolved organic carbon (DOC) abatement and significantly reduced bromate (BrO 3 - ) formation compared to conventional ozonation. However, natural organic matter (NOM) with high UV 254 absorbance, which is the major precursors of chlorination DBPs, was less efficiently abated during the E-peroxone process than conventional ozonation. Consequently, while both conventional ozonation and the E-peroxone process substantially reduced the formation of DBPs (trihalomethanes and haloacetic acids) during post-chlorination, higher DBP concentrations were generally observed during chlorination of the E-peroxone pretreated waters than conventional ozonation treated. In addition, because of conventional ozonation or the E-peroxone treatment, DBPs formed during post-chlorination shifted to more brominated species. The overall yields of brominated DBPs exhibited strong correlations with the bromide concentrations in water. Therefore, while the E-peroxone process can effectively suppress bromide transformation to bromate, it may lead to higher formation of brominated DBPs during post-chlorination compared to conventional ozonation. These results suggest that the E-peroxone process can lead to different DBP formation and speciation during water treatment trains compared to conventional ozonation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Chlorine isotope fractionation between chloride (Cl-) and dichlorine (Cl2)

NASA Astrophysics Data System (ADS)

Giunta, Thomas; Labidi, Jabrane; Eggenkamp, Hans G. M.

2017-09-01

The use of chlorine stable isotopes (35Cl and 37Cl) can help to constrain natural processes that involve chlorine species with different oxidation states. Theoretical studies based on thermodynamic and quantum mechanical approaches predict large isotope fractionation during redox reactions but to date, these reactions have not been studied experimentally. Here, we explore the chlorine isotope fractionation during the oxidation of hydrated Cl- (redox state of -I) to Cl2 (redox state of 0) at 25 °C and at 0 °C. Our apparatus consists of a sealed glass reactor where liquid HCl is mixed with liquid H2O2, a strong oxidant. Following complex reaction pathways, this mixture ultimately leads to the oxidation of Cl- and to the formation of Cl2 gas. As long as it is degassing, the Cl2 gas is flushed out of solution using N2 as a vector-gas from the glass-reactor to a potassium hydroxide (KOH) solution (pH 14) where it disproportionates into soluble species: Cl- and ClO-. After each experiment, the chlorine isotopic composition was measured in the recovered KOH-trap solution, as well as in the residual HCl solution. Consistent with theoretical predictions, the produced Cl2 gas is always enriched in the heavier 37Cl as compared to the initial Cl-reservoir. The following isotope fractionation factors are obtained: At 0 °C the isotopic fractionation 1000ln α(Cl2-Cl-) is 4.51 (+1.65/-0.49)‰ At 25 °C the isotopic fractionation 1000ln α(Cl2-Cl-) is 3.94 (+0.69/-0.18)‰. From the obtained data it is suggested that the production of Cl2 gas in our experiments is best described by a closed-system distillation. Our results are in agreement with published theoretical ab-initio calculations.

Control of Legionella Contamination and Risk of Corrosion in Hospital Water Networks following Various Disinfection Procedures

PubMed Central

Ferranti, Greta; Mansi, Antonella; Marcelloni, Anna M.; Proietto, Anna R.; Saini, Navneet; Borella, Paola; Bargellini, Annalisa

2016-01-01

Physical and chemical disinfection methods have been proposed with the aim of controlling Legionella water contamination. To date, the most effective procedures for reducing bacterial contamination have not yet been defined. The aim of this study was to assess the long-term effectiveness of various disinfection procedures in order to reduce both culturable and nonculturable (NC) legionellae in different hospital water networks treated with heat, chlorine dioxide, monochloramine, and hydrogen peroxide. The temperature levels and biocide concentrations that proved to give reliable results were analyzed. In order to study the possible effects on the water pipes, we verified the extent of corrosion on experimental coupons after applying each method for 6 months. The percentage of positive points was at its lowest after treatment with monochloramine, followed by chlorine dioxide, hydrogen peroxide, and hyperthermia. Different selections of Legionella spp. were observed, as networks treated with chlorine-based disinfectants were contaminated mainly by Legionella pneumophila serogroup 1, hyperthermia was associated with serogroups 2 to 14, and hydrogen peroxide treatment was associated mainly with non-pneumophila species. NC cells were detected only in heat-treated waters, and also when the temperature was approximately 60°C. The corrosion rates of the coupons were within a satisfactory limit for water networks, but the morphologies differed. We confirm here that chemical disinfection controls Legionella colonization more effectively than hyperthermia does. Monochloramine was the most effective treatment, while hydrogen peroxide may be a promising alternative to chlorine-based disinfectants due to its ability to select for other, less virulent or nonpathogenic species. PMID:26969696

Occurrences of nitrosamines in chlorinated and chloraminated drinking water in three representative cities, China.

PubMed

Luo, Qian; Wang, Donghong; Wang, Zijian

2012-10-15

An investigation of the occurrence of nine nitrosamines in drinking water following different water treatment processes was conducted using samples from seven drinking water treatment plants in three cities and tap waters in one city in China. The total nitrosamine levels ranged from not detected (n.d.) to 43.45 ng/L. The species and concentrations of the nine nitrosamines varied with disinfection methods and source waters. N-nitrosodimethylamine (NDMA), which is the nitrosamines of greatest concern, was identified in raw water, disinfecting water, finished water and tap water samples, ranging from 0.8 to 21.6, 0.12 to 24.2, n.d. to 8.8, and n.d. to 13.3 ng/L, respectively. Chloramination alone produced the most significant amounts of NDMA, while ozonation followed by chloramination led to moderately reduced levels. Additionally, chlorination produced relatively less NDMA, while low pressure ultraviolet radiation followed by chlorination could also significantly reduce them. Total organic carbon is one of the most important factors influencing nitrosamines formation in disinfecting water. In contrast, the addition of chlorine following any other disinfection was found to increase the formation of the other eight species of nitrosamines. The three nitrosamines recommended for monitoring by the US EPA were detected in the tap water samples, but most were present at levels below those that pose a risk to human health. Nevertheless, the occurrence and concentration of nitrosamines regulated in the Drinking Water Contaminant Candidate List could cause some potential human effects and therefore warrant attention. Copyright © 2012 Elsevier B.V. All rights reserved.

Bactericidal activity of electrolyzed acid water from solution containing sodium chloride at low concentration, in comparison with that at high concentration.

PubMed

Kiura, Hiromasa; Sano, Kouichi; Morimatsu, Shinichi; Nakano, Takashi; Morita, Chizuko; Yamaguchi, Masaki; Maeda, Toyoyuki; Katsuoka, Yoji

2002-05-01

Electrolyzed strong acid water (ESW) containing free chlorine at various concentrations is becoming to be available in clinical settings as a disinfectant. ESW is prepared by electrolysis of a NaCl solution, and has a corrosive activity against medical instruments. Although lower concentrations of NaCl and free chlorine are desired to eliminate corrosion, the germicidal effect of ESW with low NaCl and free-chlorine concentrations (ESW-L) has not been fully clarified. In this study, we demonstrated that ESW-L possesses bactericidal activity against Mycobacteria and spores of Bacillus subtilis. The effect was slightly weaker than that of ESW containing higher NaCl and free-chlorine concentrations (ESW-H), but acceptable as a disinfectant. To clarify the mechanism of the bactericidal activity, we investigated ESW-L-treated Pseudomonas aeruginosa by transmission electron microscopy, a bacterial enzyme assay and restriction fragment length polymorphism pattern (RFLP) assay. Since the bacterium, whose growth was completely inhibited by ESW-L, revealed the inactivation of cytoplasmic enzyme, blebs and breaks in its outer membrane and remained complete RFLP of DNA, damage of the outer membrane and inactivation of cytoplasmic enzyme are the important determinants of the bactericidal activity.

Determination of PCDF/PCDD in sludges from a drinking water treatment plant influence of chlorination treatment.

PubMed

Rivera, J; Eljarrat, E; Espadaler, I; Martrat, M G; Caixach, J

1997-01-01

A preliminary study to assess the origin and evolution of polichlorodibenzofurans (PCDFs) and polichlorodibenzo-p-dioxins (PCDDs) in a drinking water treatment plant (DWTP) was undertaken. Samples of coagulation sludges and exhausted granular activated carbon (GAC) were collected from a DWTP. Owing to the similar congener profiles obtained from sludges and GAC, a subsequent study of chlorination influence was carried out. Sludge samples from a treatment with and without the chlorination step were analysed. A complementary study of the PCB content was made. The results obtained did not reveal a marked influence of chlorination in the formation of PCDFs/PCDDs.

The role of microbial low-molecular-weight autoregulatory factors (alkylhydroxybenzenes) in resistance of microorganisms to radiation and heat shock

NASA Astrophysics Data System (ADS)

El-Registan, Galina I.; Mulyukin, Andrey L.; Nikolaev, Yuri A.; Stepanenko, Irina Yu.; Kozlova, Alla N.; Martirosova, Elena I.; Shanenko, Elena F.; Strakhovskaya, Marina G.; Revina, Aleksandra A.

Low-molecular-weight cell-to-cell communication factors are produced by various pro- and eukaryotes and involved in autoregulation of the growth and development of microbial cultures. As for some bacterial and yeast species, these factors were identified as isomers and homologues of alkylhydroxybenzenes (AHB). Depending on the concentration, they participate in controlling the transition to stationary phase, entering the resting state, and stress resistance of vegetative cells to gamma-irradiation, photooxidation (singlet oxygen), and heat shock. Chemical analogues of microbial AHB protected microbial cultures from stressful situations and exerted (1) the stabilizing activity toward macromolecules and (2) the ability to scavenge active oxygen species. The stabilizing effect of AHBs resulted from their complex formation with protected macromolecules due to intermolecular hydrogen bonds, hydrophobic and electrostatic interactions and was demonstrated on models of individual enzymes (trypsin). Particularly, AHBs protected the yeast from the action of (a) active oxygen species formed during gamma-irradiation (500 Gy, 1.96 Gy/s) or (b) singlet oxygen generated in cells photosensitized by chlorin e 6 (10 μg/L). It is important that microbial AHBs were not species-specific and defended cultured microbial and animal cells from the action of organic toxicants. The use of AHBs as protectants and adaptogens is discussed as well as perspectives of further investigations.

Elimination of Naegleria fowleri from bulk water and biofilm in an operational drinking water distribution system.

PubMed

Miller, Haylea C; Morgan, Matthew J; Wylie, Jason T; Kaksonen, Anna H; Sutton, David; Braun, Kalan; Puzon, Geoffrey J

2017-03-01

Global incidence of primary amoebic meningoencephalitis cases associated with domestic drinking water is increasing. The need for understanding disinfectant regimes capable of eliminating the causative microorganism, Naegleria fowleri, from bulk water and pipe wall biofilms is critical. This field study demonstrated the successful elimination of N. fowleri from the bulk water and pipe wall biofilm of a persistently colonised operational drinking water distribution system (DWDS), and the prevention of further re-colonisation. A new chlorination unit was installed along the pipe line to boost the free chlorine residual to combat the persistence of N. fowleri. Biofilm and bulk water were monitored prior to and after re-chlorination (RCl), pre-rechlorination (pre-RCl) and post-rechlorination (post-RCl), respectively, for one year. A constant free chlorine concentration of > 1 mg/L resulted in the elimination of N. fowleri from both the bulk water and biofilm at the post-RCl site. Other amoeba species were detected during the first two months of chlorination, but all amoebae were eliminated from both the bulk water and biofilm at post-RCl after 60 days of chlorination with free chlorine concentrations > 1 mg/L. In addition, a dynamic change in the biofilm community composition and a four log reduction in biofilm cell density occurred post-RCl. The pre-RCl site continued to be seasonally colonised by N. fowleri, but the constant free chlorine residual of > 1 mg/L prevented N. fowleri from recolonising the bulk and pipe wall biofilm at the post-RCl site. To our knowledge, this is the first study to demonstrate successful removal of N. fowleri from both the bulk and pipe wall biofilm and prevention of re-colonisation of N. fowleri in an operational DWDS. The findings of this study are of importance to water utilities in addressing the presence of N. fowleri and other amoeba in susceptible DWDSs. Copyright © 2016 Elsevier Ltd. All rights reserved.

40 CFR 180.940 - Tolerance exemptions for active and inert ingredients for use in antimicrobial formulations (Food...

Code of Federal Regulations, 2010 CFR

2010-07-01

... to exceed 200 ppm determined as total available chlorine Hypochlorous acid, lithium salt 13840-33-0... to exceed 200 ppm determined as total available chlorine and 30 ppm lithium Hypochlorous acid...

40 CFR 180.940 - Tolerance exemptions for active and inert ingredients for use in antimicrobial formulations (Food...

Code of Federal Regulations, 2011 CFR

2011-07-01

... to exceed 200 ppm determined as total available chlorine Hypochlorous acid, lithium salt 13840-33-0... to exceed 200 ppm determined as total available chlorine and 30 ppm lithium Hypochlorous acid...

40 CFR 180.940 - Tolerance exemptions for active and inert ingredients for use in antimicrobial formulations (Food...

Code of Federal Regulations, 2012 CFR

2012-07-01

... to exceed 200 ppm determined as total available chlorine Hypochlorous acid, lithium salt 13840-33-0... to exceed 200 ppm determined as total available chlorine and 30 ppm lithium Hypochlorous acid...

US Army Medical Bioengineering Research and Development Laboratory Annual Progress Report for FY 83.

DTIC Science & Technology

1983-10-01

Army consumes is chlorinated. Also, the water from Army wastewater treatment plants is chlorinated before it is returned to the environment.I Because...12K; CY - K; BY - OK PROBLEM DEFINITION: Chlorination of drinking water and of effluents from wastewater treatment plants is standard practice employed...FY81 indicated no research - activity on this type of photocell. Materials and chemicals have been ordered and assembled. A preliminary cell has been

Removal of Intermediate Aromatic Halogenated DBPs by Activated Carbon Adsorption: A New Approach to Controlling Halogenated DBPs in Chlorinated Drinking Water.

PubMed

Jiang, Jingyi; Zhang, Xiangru; Zhu, Xiaohu; Li, Yu

2017-03-21

During chlorine disinfection of drinking water, chlorine may react with natural organic matter (NOM) and bromide ion in raw water to generate halogenated disinfection byproducts (DBPs). To mitigate adverse effects from DBP exposure, granular activated carbon (GAC) adsorption has been considered as one of the best available technologies for removing NOM (DBP precursor) in drinking water treatment. Recently, we have found that many aromatic halogenated DBPs form in chlorination, and they act as intermediate DBPs to decompose and form commonly known DBPs including trihalomethanes and haloacetic acids. In this work, we proposed a new approach to controlling drinking water halogenated DBPs by GAC adsorption of intermediate aromatic halogenated DBPs during chlorination, rather than by GAC adsorption of NOM prior to chlorination (i.e., traditional approach). Rapid small-scale column tests were used to simulate GAC adsorption in the new and traditional approaches. Significant reductions of aromatic halogenated DBPs were observed in the effluents with the new approach; the removals of total organic halogen, trihalomethanes, and haloacetic acids by the new approach always exceeded those by the traditional approach; and the effluents with the new approach were considerably less developmentally toxic than those with the traditional approach. Our findings indicate that the new approach is substantially more effective in controlling halogenated DBPs than the traditional approach.

Removal of Emerging Contaminants and Estrogenic Activity from Wastewater Treatment Plant Effluent with UV/Chlorine and UV/H2O2 Advanced Oxidation Treatment at Pilot Scale

PubMed Central

Kuch, Bertram; Lange, Claudia; Richter, Philipp; Kugele, Amélie; Minke, Ralf

2018-01-01

Effluent of a municipal wastewater treatment plant (WWTP) was treated on-site with the UV/chlorine (UV/HOCl) advanced oxidation process (AOP) using a pilot plant equipped with a medium pressure UV lamp with an adjustable performance of up to 1 kW. Results obtained from parallel experiments with the same pilot plant, where the state of the art UV/H2O2 AOP was applied, were compared regarding the removal of emerging contaminants (EC) and the formation of adsorbable organohalogens (AOX). Furthermore, the total estrogenic activity was measured in samples treated with the UV/chlorine AOP. At an energy consumption of 0.4 kWh/m3 (0.4 kW, 1 m3/h) and in a range of oxidant concentrations from 1 to 6 mg/L, the UV/chlorine AOP had a significantly higher EC removal yield than the UV/H2O2 AOP. With free available chlorine concentrations (FAC) in the UV chamber influent of at least 5 mg/L (11 mg/L of dosed Cl2), the total estrogenic activity could be reduced by at least 97%. To achieve a certain concentration of FAC in the UV chamber influent, double to triple the amount of dosed Cl2 was needed, resulting in AOX concentrations of up to 520 µg/L. PMID:29735959

Removal of Emerging Contaminants and Estrogenic Activity from Wastewater Treatment Plant Effluent with UV/Chlorine and UV/H₂O₂ Advanced Oxidation Treatment at Pilot Scale.

PubMed

Rott, Eduard; Kuch, Bertram; Lange, Claudia; Richter, Philipp; Kugele, Amélie; Minke, Ralf

2018-05-07

Effluent of a municipal wastewater treatment plant (WWTP) was treated on-site with the UV/chlorine (UV/HOCl) advanced oxidation process (AOP) using a pilot plant equipped with a medium pressure UV lamp with an adjustable performance of up to 1 kW. Results obtained from parallel experiments with the same pilot plant, where the state of the art UV/H₂O₂ AOP was applied, were compared regarding the removal of emerging contaminants (EC) and the formation of adsorbable organohalogens (AOX). Furthermore, the total estrogenic activity was measured in samples treated with the UV/chlorine AOP. At an energy consumption of 0.4 kWh/m³ (0.4 kW, 1 m³/h) and in a range of oxidant concentrations from 1 to 6 mg/L, the UV/chlorine AOP had a significantly higher EC removal yield than the UV/H₂O₂ AOP. With free available chlorine concentrations (FAC) in the UV chamber influent of at least 5 mg/L (11 mg/L of dosed Cl₂), the total estrogenic activity could be reduced by at least 97%. To achieve a certain concentration of FAC in the UV chamber influent, double to triple the amount of dosed Cl₂ was needed, resulting in AOX concentrations of up to 520 µg/L.

Mechanism of chemical activation of sodium chloride in the presence of amino acids.

PubMed

Rahn, Anja K K; Yaylayan, Varoujan A

2015-01-01

Sodium chloride has been shown to promote chlorination of glycerol during thermal processing. However, the detailed mechanism of this reaction is not well understood. Preliminary experiments have indicated that the reaction mixture should contain an amino acid and it should be dissolved thoroughly in water in order to induce chlorination. These observations are consistent with the process of dissociation of sodium chloride and its re-association with amino acid and eventual formation of the chlorinating agent in the form of the hydrochloride salt. Release of HCl from this salt can be manifested in chlorination and hydrolytic reactions occurring during thermal processing. The generation of HCl at room temperature from a mixture of sodium chloride and glycine was confirmed through spectrophotometric monitoring of the pH. Hydrolytic and chlorination reactions were demonstrated through monitoring of formation of HMF and chlorinated products under pyrolytic conditions using glucose or sucrose and amino acid mixtures. Copyright © 2014 Elsevier Ltd. All rights reserved.

Comparison of chlorination and chloramination in carbonaceous and nitrogenous disinfection byproduct formation potentials with prolonged contact time.

PubMed

Sakai, Hiroshi; Tokuhara, Shunsuke; Murakami, Michio; Kosaka, Koji; Oguma, Kumiko; Takizawa, Satoshi

2016-01-01

Due to decreasing water demands in Japan, hydraulic retention times of water in piped supply systems has been extended, resulting in a longer contact time with disinfectants. However, the effects of extended contact time on the formation of various disinfection byproducts (DBPs), including carbonaceous DBPs such as trihalomethane (THM) and haloacetic acid (HAA), and nitrogenous DBPs such as nitrosodimethylamine (NDMA) and nitrosomorpholine (NMor), have not yet been investigated in detail. Herein, we compared the formation of these DBPs by chlorination and chloramination for five water samples collected from rivers and a dam in Japan, all of which represent municipal water supply sources. Water samples were treated by either filtration or a combination of coagulation and filtration. Treated samples were subjected to a DBP formation potential test by either chlorine or chloramine for contact times of 1 day or 4 days. Four THM species, nine HAA species, NDMA, and NMor were measured by GC-ECD or UPLC-MS/MS. Lifetime cancer risk was calculated based on the Integrated Risk Information System unit risk information. The experiment and analysis focused on (i) prolonged contact time from 1 day to 4 days, (ii) reduction efficiency by conventional treatment, (iii) correlations between DBP formation potentials and water quality parameters, and (iv) the contribution of each species to total risk. With an increased contact time from 1 day to 4 days, THM formation increased to 420% by chloramination. Coagulation-filtration treatment showed that brominated species in THMs are less likely to be reduced. With the highest unit risk among THM species, dibromochloromethane (DBCM) showed a high correlation with bromine, but not with organic matter parameters. NDMA contributed to lifetime cancer risk. The THM formation pathway should be revisited in terms of chloramination and bromine incorporation. It is also recommended to investigate nitrosamine formation potential by chloramination. Copyright © 2015 Elsevier Ltd. All rights reserved.

Analysis of Halogen-Mercury Reactions in Flue Gas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paula Buitrago; Geoffrey Silcox; Constance Senior

2010-01-01

Oxidized mercury species may be formed in combustion systems through gas-phase reactions between elemental mercury and halogens, such as chorine or bromine. This study examines how bromine species affect mercury oxidation in the gas phase and examines the effects of mixtures of bromine and chlorine on extents of oxidation. Experiments were conducted in a bench-scale, laminar flow, methane-fired (300 W), quartz-lined reactor in which gas composition (HCl, HBr, NO{sub x}, SO{sub 2}) and temperature profile were varied. In the experiments, the post-combustion gases were quenched from flame temperatures to about 350 C, and then speciated mercury was measured using amore » wet conditioning system and continuous emissions monitor (CEM). Supporting kinetic calculations were performed and compared with measured levels of oxidation. A significant portion of this report is devoted to sample conditioning as part of the mercury analysis system. In combustion systems with significant amounts of Br{sub 2} in the flue gas, the impinger solutions used to speciate mercury may be biased and care must be taken in interpreting mercury oxidation results. The stannous chloride solution used in the CEM conditioning system to convert all mercury to total mercury did not provide complete conversion of oxidized mercury to elemental, when bromine was added to the combustion system, resulting in a low bias for the total mercury measurement. The use of a hydroxylamine hydrochloride and sodium hydroxide solution instead of stannous chloride showed a significant improvement in the measurement of total mercury. Bromine was shown to be much more effective in the post-flame, homogeneous oxidation of mercury than chlorine, on an equivalent molar basis. Addition of NO to the flame (up to 400 ppmv) had no impact on mercury oxidation by chlorine or bromine. Addition of SO{sub 2} had no effect on mercury oxidation by chlorine at SO{sub 2} concentrations below about 400 ppmv; some increase in mercury oxidation was observed at SO{sub 2} concentrations of 400 ppmv and higher. In contrast, SO{sub 2} concentrations as low as 50 ppmv significantly reduced mercury oxidation by bromine, this reduction could be due to both gas and liquid phase interactions between SO{sub 2} and oxidized mercury species. The simultaneous presence of chlorine and bromine in the flue gas resulted in a slight increase in mercury oxidation above that obtained with bromine alone, the extent of the observed increase is proportional to the chlorine concentration. The results of this study can be used to understand the relative importance of gas-phase mercury oxidation by bromine and chlorine in combustion systems. Two temperature profiles were tested: a low quench (210 K/s) and a high quench (440 K/s). For chlorine the effects of quench rate were slight and hard to characterize with confidence. Oxidation with bromine proved sensitive to quench rate with significantly more oxidation at the lower rate. The data generated in this program are the first homogeneous laboratory-scale data on bromine-induced oxidation of mercury in a combustion system. Five Hg-Cl and three Hg-Br mechanisms, some published and others under development, were evaluated and compared to the new data. The Hg-halogen mechanisms were combined with submechanisms from Reaction Engineering International for NO{sub x}, SO{sub x}, and hydrocarbons. The homogeneous kinetics under-predicted the levels of mercury oxidation observed in full-scale systems. This shortcoming can be corrected by including heterogeneous kinetics in the model calculations.« less

Tolerance of anaerobic bacteria to chlorinated solvents.

PubMed

Koenig, Joanna C; Groissmeier, Kathrin D; Manefield, Mike J

2014-01-01

The aim of this research was to evaluate the effects of four chlorinated aliphatic hydrocarbons (CAHs), perchloroethene (PCE), carbon tetrachloride (CT), chloroform (CF) and 1,2-dichloroethane (1,2-DCA), on the growth of eight anaerobic bacteria: four fermentative species (Escherichia coli, Klebsiella sp., Clostridium sp. and Paenibacillus sp.) and four respiring species (Pseudomonas aeruginosa, Geobacter sulfurreducens, Shewanella oneidensis and Desulfovibrio vulgaris). Effective concentrations of solvents which inhibited growth rates by 50% (EC50) were determined. The octanol-water partition coefficient or log Po/w of a CAH proved a generally satisfactory measure of its toxicity. Most species tolerated approximately 3-fold and 10-fold higher concentrations of the two relatively more polar CAHs CF and 1,2-DCA, respectively, than the two relatively less polar compounds PCE and CT. EC50 values correlated well with growth rates observed in solvent-free cultures, with fast-growing organisms displaying higher tolerance levels. Overall, fermentative bacteria were more tolerant to CAHs than respiring species, with iron- and sulfate-reducing bacteria in particular appearing highly sensitive to CAHs. These data extend the current understanding of the impact of CAHs on a range of anaerobic bacteria, which will benefit the field of bioremediation.

Tolerance of Anaerobic Bacteria to Chlorinated Solvents

PubMed Central

Koenig, Joanna C.; Groissmeier, Kathrin D.; Manefield, Mike J.

2014-01-01

The aim of this research was to evaluate the effects of four chlorinated aliphatic hydrocarbons (CAHs), perchloroethene (PCE), carbon tetrachloride (CT), chloroform (CF) and 1,2-dichloroethane (1,2-DCA), on the growth of eight anaerobic bacteria: four fermentative species (Escherichia coli, Klebsiella sp., Clostridium sp. and Paenibacillus sp.) and four respiring species (Pseudomonas aeruginosa, Geobacter sulfurreducens, Shewanella oneidensis and Desulfovibrio vulgaris). Effective concentrations of solvents which inhibited growth rates by 50% (EC50) were determined. The octanol-water partition coefficient or log Po/w of a CAH proved a generally satisfactory measure of its toxicity. Most species tolerated approximately 3-fold and 10-fold higher concentrations of the two relatively more polar CAHs CF and 1,2-DCA, respectively, than the two relatively less polar compounds PCE and CT. EC50 values correlated well with growth rates observed in solvent-free cultures, with fast-growing organisms displaying higher tolerance levels. Overall, fermentative bacteria were more tolerant to CAHs than respiring species, with iron- and sulfate-reducing bacteria in particular appearing highly sensitive to CAHs. These data extend the current understanding of the impact of CAHs on a range of anaerobic bacteria, which will benefit the field of bioremediation. PMID:24441515

Impact of vegetation and ecosystems on chlorine(-36) cycling and its modeling: from simplified approaches towards more complex biogeochemical tools

NASA Astrophysics Data System (ADS)

Thiry, Yves; Redon, Paul-Olivier; Gustafsson, Malin; Marang, Laura; Bastviken, David

2013-04-01

Chlorine is very soluble at a global scale with chloride (Cl-), the dominating form. Because of its high mobility, chlorine is usually perceived as a good conservative tracer in hydrological studies and by analogy as little reactive in biosphere. Since 36Cl can be considered to have the same behaviour than stable Cl, a good knowledge of chlorine distribution between compartments of terrestrial ecosystems is sufficient to calibrate a specific activity model which supposes rapid dilution of 36Cl within the large pool of stable Cl and isotopic equilibrium between compartments. By assuming 36Cl redistribution similar to that of stable Cl at steady-state, specific activity models are simplified interesting tools for regulatory purposes in environmental safety assessment, especially in case of potential long term chronic contamination of agricultural food chain (IAEA, 2010). In many other more complex scenarios (accidental acute release, intermediate time frame, and contrasted natural ecosystems), new information and tools are necessary for improving (radio-)ecological realism, which entails a non-conservative behavior of chlorine. Indeed observed dynamics of chlorine in terrestrial ecosystems is far from a simple equilibrium notably because of natural processes of organic matter (SOM) chlorination mainly occurring in surface soils (Öberg, 1998) and mediated by microbial activities on a large extent (Bastviken et al. 2007). Our recent studies have strengthened the view that an organic cycle for chlorine should now be recognized, in addition to its inorganic cycle. Major results showed that: organochlorine (Clorg) formation occurs in all type of soils and ecosystems (culture, pasture, forest), leading to an average fraction of the total Cl pool in soil of about 80 % (Redon et al., 2012), chlorination in more organic soils over time leads to a larger Clorg pool and in turn to a possible high internal supply of inorganic chlorine (Clin) upon dechlorination. (Gustafsson et al., 2012), average Cl residence time in forest soils calculated for Clin and Clorg together was 5-fold higher that the residence time estimated for Clin alone (Redon et al., 2011), locally, Cl amount taken up by certain vegetation types can be larger than annual atmospheric deposits, the Cl in excess being recycled mainly by throughfall (Thiry, 2010), root uptake and chlorine transformation rates in soils are essential to calibrate dynamic compartment models since those processes control the persistence of chlorine in the whole system but data are still deficient for different land uses (Van den Hoof & Thiry, 2012). References: Bastviken, D., Thomsen, F., Svensson, T., Karlsson, S., Sandén, P., Shaw, G., Matucha, M., and Öberg, G. (2007). Chloride retention in forest soil by microbial uptake and by natural chlorination of organic matter. Geochim. Cosmochim. Acta, 71: 3182-3192. Gustavsson, M., Karlsson, S.,Öberg, G.,Sandén, P.,Svensson, T.,Valinia, S.,Thiry, Y. and Bastviken, D. (2012). Organic matter chlorination rates in different boreal soils: the role of soil organic matter content. Environmental Science & Technology, 46 (3): 1504-1510 Thiry, Y., 2010. Contribution à l'étude du cycle biogéochimique du chlore en écosystème forestier: cas d'un peuplement de pin sylvestre. Rapport Andra n° ENV.NT.ASTR.10.0068. IAEA (2010). Handbook of parameter values for the prediction of radionuclide transfer to humans in terrestrial and freshwater environments. Technical Report Series n° 472, Vienna, Austria. Öberg, G. (1998). Chloride and organic chlorine in soil. Acta hydrochimica et hydrobiologica, 26 (3): 137-144. Redon, P-O., Abdelouas, A., Bastviken, D., Cecchini, S. Nicolas, M. and Thiry, Y. (2011). Chloride and organic chlorine in forest soils: storage, residence times, and influence of ecological conditions. Environmental Science & Technology, 45: 7202-7208. Redon, P-O., Jolivet, C., Saby, N., Abdelouas, A.and Thiry, Y. (2012). Occurrence of natural organic chlorine in soils for different land uses. Biogeochemistry (In press), doi: 10.1007/s10533-012-9771-7. Van den Hoof, C. and Thiry, Y. (2012). Modelling of the natural chlorine cycling in a coniferous stand: implications for chlorine-36 behaviour in a contaminated forest environment. Journal of Environmental Radioactivity., 107: 56-67.

IN-PLACE REGENERATION OF GAC USING FENTON'S REAGENTS

EPA Science Inventory

This paper evaluates the feasibility of using Fenton’s reagents for in-place recovery of spent granular activated carbon (GAC). Fenton’s reagents are cycled through spent GAC to degrade sorbed chlorinated hydrocarbons with little loss of carbon capacity. Seven chlorinated compou...

Assessing the Fate and Transformation By-Product Potential of Trenbolone during Chlorination

EPA Science Inventory

Chlorine disinfection is an effective means for managing microbiological activity during drinking water treatment and can eliminate a number of known organic contaminants. Trenbolone is an androgenic steroidal hormone used primarily as a growth stimulant in the animal feedstock ...

High energy chemical laser system

DOEpatents

Gregg, D.W.; Pearson, R.K.

1975-12-23

A high energy chemical laser system is described wherein explosive gaseous mixtures of a reducing agent providing hydrogen isotopes and interhalogen compounds are uniformly ignited by means of an electrical discharge, flash- photolysis or an electron beam. The resulting chemical explosion pumps a lasing chemical species, hydrogen fluoride or deuterium fluoride which is formed in the chemical reaction. The generated lasing pulse has light frequencies in the 3- micron range. Suitable interhalogen compounds include bromine trifluoride (BrF$sub 3$), bromine pentafluoride (BrF$sub 5$), chlorine monofluoride (ClF), chlorine trifluoride (ClF$sub 3$), chlorine pentafluoride (ClF$sub 5$), iodine pentafluoride (IF$sub 5$), and iodine heptafluoride (IF$sub 7$); and suitable reducing agents include hydrogen (H$sub 2$), hydrocarbons such as methane (CH$sub 4$), deuterium (D$sub 2$), and diborane (B$sub 2$H$sub 6$), as well as combinations of the gaseous compound and/or molecular mixtures of the reducing agent.

DISINFECTION OF EMERGING PATHOGENS

EPA Science Inventory

There is a growing awareness of the need to control waterborne microbial pathogens. This presentation will concentate on the role of chemical inactivation, using chlorine, chloramines and ozone as a means of controlling bacterial and protozoan species. Information will be present...

Rate constants for reactions of ClO/x/ of atmospheric interest

NASA Technical Reports Server (NTRS)

Watson, R. T.

1977-01-01

Chemical kinetics measurements on 82 gas phase reactions of chlorine containing species are reviewed. Recommended rate constants are given. The principal species of interest are Cl, Cl2, ClO, Cl2O, ClOO, OClO, CINO, HCl and halo derivatives of methane and ethane. Absorption spectra are given for 21 species. In addition the chemical kinetics methods used to obtain these data are discussed with regard to their applicability and reliability.

Antimicrobial Cellulose: Preparation and Application of 5-Methyl-5-Aminomethylhydantoin

DTIC Science & Technology

2006-08-01

they release active chlorine to microbes relatively more rapidly and kill the pathogens in the shortest time. Amide N-Cl bonds being relatively more...for 5~35 min. A 1% Clorox solution was used for chlorination without pH adjustment. bCoating solution: 5 % AH in distilled water. cCoating solution...0.37% 0.75 % 0.94 % 0.80 % 0.80 % aThe cloth samples were cured at 1450C for 35 min and then chlorinated with 1% Clorox 12 without pH adjustment

Structure-activity relationships for the impact of selected isothiazol-3-one biocides on glutathione metabolism and glutathione reductase of the human liver cell line Hep G2.

PubMed

Arning, Jürgen; Dringen, Ralf; Schmidt, Maike; Thiessen, Anette; Stolte, Stefan; Matzke, Marianne; Bottin-Weber, Ulrike; Caesar-Geertz, Birgit; Jastorff, Bernd; Ranke, Johannes

2008-04-18

To investigate the toxic mode of action of isothiazol-3-one biocides the four compounds N-methylisothiazol-3-one (MIT), 5-chloro-N-methylisothiazol-3-one (CIT), N-octylisothiazol-3-one (OIT) and 4,5-dichloro-N-octylisothiazol-3-one (DCOIT) were purified and tested as single chemical entities for their effects on the human hepatoblastoma cell line Hep G2 and on isolated and cellular glutathione reductase GR). The two chlorinated substances CIT and DCOIT significantly decreased the amount of total cellular glutathione (GSx) in a dose and time dependent manner. Concomitantly, an increase in the level of oxidised glutathione (GSSG) was observed. The resulting shift in the GSH/GSSG ratio entailing the breakdown of the cellular thiol reduction potential was accompanied by necrotic morphological changes like swelling of the plasma membrane and subsequent lysis of the cells. Additionally, CIT and DCOIT were found to inhibit cellular GR in the cells in a concentration dependent manner. The T-SAR-based (thinking in terms of structure-activity relationships) comparison of the chlorine-substituted structures CIT and DCOIT with their non-chlorinated and less active analogues MIT and OIT identified the chlorine substituents and the resulting reaction mechanisms to be the key structural mediators of the observed toxic effects. Furthermore, differences in the activity of both chlorinated substances could be explained using the T-SAR approach to link the lipophilicity and the intrinsic glutathione-reactivity of the compounds to the expected target site concentrations inside the cells.

Site-Directed Photoproteolysis of 8-Oxoguanine DNA Glycosylase 1 (OGG1) by Specific Porphyrin-Protein Probe Conjugates: A Strategy to Improve the Effectiveness of Photodynamic Therapy for Cancer

PubMed Central

Conlon, Kimberly A.; Berrios, Miguel

2007-01-01

The specific light-induced, non-enzymatic photolysis of mOGG1 by porphyrin-conjugated or rose bengal-conjugated streptavidin and porphyrin-conjugated or rose bengal-conjugated first specific or secondary anti-IgG antibodies is reported. The porphyrin chlorin e6 and rose bengal were conjugated to either streptavidin, rabbit anti-mOGG1 primary specific antibody fractions or goat anti-rabbit IgG secondary antibody fractions. Under our experimental conditions, visible light of wavelengths greater than 600 nm induced the non-enzymatic degradation of mOGG1 when this DNA repair enzyme either directly formed a complex with chlorin e6-conjugated anti-mOGG1 primary specific antibodies or indirectly formed complexes with either streptavidin-chlorin e6 conjugates and biotinylated first specific anti-mOGG1 antibodies or first specific anti-mOGG1antibodies and chlorin e6-conjugated anti-rabbit IgG secondary antibodies. Similar results were obtained when rose bengal was used as photosensitizer instead of chlorine e6. The rate of the photochemical reaction of mOGG1 site-directed by all three chlorine e6 antibody complexes was not affected by the presence of the singlet oxygen scavenger sodium azide. Site-directed photoactivatable probes having the capacity to generate reactive oxygen species (ROS) while destroying the DNA repair system in malignant cells and tumors may represent a powerful strategy to boost selectivity, penetration and efficacy of current photodynamic (PDT) therapy methodologies. PMID:17251034

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

PubMed

Yuan, Jing; Wu, Xin-Jiang; Lu, Wen-Qing; Cheng, Xiao-Li; Chen, Dan; Li, Xiao-Yan; Liu, Ai-Lin; Wu, Jian-Jun; Xie, Hong; Stahl, Thorsten; Mersch-Sundermann, Volker

2005-01-01

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.

Molecular mechanisms in the pyrolysis of unsaturated chlorinated hydrocarbons: formation of benzene rings. 1. Quantum chemical studies.

PubMed

McIntosh, Grant J; Russell, Douglas K

2013-05-23

Analogues of important aromatic growth mechanisms in hydrocarbon pyrolysis and combustion systems are extended to chlorinated systems. We consider the addition of C2Cl2 to both C4Cl3 and C4Cl5 radicals at the M06-2X/6-311+G(3df,3p)//B3LYP/6-31G(d) level of theory, and we demonstrate that these reaction systems have much in common with those of nonchlorinated species. In particular, we find that these radicals appear to lead preferentially to fulvenes, and not to the observed aromatic products, as is found in nonchlorinated systems. We have therefore also considered nonradical C4/C2 channels by way of Diels-Alder cyclization of C4Cl4/C2Cl2 and C4H2Cl2/C2HCl pairs to describe aromatic formation. While the latter pair readily leads to the formation of partially chlorinated benzenes, the fully chlorinated congeners are sterically prohibited from ring closing directly; this leads to a series of novel rearrangement processes which predict the formation of hexachloro-1,5-diene-3-yne, in addition to hexachlorobenzene, in good agreement with experiment. This suggests, for the first time, that facile nonradical routes to aromatic formation are operative in partially and fully chlorinated pyrolysis and combustion systems.

Removal of estrogens and estrogenicity through drinking water treatment.

PubMed

Schenck, Kathleen; Rosenblum, Laura; Wiese, Thomas E; Wymer, Larry; Dugan, Nicholas; Williams, Daniel; Mash, Heath; Merriman, Betty; Speth, Thomas

2012-03-01

Estrogenic compounds have been shown to be present in surface waters, leading to concerns over their possible presence in finished drinking waters. In this work, two in vitro human cell line bioassays for estrogenicity were used to evaluate the removal of estrogens through conventional drinking water treatment using a natural water. Bench-scale studies utilizing chlorine, alum coagulation, ferric chloride coagulation, and powdered activated carbon (PAC) were conducted using Ohio River water spiked with three estrogens, 17β-estradiol, 17α-ethynylestradiol, and estriol. Treatment of the estrogens with chlorine, either alone or with coagulant, resulted in approximately 98% reductions in the concentrations of the parent estrogens, accompanied by formation of by-products. The MVLN reporter gene and MCF-7 cell proliferation assays were used to characterize the estrogenic activity of the water before and after treatment. The observed estrogenic activities of the chlorinated samples showed that estrogenicity of the water was reduced commensurate with removal of the parent estrogen. Therefore, the estrogen chlorination by-products did not contribute appreciably to the estrogenic activity of the water. Coagulation alone did not result in significant removals of the estrogens. However, addition of PAC, at a typical drinking water plant dose, resulted in removals ranging from approximately 20 to 80%.

Short-chain chlorinated paraffins in marine organisms from the Pearl River Estuary in South China: Residue levels and interspecies differences.

PubMed

Sun, Runxia; Luo, Xiaojun; Tang, Bin; Li, Zongrui; Huang, Liqian; Wang, Tao; Mai, Bixian

2016-05-15

There is limited information available on the bioaccumulation of short-chain chlorinated paraffins (SCCPs), a complicated group of persistent organic pollutants (POPs) candidates listed in the Stockholm Convention, in estuarine ecosystem. This study analyzed SCCPs in marine organisms (five fish and six invertebrates) from the Pearl River Estuary in South China. The concentrations of total SCCPs ranged from 210 to 21,000 ng · g(-1) lipid weight, with relatively higher levels in benthic invertebrates (shrimp, crabs and bivalves) than in non-benthic species (pelagic and mesopelagic fish and squid). SCCPs were biomagnified from prey fish (tapertail anchovy, Coilia mystus) to predator fish (Bombay duck, Harpadon nehereus), and the biomagnification factors (BMFs) of SCCP congeners ranged from 1.1 (C10H16Cl6) to 3.4 (C13H18Cl10). Species-specific homologue group patterns were also observed, with significantly lower proportions of C10 congeners in the shrimp, bivalves and Bombay duck than in the other species. Copyright © 2016. Published by Elsevier B.V.

Chlorination of low-band-gap polymers: Toward high-performance polymer solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mo, Daize; Wang, Huan; Chen, Hui

Here, halogenation is an effective way to tune the energy levels of organic semiconducting materials. To date, fluorination of organic semiconducting materials to fabricate polymer solar cells (PSCs) has been used far more than chlorination; however, fluorine exchange reactions suffer from low yields and the resulting fluorinated polymer always comes with higher price, which will greatly hinder their commercial applications. Herein, we designed and synthesized a series of chlorinated donor-acceptor (D-A) type polymers, in which benzo[1,2-b:4,5- b]dithiophene and chlorinated benzothiadiazole units are connected by thiophene π-bridges with an asymmetric alkyl chain. These chlorinated polymers showed deep highest occupied molecular orbitalmore » energy levels, which promoted the efficiency of their corresponding PSCs by increasing the device open circuit voltage. The asymmetric alkyl chain on the thiophene moieties gave the final polymer sufficient solubility for solution processing and strong π-π stacking in films allowed for high mobility. Although the introduction of a large chlorine atom increased the torsion angle of the polymer backbone, the chlorinated polymers maintained high crystallinity and a favorable backbone orientation in the blended films. These factors contributed to respectable device performances from thick-film devices, which showed PCEs as high as 9.11% for a 250 nm-thick active layer. These results demonstrate that chlorination is a promising method to fine tune the energy levels of conjugated polymers, and chlorinated benzothiadiazole may be a versatile building block in materials for efficient solar energy conversion.« less

Chlorination of low-band-gap polymers: Toward high-performance polymer solar cells

DOE PAGES

Mo, Daize; Wang, Huan; Chen, Hui; ...

2017-03-08

Here, halogenation is an effective way to tune the energy levels of organic semiconducting materials. To date, fluorination of organic semiconducting materials to fabricate polymer solar cells (PSCs) has been used far more than chlorination; however, fluorine exchange reactions suffer from low yields and the resulting fluorinated polymer always comes with higher price, which will greatly hinder their commercial applications. Herein, we designed and synthesized a series of chlorinated donor-acceptor (D-A) type polymers, in which benzo[1,2-b:4,5- b]dithiophene and chlorinated benzothiadiazole units are connected by thiophene π-bridges with an asymmetric alkyl chain. These chlorinated polymers showed deep highest occupied molecular orbitalmore » energy levels, which promoted the efficiency of their corresponding PSCs by increasing the device open circuit voltage. The asymmetric alkyl chain on the thiophene moieties gave the final polymer sufficient solubility for solution processing and strong π-π stacking in films allowed for high mobility. Although the introduction of a large chlorine atom increased the torsion angle of the polymer backbone, the chlorinated polymers maintained high crystallinity and a favorable backbone orientation in the blended films. These factors contributed to respectable device performances from thick-film devices, which showed PCEs as high as 9.11% for a 250 nm-thick active layer. These results demonstrate that chlorination is a promising method to fine tune the energy levels of conjugated polymers, and chlorinated benzothiadiazole may be a versatile building block in materials for efficient solar energy conversion.« less

Control of Legionella Contamination and Risk of Corrosion in Hospital Water Networks following Various Disinfection Procedures.

PubMed

Marchesi, Isabella; Ferranti, Greta; Mansi, Antonella; Marcelloni, Anna M; Proietto, Anna R; Saini, Navneet; Borella, Paola; Bargellini, Annalisa

2016-05-15

Physical and chemical disinfection methods have been proposed with the aim of controlling Legionella water contamination. To date, the most effective procedures for reducing bacterial contamination have not yet been defined. The aim of this study was to assess the long-term effectiveness of various disinfection procedures in order to reduce both culturable and nonculturable (NC) legionellae in different hospital water networks treated with heat, chlorine dioxide, monochloramine, and hydrogen peroxide. The temperature levels and biocide concentrations that proved to give reliable results were analyzed. In order to study the possible effects on the water pipes, we verified the extent of corrosion on experimental coupons after applying each method for 6 months. The percentage of positive points was at its lowest after treatment with monochloramine, followed by chlorine dioxide, hydrogen peroxide, and hyperthermia. Different selections of Legionella spp. were observed, as networks treated with chlorine-based disinfectants were contaminated mainly by Legionella pneumophila serogroup 1, hyperthermia was associated with serogroups 2 to 14, and hydrogen peroxide treatment was associated mainly with non-pneumophila species. NC cells were detected only in heat-treated waters, and also when the temperature was approximately 60°C. The corrosion rates of the coupons were within a satisfactory limit for water networks, but the morphologies differed. We confirm here that chemical disinfection controls Legionella colonization more effectively than hyperthermia does. Monochloramine was the most effective treatment, while hydrogen peroxide may be a promising alternative to chlorine-based disinfectants due to its ability to select for other, less virulent or nonpathogenic species. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Kinetics of chlorination of zirconia in mixture with petroleum coke by chlorine gas

NASA Astrophysics Data System (ADS)

Jena, P. K.; Brocchi, E. A.; Reis, M. L. Dos

1999-06-01

Studies on the kinetics of carbothermic chlorination of zirconium dioxide in gaseous chlorine were carried out with petroleum coke fines in powder form. The amounts of ZrO2 chlorinated were found to be directly proportional to the time of chlorination in the temperature range studied (973 to 1273 K). The activation energy values for chlorination of ZrO2, in mixture with petroleum coke, was found to be 18.3 kJ/mole. The influence of particle size of petroleum coke on the chlorination of ZrO2 (-38 + 25 µm) was studied, and it was found that the rate of chlorination increased up to the size range of -75 to +53 µm, and the size finer than this produced negligible increase. The amount of petroleum coke in the mixture above 17.41 pct in excess of the stoichiometry resulted in very little increase in the rate. The effect of the partial pressure of chlorine ( pCl2) on the rate of chlorination was found to obey the following relationship, derived from the Langmuir adsorption isotherm: v = {k \\cdot K \\cdot pCl_2 }/{l + K \\cdot pCl_2 } where v is the amount of ZrO2 (g/min) reacted, k is the rate constant, and K is the equilibrium constant for adsorption of two chlorine atoms (obtained from the dissociation of a molecule of Cl2 at the carbon surface) on the surface of ZrO2. By plotting 1/ v vs 1/ pCl2, a straight-line relationship with an intercept in x-axis is obtained, further supporting the preceding equation. The dissociation of the adsorbed complex, Cl … ZrO2 … Cl to ZrCl2 and O2 is suggested to be the rate-controlling step. Subsequently, the less stable ZrCl2 combines with Cl2 to form ZrCl4 and the oxygen combines with C to form CO and CO2.

Molecular Genotyping of Viable Cryptosporidium Oocysts

EPA Science Inventory

Cryptosporidium is a chlorination-resistant protozoan parasite that causes a self-limiting diarrheal disease in the immunocompetent or severe chronic diarrhea in the immunocompromised. Two species, C. parvum and C. hominis, cause most cases of cryptosporidiosis in humans, while C...

SAGE III L2 Lunar Event Species Profiles (Binary)

Atmospheric Science Data Center

2017-10-27

... Search and Order:  Earthdata Search   FTP Access:  Data Pool Parameters:  Chlorine Dioxide Nitrogen Dioxide ... Data Additional Info:  Data Format: Big Endian/IEEE Binary; Avg Size in MB: 0.017 SCAR-B Block:  ...

3D Chlorine and Monochloramine Penetration and Nitrifying Biofilm Activity and Viability: Periodic Chlorine Switch Implications

EPA Science Inventory

Biofilm formation in drinking water distribution systems has been associated with water quality degradation and may result in non-compliance with existing regulations. United States water utilities report biofilm survival and regrowth despite disinfectant presence, and systems t...

Removal of diclofenac by conventional drinking water treatment processes and granular activated carbon filtration.

PubMed

Rigobello, Eliane Sloboda; Dantas, Angela Di Bernardo; Di Bernardo, Luiz; Vieira, Eny Maria

2013-06-01

This study was carried out to evaluate the efficiency of conventional drinking water treatment processes with and without pre-oxidation with chlorine and chlorine dioxide and the use of granular activated carbon (GAC) filtration for the removal of diclofenac (DCF). Water treatment was performed using the Jar test with filters on a lab scale, employing nonchlorinated artesian well water prepared with aquatic humic substances to yield 20HU true color, kaolin turbidity of 70 NTU and 1mgL(-1) DCF. For the quantification of DCF in water samples, solid phase extraction and HPLC-DAD methods were developed and validated. There was no removal of DCF in coagulation with aluminum sulfate (3.47mgAlL(-1) and pH=6.5), flocculation, sedimentation and sand filtration. In the treatment with pre-oxidation and disinfection, DCF was partially removed, but the concentration of dissolved organic carbon (DOC) was unchanged and byproducts of DCF were observed. Chlorine dioxide was more effective than chorine in oxidizing DCF. In conclusion, the identification of DCF and DOC in finished water indicated the incomplete elimination of DCF through conventional treatments. Nevertheless, conventional drinking water treatment followed by GAC filtration was effective in removing DCF (⩾99.7%). In the oxidation with chlorine, three byproducts were tentatively identified, corresponding to a hydroxylation, aromatic substitution of one hydrogen by chlorine and a decarboxylation/hydroxylation. Oxidation with chlorine dioxide resulted in only one byproduct (hydroxylation). Copyright © 2013 Elsevier Ltd. All rights reserved.

Analytical strategy for the determination of various arsenic species in landfill leachate containing high concentrations of chlorine and organic carbon by HPLC-ICPMS

NASA Astrophysics Data System (ADS)

Bae, J.; An, J.; Kim, J.; Jung, H.; Kim, K.; Yoon, C.; Yoon, H.

2012-12-01

As a variety of wastes containing arsenic are disposed of in landfills, such facilities can play a prominent role in disseminating arsenic sources to the environment. Since it is widely recognized that arsenic toxicity is highly dependent on its species, accurate determination of various arsenic species should be considered as one of the essential goals to properly account for the potential health risk of arsenic in human and the environment. The inductively coupled plasma mass spectrometry linked to high performance liquid chromatography (HPLC-ICPMS) is acknowledged as one of the most important tools for the trace analysis of metallic speciation because of its superior separation capability and detectability. However, the complexity of matrices can cause severe interferences in the analysis results, which is the problem often encountered with HPLC-ICPMS system. High concentration of organic carbon in a sample solution causes carbon build-up on the skimmer and sampling cone, which reduces analytical sensitivity and requires a high maintenance level for its cleaning. In addition, argon from the plasma and chlorine from the sample matrix may combine to form 40Ar35Cl, which has the same nominal mass to charge (m/z) ratio as arsenic. In this respect, analytical strategy for the determination of various arsenic species (e.g., inorganic arsenite and arsenate, monomethylarsonic acid, dimethylarsinic acid, dimethyldithioarsinic acid, and arsenobetaine) in landfill leachate containing high concentrations of chlorine and organic carbon was developed in the present study. Solid phase extraction disk (i.e., C18 disk), which does not significantly adsorb any target arsenic species, was used to remove organic carbon in sample solutions. In addition, helium (He) gas was injected into the collision reaction cell equipped in ICPMS to collapse 40Ar35Cl into individual 40Ar and 35Cl. Although He gas also decreased arsenic intensity by blocking 75As, its signal to noise ratio significantly increased after injecting He gas. We demonstrated that the analytical strategy was achieved improved sensitivity for the determination of various arsenic species in the landfill leachate as one of the complex matrices.

Nanodetection of the disinfection by-products on GC-MS techniques

NASA Astrophysics Data System (ADS)

Ristoiu, Dumitru; Haydee, Melinda; Ristoiu, Tania

2009-01-01

Exposures to disinfection by-products (DBPs) in residential drinking water occur through multiple routes and vary across the population because of differences in the amount and ways people use water. Municipal water in the Romania is disinfected, with chlorine being the most common disinfectant agent. Disinfection of water, in additional to having the benefit of destroying microbes that can transmit diseases, has the drawback of producing a series of compounds known as disinfection by-products (DBPs). Chlorination produces many compounds containing chlorine and/or bromine, some of which have been shown to be carcinogenic, mutagenic, and/or teratogenic in animal studies. The most abundant class of DBPs that result from chlorination of drinking water are trihalomethanes (THMs) - chloroform (CHCl3), dichlorobromomethane (CHCl2Br), dibromochloromethane (CHBr2Cl) and bromoform (CHBr3). The most predominant THM species was CHCl3 and it highest concentration was 85•106 ng/m3. The others THMs compounds concentration were lower, between 65•104 ng/m3 and 12•106 ng/m3. THMs compounds were analyzed on gas chromatography coupled with mass spectrometer detector (GC-MS) and head space technique (HS) was used for all analysis.

Identification of reaction products from reactions of free chlorine with the lipid-regulator gemfibrozil.

PubMed

Krkošek, Wendy H; Koziar, Stephen A; White, Robert L; Gagnon, Graham A

2011-01-01

High global consumption rates have led to the occurrence of pharmaceutically active compounds (PhACs) in wastewater. The use of chlorine to disinfect wastewater prior to release into the environment may convert PhACs into uncharacterized chlorinated by-products. In this investigation, chlorination of a common pharmaceutical, the antihyperlipidemic agent gemfibrozil, was documented. Gemfibrozil (2,2-dimethyl-5-(2,5-dimethylphenoxy)pentanoic acid) was reacted with sodium hypochlorite and product formation was monitored by gas chromatography-mass spectrometry (GC-MS). The incorporation of one, two or three chlorine atoms into the aromatic region of gemfibrozil was demonstrated using negative-ion electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS/MS). Further analysis using (1)H nuclear magnetic resonance (NMR) spectroscopy identified the reaction products as 4'-ClGem (5-(4-chloro-2,5-dimethylphenoxy)-2,2-dimethylpentanoic acid) 4',6'-diClGem (5-(4,6-dichloro-2,5-dimethylphenoxy)-2,2-dimethylpentanoic acid), and 3',4',6'-triClGem (5-(3,4,6-trichloro-2,5-dimethylphenoxy)-2,2-dimethylpentanoic acid), products consistent with electrophilic aromatic substitution reactions. The rapid reaction of gemfibrozil with free chlorine at pH conditions relevant to water treatment indicates that a mixture of chlorinated gemfibrozils is likely to be found in wastewater disinfected with chlorine. Copyright © 2010 Elsevier Ltd. All rights reserved.

Stable Chlorine Isotopes and Elemental Chlorine by Thermal Ionization Mass Spectrometry and Ion Chromatography; Martian Meteorites, Carbonaceous Chondrites and Standard Rocks

NASA Technical Reports Server (NTRS)

Nakamura, N.; Nyquist, L. E.; Reese, Y.; Shih, C.-Y.; Fujitani, T.; Okano, O.

2011-01-01

Recently significantly large mass fractionation of stable chlorine isotopes has been reported for terrestrial and lunar samples [1,2]. In addition, in view of possible early solar system processes [3] and also potential perchlorate-related fluid/microbial activities on the Martian surface [4,5], a large chlorine isotopic fractionation might be expected for some types of planetary materials. Due to analytical difficulties of isotopic and elemental analyses, however, current chlorine analyses for planetary materials are controversial among different laboratories, particularly between IRMS (gas source mass spectrometry) and TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1,6,7] for isotopic analyses, as well as between those doing pyrohydrolysis and other groups [i.e. 6,8]. Additional careful investigations of Cl isotope and elemental abundances are required to confirm real chlorine isotope and elemental variations for planetary materials. We have developed a TIMS technique combined with HF-leaching/ion chromatography at NASA JSC that is applicable to analysis of small amounts of meteoritic and planetary materials. We present here results for several standard rocks and meteorites, including Martian meteorites.

In vitro genotoxicity of chlorinated drinking water processed from humus-rich surface water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liimatainen, A.; Grummt, T.

Chlorination by-products of drinking waters are capable of inducing sister chromatid exchanges (SCE) and chromosome aberrations (CA) in vitro, in addition to their mutagenic activity in the Ames test. Finnish drinking waters, processed from humus-rich surface water using chlorine disinfection, have been found to be highly mutagenic in the Ames' test. The highest activities have been found in the acidic, non-volatile fraction of the water concentrates using tester strain TA100 without metabolic activation by S9mix. The mutagenicities have varied between 500 and 14,000 induced revertants per liter. These figures are one to two magnitudes higher than those reported elsewhere. Themore » authors studied five Finnish drinking water samples for their potency to exert genotoxic effects, SCEs and CAs, in mammalian cells in vitro (human peripheral lymphocytes and Chinese hamster lung fibroblasts).« less

Preliminary GRS Measurement of Chlorine Distribution on Surface of Mars

NASA Astrophysics Data System (ADS)

Keller, J. M.; Boynton, W. V.; Taylor, G. J.; Hamara, D.; Janes, D. M.; Kerry, K.

2003-12-01

Ongoing measurements with the Gamma Ray Spectrometer (GRS) aboard Mars Odyssey provide preliminary detection of chlorine at the surface of Mars. Summing all data since boom deployment and using a forward calculation model, we estimate values for chlorine concentration at 5° resolution. Rebinning this data and smoothing with a 15-degree-radius boxcar filter reveal regions of noticeable chlorine enrichment at scales larger than the original 5° resolution and allow for preliminary comparison with previous Mars datasets. Analyzing chlorine concentrations within 30 degrees of the equator, we find a negative correlation with thermal inertia (R2=0.55) and positive correlation with albedo (R2=0.52), indicating that chlorine is associated with fine, non-rock surface materials. Although possibly a smoothing artifact, the spatial correlation is more noticeable in the region covering Tharsis and Amazonis than around Arabia and Elysium. Additionally, a noticeable region of chlorine enrichment appears west of Tharsis Montes ( ˜0 to 20N, ˜110 to 150W) and chlorine concentration is estimated to vary in the equatorial region by over a factor of two. A simplified two-component model involving chlorine-poor rocks and a homogenous chlorine-rich fine material requires rock abundance to vary from zero to over 50%, a result inconsistent with previous measurements and models. In addition to variations in rock composition and distribution, substantial variations in chlorine content of various types of fine materials including dust, sand, and duricrust appear important in explaining this preliminary observation. Surprisingly, visual comparison of surface units mapped by Christensen and Moore (1992) does not show enrichment in chlorine associated with regions of indurated surfaces, where cementation has been proposed. Rather, Tharsis, a region of active deposition with proposed mantling of 0.1 to 2 meters of recent dust (Christensen 1986), shows the greatest chlorine signal. In light of suggested fine material formation mechanisms, this preliminary result is intriguing. Tentative models involving venting of chlorine from hydrothermal systems (Newsom 1999), enrichment of chlorine through volcanic aerosols (Settle 1979) or acid fog reactions (Banin et al 1997), and preferential deposition of a proposed salt component in Mars fines (Clark 1993), if more easily mobilized from the Martian duricrust, are viable. Finally, this preliminary measurement will be improved through further data collection by Mars Odyssey and comparisons with MER and future missions.

Use of biological assay systems to assess the relative carcinogenic hazards of disinfection by-products.

PubMed Central

Bull, R J; Robinson, M; Meier, J R; Stober, J

1982-01-01

Other workers have clearly shown that most, if not all, drinking water in the U.S. contains chemicals that possess mutagenic and/or carcinogenic activity by using bacterial and in vitro methods. In the present work, increased numbers of tumors were observed with samples of organic material isolated from 5 U.S. cities administered as tumor initiators in mouse skin initiation/promotion studies. Only in one case was the result significantly different from control. In studies designed to test whether disinfection practice contributes significantly to the tumor initiating activity found in drinking water mixed results have been obtained. In one experiment, water disinfected by chlorination, ozonation or combined chlorine resulted in a significantly greater number of papillomas when compared to nondisinfected water. In two subsequent experiments, where water was obtained from the Ohio River at different times of the year, no evidence of increased initiating activity was observed with any disinfectant. Analysis of water obtained at the comparable times of the year for total organic halogen, and trihalomethane formation revealed a substantial variation in the formation of these products. Considering the problems such variability poses for estimating risks associated with disinfection by-products, a model system which makes use of commercially obtained humic acid as a substrate for chlorination was investigated using the Ames test. Humic and fulvic acids obtained from two surface waters as well as the commercially obtained humic acid were without activity in TA 1535, TA 1537, TA 1538, TA 98 or TA 100 strains of S. typhimurium. Following treatment with a 0.8 molar ratio of chlorine (based on carbon) significant mutagenic activity was observed with all humic and fulvic acid samples. Comparisons of the specific mutagenic activity of the chlorinated products suggests that the commercial material might provide a useful model for studying health hazards associated with disinfection reactions by-products. PMID:7151763

The fate of chlorinated aliphatics in anaerobic treatment under transient loading

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chiu, Y.C.

1993-01-01

A CSTR with dispersed-growth anaerobic bacteria that simultaneously remove COD and chlorinated aliphatics was used. Seven chlorinated aliphatics (methylene chloride, chloroform, carbon tetrachloride, 1,1,1-trichloroethane, 1,1-dichloroethylene, trichloroethylene, and tetrachloroethylene) were biotransformed into lower-chlorinated compounds by anaerobic treatment, utilizing propionic acid (HPr) or acetic acid (HAc). The microorganisms supplied with HAc grew and were sustained at higher BSS concentrations (4,500 to 11,000 mg/L) than those with HPr (2,000 to 5,000 mg/L). The anaerobic treatment process has a considerable potential for acclimation to and biotransformation of toxic chlorinated aliphatics. For providing a safe operation range, the maximum loading rates of the chlorinated aliphaticsmore » are defined as the observed daily injection of those compounds which resulted in 50% activity of the biomass. Based on the reactor volume, the maximum chlorinated compound loading rates to the microorganisms metabolizing HPr were from 0.4 to 90 mg/L-day, while the rates ranged from 0.6 to 190 mg/L-day for the microorganisms metabolizing HAc. When based on biomass, the maximum loading rates of the microorganisms metabolizing HPr were from 0.2 to 26 mg/g cell-day, while rates for the microorganisms metabolizing HAc ranged from 0.1 to 19 mg/g cell-day. Anaerobic microorganisms have higher resistance to chlorinated aliphatic alkenes than alkanes, and can biotransform about 0.04 to 68 pound chlorinated aliphatics while simultaneously metabolizing 1,000 pounds COD. Therefore, within the safe operation range, the anaerobic process can stabilize organic pollution at a high rate while still biotransforming chlorinated aliphatics.« less

Transformation of Organophosphorus Pesticides in the Presence of Aqueous Chlorine: Kinetics, Pathways, and Structure-Activity Relationships

EPA Science Inventory

The fate of organophosphorus (OP) pesticides in the presence of aqueous chlorine was investigated under simulated drinking water treatment conditions. Intrinsic rate coefficients were found for the reaction of hypochlorous acid (kHOCl,OP) and hypochlorite ion (kOCl,OP) for eight...

Influence of Chlorine Substituents on Rates of Oxidation of Chlorinated Biphenyls by the Biphenyl Dioxygenase of Burkholderia sp. Strain LB400

PubMed Central

Arnett, Clint M.; Parales, Juan V.; Haddock, John D.

2000-01-01

Biphenyl dioxygenase from Burkholderia (Pseudomonas) sp. strain LB400 catalyzes the first reaction of a pathway for the degradation of biphenyl and a broad range of chlorinated biphenyls (CBs). The effect of chlorine substituents on catalysis was determined by measuring the specific activity of the enzyme with biphenyl and 18 congeners. The catalytic oxygenase component was purified and incubated with individual CBs in the presence of electron transport proteins and cofactors that were required for enzyme activity. The rate of depletion of biphenyl from the assay mixture and the rate of formation of cis-biphenyl 2,3-dihydrodiol, the oxidation product, were almost equal, indicating that the assay accurately measured enzyme-specific activity. Four classes of CBs were defined based on their oxidation rates. Class I contained 3-CB and 2,5-CB, which gave rates that were approximately twice that of biphenyl. Class II contained 2,5,3′,4′-CB, 2,3,2′,5′-CB, 2,3,4,5-CB, 2,3,2′,3′-CB, 2,4,5,2′,5′-CB, 2,5,3′-CB, 2,5,4′-CB, 2-CB, and 3,4,5-CB, which gave rates that ranged from 97 to 35% of the biphenyl rate. Class III contained only 2,3,4,2′,5′-CB, which gave a rate that was 4% of the biphenyl rate. Class IV contained 2,4,4′-CB, 2,4,2′,4′-CB, 3,4,5,2′-CB, 3,4,5,3′-CB, 3,5,3′,5′-CB, and 3,4,5,2′,5′-CB, which showed no detectable depletion. Rates were not significantly correlated with the aqueous solubilities of the CBs or the number of chlorine substituents on the rings. Oxidation products were detected for all class I, II, and III congeners and were identified as chlorinated cis-dihydrodiols for classes I and II. The specificity of biphenyl dioxygenase for the CBs examined in this study was determined by the relative positions of the chlorine substituents on the aromatic rings rather than the number of chlorine substituents on the rings. PMID:10877788

The use of multiple indices of physiological activity to access viability in chlorine disinfected Escherichia coli O157:H7

NASA Technical Reports Server (NTRS)

Lisle, J. T.; Pyle, B. H.; McFeters, G. A.

1999-01-01

A suite of fluorescent intracellular stains and probes was used, in conjunction with viable plate counts, to assess the effect of chlorine disinfection on membrane potential (rhodamine 123; Rh123 and bis-(1,3-dibutylbarbituric acid) trimethine oxonol; DiBAC4(3)), membrane integrity (LIVE/DEAD BacLight kit), respiratory activity (5-cyano-2,3-ditolyl tetrazolium chloride; CTC) and substrate responsiveness (direct viable counts; DVC) in the commensal pathogen Escherichia coli O157:H7. After a 5 min exposure to the disinfectant, physiological indices were affected in the following order: viable plate counts > substrate responsiveness > membrane potential > respiratory activity > membrane integrity. In situ assessment of physiological activity by examining multiple targets, as demonstrated in this study, permits a more comprehensive determination of the site and extent of injury in bacterial cells following sublethal disinfection with chlorine. This approach to assessing altered bacterial physiology has application in various fields where detection of stressed bacteria is of interest.

Role of ozone and granular activated carbon in the removal of mutagenic compounds.

PubMed Central

Bourbigot, M M; Hascoet, M C; Levi, Y; Erb, F; Pommery, N

1986-01-01

The identification of certain organic compounds in drinking water has led water treatment specialists to be increasingly concerned about the eventual risks of such pollutants to the health of consumers. Our experiments focused on the role of ozone and granular activated carbon in removing mutagenic compounds and precursors that become toxic after chlorination. We found that if a sufficient dose of ozone is applied, its use does not lead to the creation of mutagenic compounds in drinking water and can even eliminate the initial mutagenicity of the water. The formation of new mutagenic compounds seems to be induced by ozonation that is too weak, although these mutagens can be removed by GAC filtration. Ozone used with activated carbon can be one of the best means for eliminating the compounds contributing to the mutagenicity of water. A combined treatment of ozone and activated carbon also decreases the chlorine consumption of the treated water and consequently reduces the formation of chlorinated organic compounds. PMID:3816720

AN ISOMER PREDICTION MODEL FOR PCNS, PCDD/FS, AND PCBS FROM MUNICIPAL WASTE INCINERATORS

EPA Science Inventory

Isomer patterns of polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated biphenyls (PCBs) from municipal waste incinerators (MWIs) were predicted by a model based on dechlorination kinetics from the most-chlorinated species. Successfu...

[Water disinfection by the combined exposure to super-high frequency energy and available chlorine produced during water electrolysis].

PubMed

Klimarev, S I; Siniak, Iu E

2014-01-01

The article reports the results of studying the effects on polluted water of SHF-energy together with the residual free (active) chlorine as a by-product of electrolysis action on dissolved chlorine-containing salts. Purpose of the studies was to evaluate input of these elements to the water disinfection effect. The synergy was found to kill microorganisms without impacts on the physicochemical properties of processed water or nutrient medium; therefore, it can be used for water treatment, and cultivation of microorganisms in microbiology.

Dioxin-like activity of brominated dioxins as individual compounds or mixtures in in vitro reporter gene assays with rat and mouse hepatoma cell lines.

PubMed

Suzuki, G; Nakamura, M; Michinaka, C; Tue, N M; Handa, H; Takigami, H

2017-10-01

In vitro reporter gene assays detecting dioxin-like compounds have been developed and validated since the middle 1990's, and applied to the determination of dioxin-like activities in various samples for their risk management. Data on characterizing the potency of individual brominated dioxins and their activity in mixture with chlorinated dioxins are still limited on the cell-based assay. This study characterized the dioxin-like activities of the 32 brominated dioxins, such as polybrominated dibenzo-p-dioxins, polybrominated dibenzofurans (PBDFs), coplanar polybrominated biphenyls, mixed halogenated dibenzo-p-dioxins and dibenzofurans (PXDFs), as a sole component or in a mixture by DR-CALUX (dioxin-responsive chemically activated luciferase expression) using the rat hepatoma H4IIE cell line and XDS-CALUX (xenobiotic detection systems-chemically activated luciferase expression) assays using the mouse hepatoma H1L6.1 cell line. The 2,3,7,8-TCDD-relative potencies (REPs) of most of the brominated dioxins were within a factor of 10 of the WHO toxicity equivalency factor (WHO-TEF) for the chlorinated analogues. The REPs of a few PXDFs were an order of magnitude higher than the corresponding WHO-TEFs, indicating their toxicological importance. Results with reconstituted mixtures suggest that the activity of brominated and chlorinated dioxins in both CALUX assays was dose-additive. Thus, obtained results indicated the applicability of the CALUX assays as screening tools of brominated dioxins together with their chlorinated analogues. Copyright © 2017 Elsevier Ltd. All rights reserved.

RHIZOSPHERE MICROBIOLOGY OF CHLORINATED ETHENE CONTAMINATED SOILS: EFFECTS ON PHOSPHOLIPID FATTY ACID CONTENT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brigmon, R. L.; Stanhopc, A.; Franck, M. M.

2005-05-26

Microbial degradation of chlorinated ethenes (CE) in rhizosphere soils was investigated at seepline areas impacted by CE plumes. Successful bioremediation of CE in rhizosphere soils is dependent on microbial activity, soil types, plant species, and groundwater CE concentrations. Seepline soils were exposed to trichloroethylene (TCE) and perchloroethylene (PCE) in the 10-50 ppb range. Greenhouse soils were exposed to 2-10 ppm TCE. Plants at the seepline were poplar and pine while the greenhouse contained sweet gum, willow, pine, and poplar. Phospholipid fatty acid (PLFA) analyses were performed to assess the microbial activity in rhizosphere soils. Biomass content was lowest in themore » nonvegetated control soil and highest in the Sweet Gum soil. Bacterial rhizhosphere densities, as measured by PLFA, were similar in different vegetated soils while fungi biomass was highly variable. The PLFA soil profiles showed diverse microbial communities primarily composed of Gram-negative bacteria. Adaptation of the microbial community to CE was determined by the ratio of {omega}7t/{omega}7c fatty acids. Ratios (16:1{omega}7v16:1{omega}7c and 18:l{omega}7t/18:1{omega}7c) greater than 0.1 were demonstrated in soils exposed to higher CE concentrations (10-50 ppm), indicating an adaptation to CE resulting in decreased membrane permeability. Ratios of cyclopropyl fatty acids showed that the vegetated control soil sample contained the fastest microbial turnover rate and least amount of environmental stress. PLFA results provide evidence that sulfate reducing bacteria (SRB) are active in these soils. Microcosm studies with these soils showed CE dechlorinating activity was occurring. This study demonstrates microbial adaptation to environmental contamination and supports the application of natural soil rhizosphere activity as a remedial strategy.« less

Chlorination Kinetics of Titanium Nitride for Production of Titanium Tetrachloride from Nitrided Ilmenite

NASA Astrophysics Data System (ADS)

Ahmadi, Eltefat; Rezan, Sheikh Abdul; Baharun, Norlia; Ramakrishnan, Sivakumar; Fauzi, Ahmad; Zhang, Guangqing

2017-10-01

The kinetics of chlorination of titanium nitride (TiN) was investigated in the temperature range of 523 K to 673 K (250 °C to 400 °C). The results showed that the extent of chlorination slightly increased with increasing temperature and decreasing particle size of titanium nitride at constant flow rate of N2-Cl2 gas mixture. At 523 K (250 °C), the extent of chlorination was 85.6 pct in 60 minutes whereas at 673 K (400 °C), it was 97.7 pct investigated by weight loss measurement and confirmed by ICP analyses. The experimental results indicated that a shrinking unreacted core model with mixed-control mechanism governed the chlorination rate. It was observed that the surface chemical reaction of chlorine gas on the surface of TiN particles was rate controlling in the initial stage and, during later stage, internal (pore) diffusion through the intermediate product layer was rate controlling step. Overall the process follows the mixed-control model incorporating both chemical reaction and internal diffusion control. The activation energy for the chlorination of TiN was found to be about 10.97 kJ mol-1. In processing TiCl4 from TiN and TiO0.02C0.13N0.85, the solids involved in the chlorination process were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM) and Energy-dispersive X-ray spectrometer (EDX). The SEM/EDX results demonstrated the consumption of TiN particles with extent of chlorination that showed shrinking core behavior.

Differential toxicity of drinking water disinfected with combinations of ultraviolet radiation and chlorine.

PubMed

Plewa, Michael J; Wagner, Elizabeth D; Metz, Deborah H; Kashinkunti, Ramesh; Jamriska, Katherine J; Meyer, Maria

2012-07-17

Alternative technologies to disinfect drinking water such as ultraviolet (UV) disinfection are becoming more widespread. The benefits of UV disinfection include reduced risk of microbial pathogens such as Cryptosporidium and reduced production of regulated drinking water disinfection byproducts (DBPs). The objective of this research was to determine if mammalian cell cytotoxicity and genotoxicity varied in response to different chlorination protocols with and without polychromatic medium pressure UV (MPUV) and monochromatic low pressure UV (LPUV) disinfection technologies. The specific aims were to analyze the mammalian cell cytotoxicity and genotoxicity of concentrated organic fractions from source water before and after chlorination and to determine the cytotoxicity and genotoxicity of the concentrated organic fractions from water samples treated with UV alone or UV before or after chlorination. Exposure of granular activated carbon-filtered Ohio River water to UV alone resulted in the lowest levels of mammalian cell cytotoxicity and genotoxicity. With combinations of UV and chlorine, the lowest levels of cytotoxicity and genotoxicity were observed with MPUV radiation. The best combined UV plus chlorine methodology that generated the lowest cytotoxicity and genotoxicity employed chlorination first followed by MPUV radiation. These data may prove important in the development of multibarrier methods of pathogen inactivation of drinking water, while limiting unintended toxic consequences.

Kinetics and mechanism of styrene epoxidation by chlorite: role of chlorine dioxide.

PubMed

Leigh, Jessica K; Rajput, Jonathan; Richardson, David E

2014-07-07

An investigation of the kinetics and mechanism for epoxidation of styrene and para-substituted styrenes by chlorite at 25 °C in the pH range of 5-6 is described. The proposed mechanism in water and water/acetonitrile includes seven oxidation states of chlorine (-I, 0, I, II, III, IV, and V) to account for the observed kinetics and product distributions. The model provides an unusually detailed quantitative mechanism for the complex reactions that occur in mixtures of chlorine species and organic substrates, particularly when the strong oxidant chlorite is employed. Kinetic control of the reaction is achieved by the addition of chlorine dioxide to the reaction mixture, thereby eliminating a substantial induction period observed when chlorite is used alone. The epoxidation agent is identified as chlorine dioxide, which is continually formed by the reaction of chlorite with hypochlorous acid that results from ClO produced by the epoxidation reaction. The overall stoichiometry is the result of two competing chain reactions in which the reactive intermediate ClO reacts with either chlorine dioxide or chlorite ion to produce hypochlorous acid and chlorate or chloride, respectively. At high chlorite ion concentrations, HOCl is rapidly eliminated by reaction with chlorite, minimizing side reactions between HOCl and Cl2 with the starting material. Epoxide selectivity (>90% under optimal conditions) is accurately predicted by the kinetic model. The model rate constant for direct reaction of styrene with ClO2(aq) to produce epoxide is (1.16 ± 0.07) × 10(-2) M(-1) s(-1) for 60:40 water/acetonitrile with 0.20 M acetate buffer. Rate constants for para substituted styrenes (R = -SO3(-), -OMe, -Me, -Cl, -H, and -NO2) with ClO2 were determined. The results support the radical addition/elimination mechanism originally proposed by Kolar and Lindgren to account for the formation of styrene oxide in the reaction of styrene with chlorine dioxide.

Degradation Investigation of Selected Taste and Odor Compounds by a UV/Chlorine Advanced Oxidation Process

PubMed Central

Fang, Jingyun; Liu, Jiajian; Shang, Chii; Fan, Chihhao

2018-01-01

Taste- and odor-causing (T&O) compounds are a major concern in drinking water treatment plants due to their negative impacts on the safety and palatability of water supply. This study explored the degradation kinetics and radical chemistry of four often-detected T&O compounds, geosmin (GSM), 2-methylisoborneol (MIB), benzothiazole (BT), and 2-isobutyl-3-methoxypyrazine (IBMP), in the ultraviolet/chlorine (UV/chlorine) advanced oxidation process. All experiments were carried out in a 700 mL photoreactor and the process effectively degraded the investigated T&O compounds in a slightly acidic environment. The degradation of T&O decreased with increasing pH but slightly with decreasing chlorine dosage. When the pH increased from 6 to 8, the pseudo-first-order rate constants of GSM, MIB, BT, and IBMP dropped from 2.84 × 10−3, 2.29 × 10−3, 3.64 × 10−3, and 2.76 × 10−3 s−1 to 3.77 × 10−4, 2.64 × 10−4, 6.48 × 10−4, and 6.40 × 10−4 s−1, respectively. Increasing the chlorine dosage slightly accelerated the degradation of the investigated T&O compounds, but excessive hypochlorous acid and hypochlorite scavenged the HO• radicals and reactive chlorine species (RCS). Generally, HO• primarily contributed to the degradation of all of the investigated T&O compounds as compared to RCS. The degradation by RCS was found to be structurally selective. RCS could not degrade GSM, but contributed to the degradation of MIB, BT, and IBMP. The results confirmed that the proposed oxidation process effectively degraded typical T&O compounds in aqueous phase. PMID:29414884

Preparation, structure and luminescent characterization of a series of metal-organic frameworks based on flexible ligands with nitrogen heterocycles and carboxyl

NASA Astrophysics Data System (ADS)

Dai, Hai-yu; Tang, Yu-yuan; Wang, Cui-juan; Chen, Shuang; Tong, Yan; Zhang, Zhi-Bing

2017-12-01

Seven new compounds, [Zn(pypymba)2]n(1), [Co(pypymba)2]n(2), [Cd(pypymba)2]n(3), [Cd(Hpypymba)Cl2]n(4), {[Cd(pypymba)Cl]·C2H5OH·H2O}n(5), [Cd(pypyaa)Cl]n(6), {[Cd2(pyznpy)2Cl2H2O]·H2O}n(7) [Hpypymba = 4-((3-(pyrazin-2-yl)-1H-pyrazol-1-yl)methyl)benzoic acid, Hpyznpy = 4-((3-(pyridin-2-yl)-1H-pyrazol-1-yl)methyl)benzoic acid, Hpypyaa = 2-(3-pyridin-2-yl)-1H-pyrazol-1-yl)acetic acid], were hydrothermally synthesized by tuning the metal ion's species, counter anions, solvents and pH values and characterized by routine methods: XRD, elemental analysis, fluorescence properties analysis, TGA and crystal structure analysis and single-crystal X-ray crystallography. The main structures of the compounds 1, 2, and 3 are extended to similar 3D structures by C-H…N, C-H…O hydrogen bonds and π…π stacking under the same synthesis method. Each Cd(II) node of compound 4 has four chlorine bridges (two pairs of double chlorine); Each Cd(II) node of compounds 5, 6 has two chlorine bridges (a pair of double chlorine bridges), while their spatial structures are expanded in different ways. Compound 7 also contains chlorine atoms, but does not contain chlorine bridged structures. The luminescent properties of compound 7 and the ones immersed in various kinds of organic compounds and nitrate@EtOH solutions have been investigated. Importantly, 7 shows highly sensitive response to nitrobenzene and Fe3+ through luminescence quenching effects, making it a promising luminescent sensor for nitrobenzene and Fe3+.

The Potential Feasibility of Chlorinic Photosynthesis on Exoplanets

NASA Astrophysics Data System (ADS)

Haas, Johnson R.

2010-11-01

The modern search for life-bearing exoplanets emphasizes the potential detection of O2 and O3 absorption spectra in exoplanetary atmospheres as ideal signatures of biology. However, oxygenic photosynthesis may not arise ubiquitously in exoplanetary biospheres. Alternative evolutionary paths may yield planetary atmospheres tinted with the waste products of other dominant metabolisms, including potentially exotic biochemistries. This paper defines chlorinic photosynthesis (CPS) as biologically mediated photolytic oxidation of aqueous Cl- to form halocarbon or dihalogen products, coupled with CO2 assimilation. This hypothetical metabolism appears to be feasible energetically, physically, and geochemically, and could potentially develop under conditions that approximate the terrestrial Archean. It is hypothesized that an exoplanetary biosphere in which chlorinic photosynthesis dominates primary production would tend to evolve a strongly oxidizing, halogen-enriched atmosphere over geologic time. It is recommended that astronomical observations of exoplanetary outgoing thermal emission spectra consider signs of halogenated chemical species as likely indicators of the presence of a chlorinic biosphere. Planets that favor the evolution of CPS would probably receive equivalent or greater surface UV flux than is produced by the Sun, which would promote stronger abiotic UV photolysis of aqueous halides than occurred during Earth's Archean era and impose stronger evolutionary selection pressures on endemic life to accommodate and utilize halogenated compounds. Ocean-bearing planets of stars with metallicities equivalent to, or greater than, the Sun should especially favor the evolution of chlorinic biospheres because of the higher relative seawater abundances of Cl, Br, and I such planets would tend to host. Directed searches for chlorinic biospheres should probably focus on G0-G2, F, and A spectral class stars that have bulk metallicities of +0.0 Dex or greater.

The potential feasibility of chlorinic photosynthesis on exoplanets.

PubMed

Haas, Johnson R

2010-11-01

The modern search for life-bearing exoplanets emphasizes the potential detection of O(2) and O(3) absorption spectra in exoplanetary atmospheres as ideal signatures of biology. However, oxygenic photosynthesis may not arise ubiquitously in exoplanetary biospheres. Alternative evolutionary paths may yield planetary atmospheres tinted with the waste products of other dominant metabolisms, including potentially exotic biochemistries. This paper defines chlorinic photosynthesis (CPS) as biologically mediated photolytic oxidation of aqueous Cl(-) to form halocarbon or dihalogen products, coupled with CO(2) assimilation. This hypothetical metabolism appears to be feasible energetically, physically, and geochemically, and could potentially develop under conditions that approximate the terrestrial Archean. It is hypothesized that an exoplanetary biosphere in which chlorinic photosynthesis dominates primary production would tend to evolve a strongly oxidizing, halogen-enriched atmosphere over geologic time. It is recommended that astronomical observations of exoplanetary outgoing thermal emission spectra consider signs of halogenated chemical species as likely indicators of the presence of a chlorinic biosphere. Planets that favor the evolution of CPS would probably receive equivalent or greater surface UV flux than is produced by the Sun, which would promote stronger abiotic UV photolysis of aqueous halides than occurred during Earth's Archean era and impose stronger evolutionary selection pressures on endemic life to accommodate and utilize halogenated compounds. Ocean-bearing planets of stars with metallicities equivalent to, or greater than, the Sun should especially favor the evolution of chlorinic biospheres because of the higher relative seawater abundances of Cl, Br, and I such planets would tend to host. Directed searches for chlorinic biospheres should probably focus on G0-G2, F, and A spectral class stars that have bulk metallicities of +0.0 Dex or greater.

Factors affecting the formation of nitrogenous disinfection by-products during chlorination of aspartic acid in drinking water.

PubMed

Chen, Wei; Liu, Zhigang; Tao, Hui; Xu, Hang; Gu, Yanmei; Chen, Zhaolin; Yu, Jingjing

2017-01-01

The formation of emerging nitrogenous disinfection by-products (N-DBPs) from the chlorination of aspartic acid (Asp) was investigated. The yield of dichloroacetonitrile (DCAN) was higher than other N-DBPs, such as dichloroacetamide(DCAcAm) and chloropicrin (TCNM) during the chlorination of Asp. The formation of DCAN, DCAcAm, and TCNM all showed a trend of first increasing and then decreasing during the chlorination of Asp with increasing contact time. The dosage of chlorine had an impact on the formation of DCAN, DCAcAm, and TCNM. The highest yields of DCAN and DCAcAm appeared when the Cl 2 /Asp molar ratio was about 20, the yield of TCNM increased with increasing the Cl 2 /Asp molar ratio from 5 to 30 and TCNM was not produced when the ratio was less than 5. Cyanogen chloride (CNCl) was detected when the Cl 2 /Asp molar ratio was lower than 5. N-DBPs formation was influenced by pH. DCAN formation increased with increasing pH from 5 to 6 and then decreased with increasing pH from 6 to 9, but DCAcAm and TCNM increased with increasing pH from 5 to 8 and then decreased. Higher temperatures reduced the formation of DCAN and DCAcAm, but increased TCNM formation. DCAN and DCAcAm formation decreased, and relatively stable TCNM formation increased, with increasing free chlorine contact time during chloramination. N-nitrosodimethylamine (NDMA) was produced during chloramination of Asp and increased with prolonged chloramination contact time. The presence of bromide ions enhanced the yields of haloacetonitriles and shifted N-DBPs to more brominated species. Copyright © 2016 Elsevier B.V. All rights reserved.

The Chlorine Isotopic Composition Of Lunar UrKREEP

NASA Technical Reports Server (NTRS)

Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

2016-01-01

Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. Numerous studies have examined the abundances and isotopic compositions of volatiles in lunar apatite, Ca5(PO4)3(F,Cl,OH). In particular, apatite has been used as a tool for assessing the sources of H2O in the lunar interior. However, current models for the Moon's formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. For ex-ample, in the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs (Rare Earth Elements), and P, collectively called KREEP, and in its primitive form - urKREEP, given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon (BSM). In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes in lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

Modeling bromide effects on yields and speciation of dihaloacetonitriles formed in chlorinated drinking water.

PubMed

Roccaro, Paolo; Chang, Hyun-shik; Vagliasindi, Federico G A; Korshin, Gregory V

2013-10-15

This study examined effects of bromide on yields and speciation of dihaloacetonitrile (DHAN) species that included dichloro-, bromochloro- and dibromoacetonitriles generated in chlorinated water. Experimental data obtained using two water sources, varying concentrations and characters of Natural Organic Matter (NOM), bromide concentrations, reaction times, chlorine doses, temperatures and pHs were interpreted using a semi-phenomenological model that assumed the presence of three kinetically distinct sites in NOM (denoted as sites S1, S2 and S3) and the occurrence of sequential incorporation of bromine and chlorine into them. One site was found to react very fast with the chlorine and bromine but its contribution in the DHAN generation was very low. The site with the highest contribution to the yield of DHAN (>70%) has the lowest reaction rates. The model introduced dimensionless coefficients (denoted as φ1(DHAN), φ2(DHAN) and φ3(DHAN)) applicable to the initial DHAN generation sites and their monochlorinated and monobrominated products, respectively. These parameters were used to quantify the kinetic preference to bromine incorporation over that of chlorine. Values of these coefficients optimized for DHAN formation were indicative of the strongly preferential incorporation of bromine into the engaged NOM sites. The same set of φ(i)(DHAN) coefficients could be used to model the speciation of DHAN released from their kinetically different precursors. The dimensionless speciation coefficients φ(i)(DHAN) were determined to be site specific and dependent on the NOM content and character as well as pH. The presented model of DHAN formation and speciation can help quantify in more detail the generation of DHAN and provide more insight necessary for further assessment of their potential health effects. Copyright © 2013 Elsevier Ltd. All rights reserved.

A spore counting method and cell culture model for chlorine disinfection studies of Encephalitozoon syn. Septata intestinalis.

PubMed

Wolk, D M; Johnson, C H; Rice, E W; Marshall, M M; Grahn, K F; Plummer, C B; Sterling, C R

2000-04-01

The microsporidia have recently been recognized as a group of pathogens that have potential for waterborne transmission; however, little is known about the effects of routine disinfection on microsporidian spore viability. In this study, in vitro growth of Encephalitozoon syn. Septata intestinalis, a microsporidium found in the human gut, was used as a model to assess the effect of chlorine on the infectivity and viability of microsporidian spores. Spore inoculum concentrations were determined by using spectrophotometric measurements (percent transmittance at 625 nm) and by traditional hemacytometer counting. To determine quantitative dose-response data for spore infectivity, we optimized a rabbit kidney cell culture system in 24-well plates, which facilitated calculation of a 50% tissue culture infective dose (TCID(50)) and a minimal infective dose (MID) for E. intestinalis. The TCID(50) is a quantitative measure of infectivity and growth and is the number of organisms that must be present to infect 50% of the cell culture wells tested. The MID is as a measure of a system's permissiveness to infection and a measure of spore infectivity. A standardized MID and a standardized TCID(50) have not been reported previously for any microsporidian species. Both types of doses are reported in this paper, and the values were used to evaluate the effects of chlorine disinfection on the in vitro growth of microsporidia. Spores were treated with chlorine at concentrations of 0, 1, 2, 5, and 10 mg/liter. The exposure times ranged from 0 to 80 min at 25 degrees C and pH 7. MID data for E. intestinalis were compared before and after chlorine disinfection. A 3-log reduction (99.9% inhibition) in the E. intestinalis MID was observed at a chlorine concentration of 2 mg/liter after a minimum exposure time of 16 min. The log(10) reduction results based on percent transmittance-derived spore counts were equivalent to the results based on hemacytometer-derived spore counts. Our data suggest that chlorine treatment may be an effective water treatment for E. intestinalis and that spectrophotometric methods may be substituted for labor-intensive hemacytometer methods when spores are counted in laboratory-based chlorine disinfection studies.

Defect formation during chlorine-based dry etching and their effects on the electronic and structural properties of InP/InAsP quantum wells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Landesman, Jean-Pierre, E-mail: jean-pierre.landesman@univ-rennes1.fr; Jiménez, Juan; Torres, Alfredo

The general objective is the investigation of the defects formed by dry etching tools such as those involved in the fabrication of photonic devices with III–V semiconductors. Emphasis is put on plasma exposures with chlorine-based chemistries. In addition to identifying these defects and describing their effects on the electro-optic and structural properties, the long-term target would be to predict the impact on the parameters of importance for photonic devices, and possibly include these predictions in their design. The work is first centered on explaining the experimental methodology. This methodology starts with the design and growth of a quantum well structuremore » on indium phosphide, including ternary indium arsenide/phosphide quantum wells with graded arsenic/phosphor composition. These samples have then been characterized by luminescence methods (photo- and cathodoluminescence), high-resolution transmission electron microscopy, and secondary ion mass spectrometry. As one of the parameters of importance in this study, the authors have also included the doping level. The samples have been exposed to the etching plasmas for “short” durations that do not remove completely the quantum wells, but change their optical signature. No masking layer with lithographic features was involved as this work is purely oriented to study the interaction between the plasma and the samples. A significant difference in the luminescence spectra of the as-grown undoped and doped samples is observed. A mechanism describing the effect of the built-in electric field appearing as a consequence of the doping profile is proposed. This mechanism involves quantum confined Stark effect and electric-field induced carrier escape from the quantum wells. In the following part, the effects of exposure to various chlorine-based plasmas were explored. Differences are again observed between the undoped and doped samples, especially for chemistries containing silicon tetrachloride. Secondary ion mass spectrometry indicates penetration of chlorine in the structures. Transmission electron microscopy is used to characterize the quantum well structure before and after plasma bombardment. By examining carefully the luminescence spectral properties, the authors could demonstrate the influence of the etching plasmas on the built-in electric field (in the case of doped samples), and relate it to some ionic species penetrating the structures. Etching plasmas involving both chlorine and nitrogen have also been studied. The etching rate for these chemistries is much slower than for some of the silicon tetrachloride based chemistries. Their effects on the samples are also very different, showing much reduced effect on the built-in electric field (for the doped samples), but significant blue-shifts of the luminescence peaks that the authors attributed to the penetration of nitrogen in the structures. Nitrogen, in interstitial locations, induces mechanical compressive stress that accounts for the blue-shifts. Finally, from the comparison between secondary ion mass spectrometry and luminescence spectra, the authors suggest some elements for a general mechanism involved in the etching by chloride-chemistries, in which a competition takes place between the species at the surface, active for the etching mechanism, and the species that penetrate the structure, lost for the etching process, but relevant in terms of impact on the electro-optic and structural features of the exposed materials.« less

Contrast Between 1992 and 1997 High Latitude Spring Haloe Observations of Lower Stratospheric HCl

NASA Technical Reports Server (NTRS)

Douglass, A. R.; Kawa, S. R.

1998-01-01

HCl measurements from HALOE in the northern hemisphere during mid-May 1997 revealed vortex fragments in which the chlorine reservoir partitioning was strongly pushed toward HCl (approx. 90% HCl, approx. 10% ClONO2), similar to partitioning previously observed in the Antarctic vortex region. In contrast, observations of ClONO2 and HCl in the northern polar spring, 1992, and in other years, show these species established the balance typical for gas phase photochemical reactions in this region (approx. 60% HCl, approx. 40% ClONO2). Annually, chlorine reservoirs in the winter lower stratosphere polar vortex are converted to chlorine radicals via heterogeneous reactions on particle surfaces at very cold temperatures (less than about 200 K). As temperatures warm in spring, the heterogeneous processes become insignificant compared with gas phase reactions, and the chlorine reservoirs are reformed. Measurements through the northern winter/spring in 1992 show rapid formation of ClONO2, followed by steady loss of ClONO2 and increasing HCl. Although ClONO2 measurements are not available for 1997, the HCl increase in 1997 is observed to be much more rapid and the eventual HCl mixing ratio is about 50% greater than that of 1992. The observations are examined through comparison with the Goddard three-dimensional chemistry and transport model. This model utilizes winds and temperatures from the Goddard Earth Observing System Data Assimilation System and a complete integration scheme for stratospheric photochemistry. Analysis of the evolution of HCl and ClONO2 shows that the observed difference in the overall rate of HCl formation is explained by the sensitivity of the gas-phase chemistry to the ozone mixing ratio and the temperature. The results show that the model accurately simulates HCl and ClONO2 evolution during these two winters. Model validity is further supported by comparisons with O3 and reactive nitrogen species NO and NO2. This analysis provides a sensitive test of the lower stratospheric chlorine photochemistry, particularly because the analysis considers constituent evolution at a time when the HCl and ClONO2 are far from a photochemical stationary state.

Congener-specific polychlorinated biphenyl patterns in eggs of aquatic birds from the lower Laguna Madre, Texas

USGS Publications Warehouse

Mora, Miguel A.

1996-01-01

Eggs from four aquatic bird species nesting in the Lower Laguna Madre, Texas, were collected to determine differences and similarities in the accumulation of congener-specific polychlorinated biphenyls (PCBs) and to evaluate PCB impacts on reproduction. Because of the different toxicities of PCB congeners, it is important to know which congeners contribute most to total PCBs. The predominant PCB congeners were 153, 138, 180, 110, 118, 187, and 92. Collectively, congeners 153, 138, and 180 accounted for 26 to 42% of total PCBs. Congener 153 was the most abundant in Caspian terns (Sterna caspia) and great blue herons (Ardea herodias) and congener 138 was the most abundant in snowy egrets (Egretta thula) and tricolored herons (Egretta tricolor). Principal component analysis indicated a predominance of higher chlorinated biphenyls in Caspian terns and great blue herons and lower chlorinated biphenyls in tricolored herons. Snowy egrets had a predominance of pentachlorobiphenyls. These results suggest that there are differences in PCB congener patterns in closely related species and that these differences are more likely associated with the species' diet rather than metabolism. Total PCBs were significantly greater (p < 0.05) in Caspian terns than in the other species. Overall, PCBs in eggs of birds from the Lower Laguna Madre were below concentrations known to affect bird reproduction.

Atmospheric Production of Perchlorate on Earth and Mars

NASA Astrophysics Data System (ADS)

Claire, M.; Catling, D. C.; Zahnle, K. J.

2009-12-01

Natural production and preservation of perchlorate on Earth occurs only in arid environments. Isotopic evidence suggests a strong role for atmospheric oxidation of chlorine species via pathways including ozone or its photochemical derivatives. As the Martian atmosphere is both oxidizing and drier than the driest places on Earth, we propose an atmospheric origin for the Martian perchlorates measured by NASA's Phoenix Lander. A variety of hypothetical formation pathways can be proposed including atmospheric photochemical reactions, electrostatic discharge, and gas-solid reactions. Here, we investigate gas phase formation pathways using a 1-D photochemical model (Catling et al. 2009, accepted by JGR). Because perchlorate-rich deposits in the Atacama desert are closest in abundance to perchlorate measured at NASA's Phoenix Lander site, we start with a study of the means to produce Atacama perchlorate. We found that perchlorate can be produced in sufficient quantities to explain the abundance of perchlorate in the Atacama from a proposed gas phase oxidation of chlorine volatiles to perchloric acid. These results are sensitive to estimated reaction rates for ClO3 species. The feasibility of gas phase production for the Atacama provides justification for further investigations of gas phase photochemistry as a possible source for Martian perchlorate. In addition to the Atacama results, we will present a preliminary study incorporating chlorine chemistry into an existing Martian photochemical model (Zahnle et al. JGR 2008).

Distribution and trophic transfer of short-chain chlorinated paraffins in an aquatic ecosystem receiving effluents from a sewage treatment plant.

PubMed

Zeng, Lixi; Wang, Thanh; Wang, Pu; Liu, Qian; Han, Shanlong; Yuan, Bo; Zhu, Nali; Wang, Yawei; Jiang, Guibin

2011-07-01

Short-chain chlorinated paraffins (SCCPs) are an extremely complex group of industrial chemicals and found to be potential persistent organic pollutants (POPs), and thus have attracted extensive concern worldwide. In this study, influent, effluent, and sludge were collected from a large sewage treatment plant (STP) in Beijing, China. Water, sediment, and aquatic species were also collected from a recipient lake that receives effluents discharged from the STP. These samples were then analyzed to investigate the effect of STP effluent on distribution and trophic transfer of SCCPs in the local aquatic ecosystem. Concentrations of total SCCPs (ΣSCCPs) in lake water and surface sediments were found in the range 162-176 ng/L and 1.1-8.7 μg/g (dry weight, dw), respectively. Vertical concentration profiles of sediment cores showed ΣSCCPs decreased exponentially with increasing depth. Specific congener composition analysis in sediment layers indicated possible in situ biodegradation might be occurring. High bioaccumulation of SCCPs was observed in the sampled aquatic species. The bioaccumulation factor (BAF) generally increased with the number of chlorines in the SCCP congeners. A significantly positive correlation between lipid-normalized ΣSCCPs concentration and trophic levels (R(2) = 0.65, p < 0.05) indicate that SCCPs can biomagnify through the food chain in the effluent-receiving aquatic ecosystem.

Recovery of copper from PVC multiwire cable waste by steam gasification.

PubMed

Zabłocka-Malicka, Monika; Rutkowski, Piotr; Szczepaniak, Włodzimierz

2015-12-01

Screened multiwire, PVC insulated tinned copper cable was gasified with steam at high temperature (HTSG) under atmospheric pressure for recovery of cooper. Gases from the process were additionally equilibrated at 850°C on the bed of calcined clay granules and more than 98% of C+H content in the cable was transformed to non-condensing species. Granules prepared from local clay were generally resistant for chlorination, there was also almost no deposition of metals, Cu and Sn, on the catalytic bed. It was found that 28% of chlorine reacted to form CaCl2, 71% was retained in aqueous condensate and only 0.6% was absorbed in alkaline scrubber. More than 99% of calcium existed in the process solid residue as a mixture of calcium chloride and calcium oxide/hydroxide. PVC and other hydrocarbon constituents were completely removed from the cable sample. Copper was preserved in original form and volatilization of copper species appeared insignificant. Tin was alloying with copper and its volatilization was less than 1%. Fractionation and speciation of metals, chlorine and calcium were discussed on the basis of equilibrium model calculated with HSC Chemistry software. High temperature steam gasification prevents direct use of the air and steam/water is in the process simultaneously gaseous carrier and reagent, which may be recycled together with hydrocarbon condensates. Copyright © 2015 Elsevier Ltd. All rights reserved.

a Study on the Physical and Chemical Properties of Stratospheric Aerosols.

NASA Astrophysics Data System (ADS)

Tabazadeh, Azadeh

The physical and chemical properties of stratospheric aerosols under background and perturbed conditions are discussed. First, a multi-component aerosol physical chemistry model was developed to study the composition and reactivity of stratospheric aerosols. The compositions are predicted from an equilibrium assumption between the condensed-and gas-phases, and they are calculated as a function of ambient temperature, relative humidity, and the total mass of nitric acid and sulfuric acid present per unit volume of air. The water and solute activity parameters in the aerosol model are derived from various laboratory sources, and the set of equilibrium equations are solved using a unique numerical scheme. The aerosol model is applied to study the formation of nitric acid-containing aerosols in the stratosphere. Also, the equilibrium compositions are used to estimate the extent of aqueous phase processing of chlorine species in the aerosol solutions. This processing can contribute to the depletion of the stratospheric ozone layer, especially after major volcanic eruptions where sulfate aerosols are more abundant. Second, a surface chemistry model was constructed that includes Langmuir trace-gas adsorption and desorption, Brunauer, Emmett and Teller adsorption of water vapor, surface poisoning, solvation and diffusion of molecules on the surface, chemical activation and reaction of adsorbates, and product desorption or reaction. This model is used to study the effects of relative humidity and other physical parameters on the efficiency of heterogeneous chemical processes which occur on the surfaces of solid polar stratospheric clouds. These heterogeneous chemical processes are responsible for the formation of the "ozone hole", can contribute to global ozone depletion, and may have tropospheric significance. Finally, a fluid dynamics and thermodynamics model of volcanic eruption columns was used to develop a scheme for predicting the extent of HCl removal from volcanic plumes. If most of the volcanically emitted chlorine stays in the upper atmosphere, the chlorine concentration in the stratosphere could increase by a factor of 2 to 10, leading to severe global ozone depletions. However, model results indicate that HCl is efficiently scavenged from volcanic plumes by supercooled water droplets, which form as the plume lofts and cools. HCl dissolution in these drops, followed by rainout, prevents substantial injections of chlorine into the stratosphere.

Molecular characterization of low molecular weight dissolved organic matter in water reclamation processes using Orbitrap mass spectrometry.

PubMed

Phungsai, Phanwatt; Kurisu, Futoshi; Kasuga, Ikuro; Furumai, Hiroaki

2016-09-01

Reclaimed water has recently become an important water source for urban use, but the composition of dissolved organic matter (DOM) in reclaimed water has rarely been characterized at the compound level because of its complexity. In this study, the transformation and changes in composition of low molecular weight DOM in water reclamation processes, where secondary effluent of the municipal wastewater treatment plant was further treated by biofiltration, ozonation and chlorination, were investigated by "unknown" screening analysis using Orbitrap mass spectrometry (Orbitrap MS). The intense ions were detected over an m/z range from 100 to 450. In total, 2412 formulae with various heteroatoms were assigned, and formulae with carbon (C), hydrogen (H) and oxygen (O) only and C, H, O and sulfur (S) were the most abundant species. During biofiltration, CHO-only compounds with relatively high hydrogen to carbon (H/C) ratio or with saturated structure were preferentially removed, while CHOS compounds were mostly removed. Ozonation induced the greatest changes in DOM composition. CHOS compounds were mostly decreased after ozonation while ozone selectively removed CHO compounds with relatively unsaturated structure and produced compounds that were more saturated and with a higher degree of oxidation. After chlorination, 168 chlorine-containing formulae, chlorinated disinfection by-products (DBPs), were additionally detected. Candidate DBP precursors were determined by tracking chlorinated DBPs formed via electrophilic substitution, half of which were generated during the ozonation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Comparison of formation of disinfection by-products by chlorination and ozonation of wastewater effluents and their toxicity to Daphnia magna.

PubMed

Park, Keun-Young; Choi, Su-Young; Lee, Seung-Hoon; Kweon, Ji-Hyang; Song, Ji-Hyeon

2016-08-01

This study compared the two most frequently used disinfectants (i.e., chlorine and ozone) to understand their efficiency in wastewater effluents and the ecotoxicity of disinfection by-products created during chlorination and ozonation. Four trihalomethanes (THMs) and nine haloacetic acids (HAAs) were measured from a chlorine-disinfected sample and two aldehydes (i.e., formaldehydes and acetaldehydes) were analyzed after ozonation. Chlorination was effective for total coliform removal with Ct value in the range of 30-60 mg-min/L. Over 1.6 mg/L of ozone dose and 0.5 min of the contact time presented sufficient disinfection efficiency. The concentration of THMs increased with longer contact time (24 h), but that of HAAs showed little change with contact time. The measured concentration of formaldehyde at the ozone dose of 1.6 mg/L and the contact time of 9 min showed the greatest value in this study, approximately 330 μg L(-1), from which the corresponding ecotoxicity was determined using an indicator species, Daphnia magna. The ecotoxicity results were consistent with the toxicological features judged by occurrence, genotoxicity, and carcinogenicity. Both the disinfection efficiency as well as the DBP formation potential should therefore be considered to avoid harmful impacts on aquatic environments when a disinfection method is used for wastewater effluents. Copyright © 2016 Elsevier Ltd. All rights reserved.

Comparative photodynamic therapy cytotoxicity of mannose-conjugated chlorin and talaporfin sodium in cultured human and rat cells.

PubMed

Shinoda, Yo; Takahashi, Tsutomu; Akimoto, Jiro; Ichikawa, Megumi; Yamazaki, Hiromi; Narumi, Atsushi; Yano, Shigenobu; Fujiwara, Yasuyuki

2017-01-01

Photodynamic therapy (PDT) is a Food and Drug Administration authorized method for cancer treatment, which uses photosensitizer and laser photo-irradiation to generate reactive oxygen species to induce cell death in tumors. Photosensitizers have been progressively developed, from first to third generation, with improvements in cell specificity, reduced side effects and toxicity, increased sensitivity for irradiation and reduced persistence of photosensitizer in healthy cells. These improvements have been achieved by basic comparative experiments between current and novel photosensitizers using cell lines; however, photosensitizers should be carefully evaluated because they may have cell type specificity. In the present study, we compared a third-generation photosensitizer, β-mannose-conjugated chlorin (β-M-chlorin), with the second generation, talaporfin sodium (NPe6), using seven different rat and human cell lines and a neuronal/glial primary culture prepared from rat embryos. NPe6 was more effective than β-M-chlorin in human-derived cell lines, and β-M-chlorin was more effective than NPe6 in rat primary cultures and rat-derived cell lines, except for the rat pheochromocytoma cell line, PC12. These differences of phototoxicity in different cell types are not because of differences in photosensitivity between the photosensitizers, but rather are associated with different distribution and accumulation rates in the different cell types. These data suggest that evaluation of photosensitizers for PDT should be carried out using as large a variety of cell types as possible because each photosensitizer may have cell type specificity.

A STUDY OF GAS-PHASE MERCURY SPECIATION USING DETAILED CHEMICAL KINETICS

EPA Science Inventory

Mercury (Hg) speciation in combustion-generated flue gas is modeled using a detailed chemical mechanism consisting of 60 reactions and 21 species. This speciation model accounts for chlorination and oxidation of key flue-gas components, including elemental mercury. Results indica...

Controlling Mold on Library Materials with Chlorine Dioxide: An Eight-Year Case Study.

ERIC Educational Resources Information Center

Weaver-Meyers, Pat L.; Kowaleski, Barbara; Stolt, Wilbur A.

1998-01-01

Discusses problems associated with mold growth at the University of Oklahoma libraries and describes the results of using chlorine dioxide in aqueous and gaseous forms. Highlights include toxicity compared to other preservation treatments; environmental controls; and explanations of a preference for the use of a self-activating gas packet.…

COMPARISON OF RAPID METHODS TO EVALUATE CHLORINE INACTIVATION OF THE BIOLOGICAL AGENT E. COLI 0157:H7

EPA Science Inventory

Rapid viability tests of the Catagory B agent Escherichia coli O157:H7 were evaluated after disinfection with chlorine. The metabolic activity dyes ChemChrome V6, a modified fluorescein diacetate (FDA) and 5-cyano-2,3-ditolyl tetrazolium chloride (CTC) were compared to standard ...

Ozone Depletion at Mid-Latitudes: Coupling of Volcanic Aerosols and Temperature Variability to Anthropogenic Chlorine

NASA Technical Reports Server (NTRS)

Solomon, S.; Portmann, R. W.; Garcia, R. R.; Randel, W.; Wu, F.; Nagatani, R.; Gleason, J.; Thomason, L.; Poole, L. R.; McCormick, M. P.

1998-01-01

Satellite observations of total ozone at 40-60 deg N are presented from a variety of instruments over the time period 1979-1997. These reveal record low values in 1992-3 (after Pinatubo) followed by partial but incomplete recovery. The largest post-Pinatubo reductions and longer-term trends occur in spring, providing a critical test for chemical theories of ozone depletion. The observations are shown to be consistent with current understanding of the chemistry of ozone depletion when changes in reactive chlorine and stratospheric aerosol abundances are considered along with estimates of wave-driven fluctuations in stratospheric temperatures derived from global temperature analyses. Temperature fluctuations are shown to make significant contributions to model calculated northern mid-latitude ozone depletion due to heterogeneous chlorine activation on liquid sulfate aerosols at temperatures near 200-210 K (depending upon water vapor pressure), particularly after major volcanic eruptions. Future mid-latitude ozone recovery will hence depend not only on chlorine recovery but also on temperature trends and/or variability, volcanic activity, and any trends in stratospheric sulfate aerosol.

Chlorine-rich plasma polymer coating for the prevention of attachment of pathogenic fungal cells onto materials surfaces

NASA Astrophysics Data System (ADS)

Lamont-Friedrich, Stephanie J.; Michl, Thomas D.; Giles, Carla; Griesser, Hans J.; Coad, Bryan R.

2016-07-01

The attachment of pathogenic fungal cells onto materials surfaces, which is often followed by biofilm formation, causes adverse consequences in a wide range of areas. Here we have investigated the ability of thin film coatings from chlorinated molecules to deter fungal colonization of solid materials by contact killing of fungal cells reaching the surface of the coating. Coatings were deposited onto various substrate materials via plasma polymerization, which is a substrate-independent process widely used for industrial coating applications, using 1,1,2-trichloroethane as the process vapour. XPS surface analysis showed that the coatings were characterized by a highly chlorinated hydrocarbon polymer nature, with only a very small amount of oxygen incorporated. The activity of these coatings against human fungal pathogens was quantified using a recently developed, modified yeast assay and excellent antifungal activity was observed against Candida albicans and Candida glabrata. Plasma polymer surface coatings derived from chlorinated hydrocarbon molecules may therefore offer a promising solution to preventing yeast and mould biofilm formation on materials surfaces, for applications such as air conditioners, biomedical devices, food processing equipment, and others.

Observations of chlorine monoxide over Scott Base, Antarctica, during the ozone hole, 1996-2005

USGS Publications Warehouse

Connor, Brian; Solomon, Philip; Barrett, James; Mooney, Thomas; Parrish, Alan

2007-01-01

We report observations of chlorine monoxide, ClO, in the lower stratosphere, made from Scott Base (77.85º S, 166.77º E) in springtime during each year, 1996-2005. The ClO amounts in the atmosphere are retrieved from remote measurements of microwave emission spectra. ClO column densities of up to about 2.5 × 1015 cm-2 are recorded during September, when chlorine is present in chemically active forms due to reactions on the surface of Polar Stratospheric Cloud (PSC) particles. Maximum mixing ratios of ClO are approximately 2 ppbv. The annual average of ClO column density during the activation period is anticorrelated with similar averages of ozone column measured at nearby Arrival Heights, with correlation coefficient of –0.81, and with averages of ozone mass integrated over the entire polar region, with similar correlation coefficients. There was a substantial decrease in ClO amounts during 2002-2004. There has been no systematic change in the timing of chlorine deactivation attributable to secular change in the Antarctic vortex

Degradation of polyvinyl alcohol (PVA) by UV/chlorine oxidation: Radical roles, influencing factors, and degradation pathway.

PubMed

Ye, Bei; Li, Yue; Chen, Zhuo; Wu, Qian-Yuan; Wang, Wen-Long; Wang, Ting; Hu, Hong-Ying

2017-11-01

Polyvinyl alcohol (PVA) is widely used in industry but is difficult to degrade. In this study, the synergistic effect of UV irradiation and chlorination on degradation of PVA was investigated. UV irradiation or chlorination alone did not degrade PVA. By contrast, UV/chlorine oxidation showed good efficiency for PVA degradation via generation of active free radicals, such as OH and Cl. The relative importance of these two free radicals in the oxidation process was evaluated, and it was shown that OH contributed more to PVA degradation than Cl did. The degradation of PVA followed pseudo first order kinetics. The rate constant k increased linearly from 0 min -1 to 0.3 min -1 with increasing chlorine dosage in range of 0 mg/L to 20 mg/L. However, when the chlorine dosage was increased above 20 mg/L, scavenging effect of free radicals occurred, and the degradation efficiency of PVA did not increase much more. Acidic media increased the degradation efficiency of PVA by UV/chlorine oxidation more than basic or neutral media because of the higher ratio of [HOCl]/[OCl - ], higher free radical quantum yields, and the lower free radical quenching effect under acidic conditions. Results of Fourier Transform Infrared Spectroscopy showed that carbonyl groups in degradation products were formed during UV/chlorine oxidation, and a possible degradation pathway via alcohol to carbonyl was proposed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Behavior of Al2O3 and SiO2 with heating in a Cl2 + CO stream

NASA Technical Reports Server (NTRS)

Shchetinin, L. K.

1984-01-01

Differential thermal analysis (DTA) and Thermogravimetric analysis (TGA) were used to study the chlorination of alpha-Al2O3, gamma-Al2O3 and amorphous SiO2 in a Cl + CO stream, for the preparation of AlCl3 and SiCl4. The chlorination starting temperatures were 235 deg for Al2O3 and 680 deg for SiO2. The chlorination of alpha- and gamma-Al2O3 takes place via the formation of AlOCl as an intermediate product, and its subsequent dissociation at 480 to 560 deg, according to 3AlOCl yields AlCl3 + Al2O3. The chlorination activation energies are given for the three oxides.

Metabolism and mutagenicity of halogenated olefins--a comparison of structure and activity.

PubMed Central

Henschler, D

1977-01-01

Chlorinated ethylenes are metabolized in mammals, as a first step, to epoxides. The fate of these electrophilic intermediates may be reaction with nucleophiles (alkylation), hydrolysis, or intramolecular rearrangement. The latter reaction has been studied in the whole series of chlorinated epoxiethanes. The rearrangement products found were: acyl chlorides (tetrachloro-, trichloro-, and 1,1-dichloroethylenes), or chlorinated aldehydes (1,2-dichloroethylenes, cis- and trans-, vinyl chloride). The metabolities found in vivo are identical with, or further derivatives of these rearrangment products, with one important exception: trichloroethylene. With this compound, in vivo rearrangement yields chloral exclusively. The mechanism of the different rearrangement has been identified as a Lewis acid catalysis. All chlorinated ethylenes have been investigated in a tissue-mediated mutagenicity testing system. The prominent molecular feature of those with mutagenic effects (trichloro-, 1,1-dichloro-, and monochloroethylene) is unsymmetric chlorine substitution which renders the epoxides unstable, whereas symmetric substitution confers relative stability and nonmutagenic property. PMID:348459

Effectiveness of Neutral Electrolyzed Water on Incidence of Fungal Rot on Tomato Fruits ( Solanum lycopersicum L.).

PubMed

Vásquez-López, Alfonso; Villarreal-Barajas, Tania; Rodríguez-Ortiz, Gerardo

2016-10-01

We assessed the effect of neutral electrolyzed water (NEW) on the incidence of rot on tomato ( Solanum lycopersicum L.) fruits inoculated with Fusarium oxysporum , Galactomyces geotrichum , and Alternaria sp. at sites with lesions. The inoculated fruits were treated with NEW at 10, 30, and 60 mg liter -1 active chlorine, with copper oxychloride fungicide, and with sterile distilled water (control) for 3, 5, and 10 min. In the experiment with F. oxysporum , 50 to 80% of the control fruits and 50 to 60% of the fruits treated with the fungicide exhibited symptoms of rot at the inoculated sites. The lowest incidence recorded was 30% for fruits treated with NEW at 60 mg liter -1 active chlorine with an immersion time of 5 min. In the experiment with G. geotrichum , incidence of rot on control fruits was 70 to 90%, and for treatment with fungicide rot incidence was 50 to 90%. NEW at 60 mg liter -1 active chlorine significantly reduced incidence of symptomatic fruit: only 30% of the inoculated fruits washed for 5 min had damage from rot. In the experiment with Alternaria sp., 60 to 90% of the fruits in the control group and 60 to 70% of the fruits in the fungicide group were symptomatic. The lowest incidence was recorded for the treatment in which the fruits were submerged in NEW with 60 mg liter -1 active chlorine for 3 min. In this group, 40 to 50% of the fruits exhibited symptoms of rot. These results were obtained 8 days after inoculation. NEW, with 60 mg liter -1 active chlorine, significantly reduced incidence of rot symptoms on fruits inoculated with one of the experimental fungi relative to the control (P ≤ 0.05). NEW at 60 mg liter -1 is effective in the control of fungal rot in tomatoes.

Abatement of chlorinated compounds in groundwater contaminated by HCH wastes using ISCO with alkali activated persulfate.

PubMed

Santos, A; Fernandez, J; Rodriguez, S; Dominguez, C M; Lominchar, M A; Lorenzo, D; Romero, A

2018-02-15

In this work, in situ chemical oxidation (ISCO) with alkali activated persulfate has been tested for the elimination of HCH isomers and other chlorinated compounds in groundwater from Sabiñanigo (Sardas landfill), which was contaminated by solid and liquid wastes illegally dumped in the area by a company producing lindane. Due to the site lithology and the type of pollutants found in groundwater (HCHs and chlorobenzenes) alkali (NaOH) activated persulfate (PS) was selected as oxidant. The influence of variables such as PS concentration (42-200mM) and NaOH:PS molar ratio (2:1 to 4:1) on chlorinated compound abatement has been studied and a kinetic model to predict the composition of all chlorinated organic compounds (COCs) in the aqueous phase with time was obtained. It was found that a fast initial hydrodechlorination reaction took place in which HCH isomers reacted to trichlorobenzenes (mainly 1,2,4 TCB) at pH≥12. Mono-, di-, tri and tetrachlorobenzenes remaining were oxidized without producing aromatic intermediates. At the condition tested a first order kinetic model for COCs and PS concentration was obtained. Zero order alkali concentration was obtained while pH was being kept at 12 for the whole reaction time. Copyright © 2017 Elsevier B.V. All rights reserved.

N-Chloramines, a Promising Class of Well-Tolerated Topical Anti-Infectives

PubMed Central

Gottardi, Waldemar; Debabov, Dmitri

2013-01-01

Antibiotic resistance is a growing public health crisis. To address the development of bacterial resistance, the use of antibiotics has to be minimized for nonsystemic applications in humans, as well as in animals and plants. Possible substitutes with low potential for developing resistance are active chlorine compounds that have been in clinical use for over 180 years. These agents are characterized by pronounced differences in their chlorinating and/or oxidizing activity, with hypochlorous acid (HOCl) as the strongest and organic chloramines as the weakest members. Bacterial killing in clinical practice is often associated with unwanted side effects such as chlorine consumption, tissue irritation, and pain, increasing proportionally with the chlorinating/oxidizing potency. Since the chloramines are able to effectively kill pathogens (bacteria, fungi, viruses, protozoa), their application as anti-infectives is advisable, all the more so as they exhibit additional beneficial properties such as destruction of toxins, degradation of biofilms, and anticoagulative and anti-inflammatory activities. Within the ample field of chloramines, the stable N-chloro derivatives of ß-aminosulfonic acids are most therapeutically advanced. Being available as sodium salts, they distinguish themselves by good solubility and absence of smell. Important representatives are N-chlorotaurine, a natural compound occurring in the human immune system, and novel mono- and dichloro derivatives of dimethyltaurine, which feature improved stability. PMID:23295936

Soil gas screening for chlorinated solvents at three contaminated karst sites in Tennessee

USGS Publications Warehouse

Wolfe, W.J.; Williams, S.D.

2002-01-01

Soil gas was sampled using active sampling techniques and passive collectors at three sites in Tennessee to evaluate the effectiveness of these techniques for locating chlorinated solvent sources and flowpaths in karst aquifers. Actively collected soil gas samples were analyzed in the field with a portable gas chromatograph, and the passive soil gas collectors were analyzed in the lab with gas chromatography/mass spectrometry. Results of the sampling indicate that the effectiveness of both techniques is highly dependent on the distribution of the contaminants in the subsurface, the geomorphic and hydrogeologic characteristics of the site, and, in one case, on seasonal conditions. Both active and passive techniques identified areas of elevated subsurface chlorinated solvent concentrations at a landfill site where contamination remains concentrated in the regolith. Neither technique detected chlorinated solvents known to be moving in the bedrock at a manufacturing site characterized by thick regolith and an absence of surficial karst features. Passive soil gas sampling had varied success detecting flowpaths for chloroform in the bedrock at a train derailment site characterized by shallow regolith and abundant surficial karst features. At the train derailment site, delineation of the contaminant flowpath through passive soil gas sampling was stronger and more detailed under Winter conditions than summer.

Biodegradation of chlorinated ethenes at a karst site in middle Tennessee

USGS Publications Warehouse

Byl, Thomas Duane; Williams, Shannon D.

2000-01-01

This report presents results of field and laboratory investigations examining the biodegradation of chlorinated ethenes in a karst aquifer contaminated with trichloroethylene (TCE). The study site, located in Middle Tennessee, was selected because of the presence of TCE degradation byproducts in the karst aquifer and available site hydrologic and chlorinated-ethene information. Additional chemical, biological, and hydrologic data were gathered to evaluate whether the occurrence of TCE degradation byproducts in the karst aquifer was the result of biodegradation within the aquifer or simply transport into the aquifer. Geochemical analysis established that sulfate-reducing conditions, essential for reductive dechlorination of chlorinated solvents, existed in parts of the contaminated karst aquifer. Other areas of the aquifer fluctuated between anaerobic and aerobic conditions and contained compounds associated with cometabolism, such as ethane, methane, ammonia, and dissolved oxygen. A large, diverse bacteria population inhabits the contaminated aquifer. Bacteria known to biodegrade TCE and other chlorinated solvents, such as sulfate-reducers, methanotrophs, and ammonia-oxidizers, were identified from karst-aquifer water using the RNA-hybridization technique. Results from microcosms using raw karst-aquifer water found that aerobic cometabolism and anaerobic reductive-dechlorination degradation processes were possible when appropriate conditions were established in the microcosms. These chemical and biological results provide circumstantial evidence that several biodegradation processes are active in the aquifer. Additional site hydrologic information was developed to determine if appropriate conditions persist long enough in the karst aquifer for these biodegradation processes to be significant. Continuous monitoring devices placed in four wells during the spring of 1998 indicated that pH, specific conductance, dissolved oxygen, and oxidation-reduction potentials changed very little in areas isolated from active ground-water flow paths. These stable areas in the karst aquifer had geochemical conditions and bacteria conducive to reductive dechlorination of chlorinated ethenes. Other areas of the karst aquifer were associated with active ground-water flow paths and fluctuated between anaerobic and aerobic conditions in response to rain events. Associated with this dynamic environment were bacteria and geochemical conditions conducive to cometabolism. In summary, multiple lines of evidence developed from chemical, biological, and hydrologic data demonstrate that a variety of biodegradation processes are active in this karst aquifer.

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

PubMed

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.

New and bioactive compounds from Streptomyces strains residing in the wood of Celastraceae.

PubMed

Pullen, Christian; Schmitz, Petra; Meurer, Kristina; Bamberg, Daniel D v; Lohmann, Stephanie; De Castro França, Suzelei; Groth, Ingrid; Schlegel, Brigitte; Möllmann, Ute; Gollmick, Friedrich; Gräfe, Udo; Leistner, Eckhard

2002-11-01

Wood from three different plants of the Celastraceae growing in their natural habitats in Brazil (Maytenus aquifolia Mart.) and South Africa [Putterlickia retrospinosa van Wyk and Mostert, P. verrucosa (E. Meyer ex Sonder) Szyszyl.] was established as a source of endophytic bacteria using a medium selective for actinomycetes. Two isolates were identified as Streptomyces setonii and S. sampsonii whereas two others were not assignable to any of the known Streptomyces species. They were preliminarily named Streptomyces Q21 and Streptomyces MaB-QuH-8. The latter strain produces a new chloropyrrol and chlorinated anthracyclinone. The chloropyrrol showed high activity against a series of multiresistent bacteria and mycobacteria.

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

NASA Astrophysics Data System (ADS)

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 activated carbons. Consequently, the half-life time ranged between 50 and 700 (min) for the biosorbents and the biochars and it was equal to 41 (min) for the commercial activated carbons. The column experiment also showed positive results; A breakthrough for concentrations higher than 10(AWWA) 1990 Water quality and treatment, a handbook of community water supplies, Fourth edition, American Water Works Association Fourth edition.

Formation and Occurrence of N-Chloro-2,2-dichloroacetamide, a Previously Overlooked Nitrogenous Disinfection Byproduct in Chlorinated Drinking Waters.

PubMed

Yu, Yun; Reckhow, David A

2017-02-07

Haloacetamides (HAMs) are a class of newly identified nitrogenous disinfection byproducts (N-DBPs) whose occurrence in drinking waters has recently been reported in several DBP surveys. As the most prominent HAM species, it is commonly acknowledged that 2,2-dichloroacetamide (DCAM) is mainly generated from dichloroacetonitrile (DCAN) hydrolysis because the concentrations of these two compounds are often well correlated. Instead of DCAM, a previously unreported N-DBP, N-chloro-2,2-dichloroacetamide (N-Cl-DCAM), was confirmed in this study as the actual DCAN degradation product in chlorinated drinking waters. It is suspected that N-Cl-DCAM has been erroneously identified as DCAM, because its nitrogen-bound chlorine is readily reduced by most commonly used quenching agents. This hypothesis is supported by kinetic studies that indicate almost instantaneous N-chlorination of DCAM even at low chlorine residuals. Therefore, it is unlikely that DCAM can persist as a long-lived DCAN decomposition product in systems using free chlorine as a residual disinfectant. Instead, chlorination of DCAM will lead to the formation of an equal amount of N-Cl-DCAM by forming a hydrogen bond between hypochlorite oxygen and amino hydrogen. Alternatively, N-Cl-DCAM can be produced directly from DCAN chlorination via nucleophilic addition of hypochlorite on the nitrile carbon. Due to its relatively low pK a value, N-Cl-DCAM tends to deprotonate under typical drinking water pH conditions, and the anionic form of N-Cl-DCAM was found to be very stable in the absence of chlorine. N-Cl-DCAM can, however, undergo acid-catalyzed decomposition to form the corresponding dichloroacetic acid (DCAA) when chlorine is present, although those acidic conditions that favor N-Cl-DCAM degradation are generally atypical for finished drinking waters. For these reasons, N-Cl-DCAM is predicted to have very long half-lives in most distribution systems that use free chlorine. Furthermore, an analytical method using ultra performance liquid chromatography (UPLC)/negative electrospray ionization (ESI - )/quadrupole time-of-flight mass spectrometry (qTOF) was developed for the detection of a family of seven N-chloro-haloacetamides (N-Cl-HAMs). Combined with solid phase extraction (SPE), the occurrence of N-Cl-DCAM and its two brominated analogues (i.e., N-chloro-2,2-bromochloroacetamide and N-chloro-2,2-dibromoacetamide) was quantitatively determined for the first time in 11 real tap water samples. The discovery of N-Cl-DCAM or, more broadly speaking, N-Cl-HAMs in chlorinated drinking waters is of significance because they are organic chloramines, a family of compounds that is perceived to be more toxicologically potent than halonitriles (e.g., DCAN) and haloamides (e.g., DCAM), and therefore they may pose greater risks to drinking water consumers given their widespread occurrence and high stability.

CAN ABIOTIC (INORGANIC) PROCESSES ACCOUNT FOR HALOACETATE CONCENTRATION PROFILES?

EPA Science Inventory

Haloacetates comprise about 13% of the measurable halogenated organic matter in potable water supplies after chlorination. Some of these species have been linked with animal carcinogenesis and are regulated under the Stage 1 DBP Rule. However, it is known that post-disinfection p...

COMBUSTION CONTROL OF ORGANIC EMISSIONS FROM MUNICIPAL WASTE COMBUSTORS

EPA Science Inventory

More than two decades ago, researchers identified benzo(a)pyrene and other organic species in the emissions from incineration of solid waste. Chlorinated dibenzo-p-dioxins and-furans (CDD/CDF) were first detected in municipal waste combustor (MWC) emissions in 1977. Since then, C...

Characterization and Neutralization of Recovered Lewisite Munitions

DTIC Science & Technology

2006-12-01

chlorine being rated as 1.0.51 Oxidative Species Relative Oxidizing Strength* Fluorine 2.23 Hydroxyl Radical 2.06 Atomic Oxygen 1.78 Hydrogen...containing carbon-carbon double bonds, aldehyde groups or hydroxyl groups. As an electrophile , the permnanganate ion is strongly attracted to the electrons

Production of chlorine from chloride salts

DOEpatents

Rohrmann, Charles A.

1981-01-01

A process for converting chloride salts and sulfuric acid to sulfate salts and elemental chlorine is disclosed. A chloride salt and sulfuric acid are combined in a furnace where they react to produce a sulfate salt and hydrogen chloride. Hydrogen chloride from the furnace contacts a molten salt mixture containing an oxygen compound of vanadium, an alkali metal sulfate and an alkali metal pyrosulfate to recover elemental chlorine. In the absence of an oxygen-bearing gas during the contacting, the vanadium is reduced, but is regenerated to its active higher valence state by separately contacting the molten salt mixture with an oxygen-bearing gas.

The use of atmospheric measurements to constrain model predictions of ozone change from chlorine perturbations

NASA Technical Reports Server (NTRS)

Douglass, Anne R.; Stolarski, Richard S.

1987-01-01

Atmospheric photochemistry models have been used to predict the sensitivity of the ozone layer to various perturbations. These same models also predict concentrations of chemical species in the present day atmosphere which can be compared to observations. Model results for both present day values and sensitivity to perturbation depend upon input data for reaction rates, photodissociation rates, and boundary conditions. A method of combining the results of a Monte Carlo uncertainty analysis with the existing set of present atmospheric species measurements is developed. The method is used to examine the range of values for the sensitivity of ozone to chlorine perturbations that is possible within the currently accepted ranges for input data. It is found that model runs which predict ozone column losses much greater than 10 percent as a result of present fluorocarbon fluxes produce concentrations and column amounts in the present atmosphere which are inconsistent with the measurements for ClO, HCl, NO, NO2, and HNO3.

Ab Initio Studies of Chlorine Oxide and Nitrogen Oxide Species of Interest in Stratospheric Chemistry

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

The ability of modern state-of-the art ab initio quantum chemical techniques to characterize reliably the gas-phase molecular structure, vibrational spectrum, electronic spectrum, and thermal stability of chlorine oxide and nitrogen oxide species will be demonstrated by presentation of some example studies. In particular the geometrical structures, vibrational spectra, and heats of formation Of ClNO2, CisClONO, and trans-ClONO are shown to be in excellent agreement with the available experimental data, and where the experimental data are either not known or are inconclusive, the ab initio results are shown to fill in the gaps and to resolve the experimental controversy. In addition, ab initio studies in which the electronic spectra and the characterization of excited electronic states of ClONO2, HONO2, ClOOC17 ClOOH, and HOOH will also be presented. Again where available, the ab initio results are compared to experimental observations, and are used to aid in the interpretation of the experimental studies.

Disinfection by-products in ballast water treatment: an evaluation of regulatory data.

PubMed

Werschkun, Barbara; Sommer, Yasmin; Banerji, Sangeeta

2012-10-15

To reduce the global spread of invasive aquatic species, international regulations will soon require reductions of the number of organisms in ballast water discharged by ships. For this purpose, ballast water treatment systems were developed and approved by an international procedure. These systems rely on established water treatment principles which, to different degrees, have been proven to generate disinfection by-products with hazardous properties but have only scarcely been investigated in marine environments. Our study evaluates the publicly available documentation about approved ballast water treatment systems with regard to by-product formation. The most commonly employed methods are chlorination, ozonation, and ultraviolet (UV) irradiation. Chlorination systems generate trihalomethanes, halogenated acetic acids, and bromate in substantially larger quantities than reported for other areas of application. Levels are highest in brackish water, and brominated species predominate, in particular bromoform and dibromoacetic acid. Ozonation, which is less frequently utilized, produces bromoform in lower concentrations but forms higher levels of bromate, both of which were effectively reduced by active carbon treatment. In systems based on UV radiation, medium pressure lamps are employed as well as UV-induced advanced oxidation. For all UV systems, by-product formation is reported only occasionally. The most notable observations were small increases in nitrite, hydrogen peroxide, halogenated methanes and acetic acids. The assessment of by-product formation during ballast water treatment is limited by the lacking completeness and quality of available information. This concerns the extent and statistical characterisation of chemical analysis as well as the documentation of the test water parameters. Copyright © 2012 Elsevier Ltd. All rights reserved.

Polychlorinated biphenyls and biotransformation enzymes in three species of sea turtles from the Baja California peninsula of Mexico.

PubMed

Richardson, K L; Lopez Castro, M; Gardner, S C; Schlenk, D

2010-01-01

Concentrations of polychlorinated biphenyls (PCBs) as well as the expression patterns of cytochrome P450 (CYP) enzymes and glutathione-S-transferase (GST) activities were measured in livers of loggerhead (Caretta caretta), green (Chelonia mydas), and olive ridley (Lepidocheyls olivacea) sea turtles from the Baja California peninsula of Mexico. The mean concentrations of total PCBs were 18.1, 10.5, and 15.2 ng/g wet weight (ww) respectively for the three species and PCB 153 was the dominant congener in all samples. Total PCB concentrations were dominated by penta- and hexa-chlorinated biphenyls. The mean estimated TEQs were 42.8, 22.9, and 10.4 pg/g (ww) for loggerhead, green, and olive ridley, respectively, and more than 70% was accounted for by non-ortho PCBs. Western blots revealed the presence of hepatic microsomal proteins that cross-reacted with anti-CYP2K1 and anti-CYP3A27 antibodies but not with anti-CYP1A antibody. There were no significant differences in GST activities between species. Grouping congeners based on structure-activity relationships for CYP isoenzymes suggested limited activity of CYP1A contribution to PCB biotransformation in sea turtles. These results suggest potential accumulation of PCBs that are CYP1A substrates and provide evidence for biotransformation capacity, which differs from known animal models, highlighting the need for further studies in reptiles, particularly those threatened with extinction.

The toxicity of brominated and mixed-halogenated dibenzo-p-dioxins and dibenzofurans: An overview

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weber, L.W.D.; Greim, H.

1997-02-21

Brominated dibenzo-p-dioxins and dibenzofurans can be formed under laboratory conditions by pyrolysis of flame retardants based on polybrominated biphenyls and biphenyl ethers. Their occurrence in the environment, however, is due to combustion processes such as municipal waste incineration and internal combustion engines. As these processes generally take place in the presence of an excess of chlorine, predominantly mixed brominated and chlorinated compounds have been identified so far in environmental samples. Brominated dibenzo-p-dioxins or dibenzofurans bind to the cytosolic Ah receptor about as avidly as their chlorinated congeners and induce hepatic microsomal enzymes with comparable potency. The same holds true formore » mixed brominated-chlorinated compounds. Gross pathologic symptoms-hypothyroidism, thymic atrophy, wasting of body mass, lethality-also occur at doses that, on a molar concentration basis, are virtually identical to those seen with the chlorinated compounds. Their potency to induce malformations in mice following prenatal exposure is equivalent to that of chlorinated dibenzo-p-dioxins and dibenzofurans. Possible activities as (co)carcinogens and endocrine disrupters have not been evaluated, but are likely to exist. Considering the overall similarity in action of chlorinated and brominated dibenzo-p-dioxins and dibenzofurans, environmental and health assessment should be based on molar body burdens without discrimination for the nature of the halogen. 107 refs., 1 fig., 7 tabs.« less

Antimicrobial effect of electrolyzed water for inactivating Campylobacter jejuni during poultry washing.

PubMed

Park, Hoon; Hung, Yen-Con; Brackett, Robert E

2002-01-30

The effectiveness of electrolyzed (EO) water for killing Campylobacter jejuni on poultry was evaluated. Complete inactivation of C. jejuni in pure culture occurred within 10 s after exposure to EO or chlorinated water, both of which contained 50 mg/l of residual chlorine. A strong bactericidal activity was also observed on the diluted EO water (containing 25 mg/l of residual chlorine) and the mean population of C. jejuni was reduced to less than 10 CFU/ml (detected only by enrichment for 48 h) after 10-s treatment. The diluted chlorine water (25 mg/l residual chlorine) was less effective than the diluted EO water for inactivation of C. jejuni. EO water was further evaluated for its effectiveness in reducing C. jejuni on chicken during washing. EO water treatment was equally effective as chlorinated water and both achieved reduction of C. jejuni by about 3 log10 CFU/g on chicken, whereas deionized water (control) treatment resulted in only 1 log10 CFU/g reduction. No viable cells of C. jejuni were recovered in EO and chlorinated water after washing treatment, whereas high populations of C. jejuni (4 log10 CFU/ml) were recovered in the wash solution after the control treatment. Our study demonstrated that EO water was very effective not only in reducing the populations of C. jejuni on chicken, but also could prevent cross-contamination of processing environments.

The Connection between Model Performance on the CCMVal Transport Diagnostics and Simulated Sensitivity of Ozone to Chlorine Change

NASA Technical Reports Server (NTRS)

Douglass, Anne; Stolarski, Richard; Oman, Luke; Strahan, Susan

2012-01-01

The chemistry climate models that contributed simulations for past and future ozone evolution to the 2010 Scientific Assessment of Ozone Depletion were subject to extensive evaluation by the SPARC (Stratospheric Processes and their Role in Climate) CCMVal (Chemistry-Climate Model Validation) activity. The sensitivity of ozone to changes in composition and climate varies among the models, but the relationship between these variations and the model evaluations of CCMVal is not obvious. We have learned that the transport evaluation can be used to interpret the comparisons between observed and simulated columns of chlorine reservoirs, hydrochloric acid (HCl) and chlorine nitrate (ClONO2); these comparisons were part of the CCMVal evaluation of chemistry. The simulations with best performance on the transport diagnostics most faithfully reproduce the evolution and seasonal variation of the chlorine reservoirs as observed at NDACC (Network for Detection of Atmospheric Composition Change) stations (NyAlesund 78.9N, Kiruna 67.8N, Harestua 60.2N, Jungfraujoch 46.6N, Toronto 43.6N, Kitt Peak 31.9N, Izana 28.3N, Mauna Loa 19.5N, Lauder 45S and Arrival Heights 77.8S). In the simulations, the HCl in the lower stratosphere depends on total inorganic chlorine (Cly) and partitioning between HCl and ClON02. Total inorganic chlorine depends on the fractional release of chlorine from source gases, and ratio of ClON02 to HCl is inversely dependent on methane and varies quadratically with ozone. Simulated HCl from various models may agree with observations even though Cly is in error, partitioning is in error, or both. Simulated ozone sensitivity to chlorine is shown to be greater for models that produce larger values of chlorine nitrate for background chlorine levels, and vice versa. Comparisons with the NDACC data show why the models with 'best' transport have similar sensitivity to chlorine change. The realistic evolution of the simulated HCl and ClONO2 columns suggests realistic levels of Cly in the lower atmosphere. In addition, the wide range values for the sensitivity of ozone to chlorine obtained from the CCMVal simulations is explained by the wide range in lower atmospheric columns of ClONO2 and the concomitant wide range of levels for chlorine monoxide.

Bioanalytical assessment of the formation of disinfection byproducts in a drinking water treatment plant.

PubMed

Neale, Peta A; Antony, Alice; Bartkow, Michael E; Farré, Maria José; Heitz, Anna; Kristiana, Ina; Tang, Janet Y M; Escher, Beate I

2012-09-18

Disinfection of drinking water is the most successful measure to reduce water-borne diseases and protect health. However, disinfection byproducts (DBPs) formed from the reaction of disinfectants such as chlorine and monochloramine with organic matter may cause bladder cancer and other adverse health effects. In this study the formation of DBPs through a full-scale water treatment plant serving a metropolitan area in Australia was assessed using in vitro bioanalytical tools, as well as through quantification of halogen-specific adsorbable organic halogens (AOXs), characterization of organic matter, and analytical quantification of selected regulated and emerging DBPs. The water treatment train consisted of coagulation, sand filtration, chlorination, addition of lime and fluoride, storage, and chloramination. Nonspecific toxicity peaked midway through the treatment train after the chlorination and storage steps. The dissolved organic matter concentration decreased after the coagulation step and then essentially remained constant during the treatment train. Concentrations of AOXs increased upon initial chlorination and continued to increase through the plant, probably due to increased chlorine contact time. Most of the quantified DBPs followed a trend similar to that of AOXs, with maximum concentrations observed in the final treated water after chloramination. The mostly chlorinated and brominated DBPs formed during treatment also caused reactive toxicity to increase after chlorination. Both genotoxicity with and without metabolic activation and the induction of the oxidative stress response pathway showed the same pattern as the nonspecific toxicity, with a maximum activity midway through the treatment train. Although measured effects cannot be directly translated to adverse health outcomes, this study demonstrates the applicability of bioanalytical tools to investigate DBP formation in a drinking water treatment plant, despite bioassays and sample preparation not yet being optimized for volatile DBPs. As such, the bioassays are useful as monitoring tools as they provide sensitive responses even at low DBP levels.

Atmospheric Release of Organic Chlorinated Compounds from the Activated-Sludge Wastewater Treatment Process.

DTIC Science & Technology

1980-05-01

industrial wastes are from several types of industries but the waste 25 from one manufacturer included several chlorinated precusors of pesticides and flame...Saturator of Watls C Fine Noodle Control Volvo D Mogesgt:c Stirrer with Rod in (2 liter) 3 Nock Round bottomn Flook I. Islt Stream Port 2 IWOt fItirogon

Synthesis, structural investigations on organotin(IV) chlorin-e6 complexes, their effect on sea urchin embryonic development and induced apoptosis.

PubMed

Pellerito, Claudia; D'Agati, Paolo; Fiore, Tiziana; Mansueto, Caterina; Mansueto, Valentina; Stocco, Giancarlo; Nagy, László; Pellerito, Lorenzo

2005-06-01

Four new organotin(IV) chlorin derivatives, [chlorin=chlorin-e(6)=21H,23H-porphine-2-propanoic acid, 18-carboxy-20-(carboxymethyl)-8-ethenyl-13-ethyl-2,3-di-hydro-3,7,12,17-tetramethyl-(2S-trans)-], with formula (R(2)Sn)(3)(chlorin)(2).2H(2)O (R=Me, n-Bu) and (R(3)Sn)(3)chlorin.2H(2)O (R=Me, Ph) have been synthesized. The solid state and solution phase structures have been investigated by FT-IR, (119)Sn Mössbauer, (1)H and (13)C NMR spectroscopy. In the solid state, (R(2)Sn)(3)(chlorin)(2).2H(2)O complexes contain six coordinated Sn(IV), in a skew trapezoidal environment by forming trans-R(2)SnO(4) polymeric units. As far as (R(3)Sn)(3)chlorin.2H(2)O complexes are concerned, Sn(IV) is five coordinated in a polymeric (oligomeric) trigonal bipyramidal environment and eq-R(3)SnO(2) units, in the solid state. In saturated solutions, a polymeric structure comparable to the solid phase, with carboxylate groups of the ligand behaving in monoanionic bidentate fashion bridging Sn(IV) atoms, was detected for the (Me(3)Sn)(3)chlorin.2H(2)O complex, while in more diluted ones a tetrahedral configuration for the trimethyltin(IV) moieties was observed. Cytotoxic activity of the novel organotin(IV) chlorin was investigated in order to assay the effect on sea urchin embryonic development. The results obtained demonstrated that (n-Bu(2)Sn)(3)(chlorin)(2).2H(2)O and (Ph(3)Sn)(3)chlorin.2H(2)O exerted the antimitotic effect on the early stages of sea urchin development. In addition, the cytotoxic effect exerted by (n-Bu(2)Sn)(3)(chlorin)(2).2H(2)O appeared with necrosis of the blastomeres, which were clearly destroyed. After treatment with (Ph(3)Sn)(3)chlorin.2H(2)O, a programmed cell death was triggered, as shown by light microscope observations through morphological assays. The apoptotic events in 2-cell stage embryos revealed: (i) DNA fragmentation, with the TUNEL reaction (terminal deoxynucleotidyl transferase-mediated dUTP nick end labelling); (ii) phosphatidylserine translocation in the membrane, with Annexin-V assay and (iii) cytoplasm blebbing, with the TUNEL reaction. The results demonstrated that the novel compound (Ph(3)Sn)(3)chlorin.2H(2)O was the most toxic derivative, by exerting antimitotic effect very early and by triggering apoptosis in the 2-cell stage of sea urchin embryonic development.

New Metabolites and Bioactive Chlorinated Benzophenone Derivatives Produced by a Marine-Derived Fungus Pestalotiopsis heterocornis.

PubMed

Lei, Hui; Lin, Xiuping; Han, Li; Ma, Jian; Ma, Qingjuan; Zhong, Jialiang; Liu, Yonghong; Sun, Tiemin; Wang, Jinhui; Huang, Xueshi

2017-03-13

Four new compounds, including two isocoumarins, pestaloisocoumarins A and B ( 1 , 2 ), one sesquiterpenoid degradation, isopolisin B ( 4 ), and one furan derivative, pestalotiol A ( 5 ), together with one known isocoumarin, gamahorin ( 3 ), and three chlorinated benzophenone derivatives, pestalachloride B ( 6 ), pestalachloride E ( 7 ) and a mixture of pestalalactone atropisomers ( 8a/8b ), were isolated from a culture of the fungus Pestalotiopsis heterocornis associated with sponge Phakellia fusca . These new chemical structures were established using NMR and MS spectroscopic data, as well as single-crystal X-ray crystallographic analysis and CD Cotton effects. All of the isolated compounds were evaluated for their antimicrobial and cytotoxic activities. Isocoumarins 1 - 3 , showed antibacterial activities against Gram-positive bacteria Staphylococcus aureus and Bacillus subtilis with MIC values ranging from 25 to 100 μg/mL and weak antifungal activities. Chlorinated benzophenone derivatives 6 - 8 exhibited antibacterial activities against S. aureus and B. subtilis with MIC values ranging from 3.0 to 50 μg/mL and cytotoxicities against four human cancer cell lines with IC 50 values of 6.8-87.8 μM.

THE FATE OF THE HALOACETATES IN DRINKING WATER - CHEMICAL KINETICS IN AQUEOUS SOLUTION

EPA Science Inventory

Haloacetates comprise about 13% of the measurable halogenated organic matter in potable water supplies after chlorination. Some of these species have been linked with animal carcinogenesis and are regulated under the Stage 1 Disinfection Byproduct (DBP) Rule. However, it is known...

Global Implications of Great Lakes Wildlife Research.

ERIC Educational Resources Information Center

Colborn, Theo

1991-01-01

Data on the health of wildlife in the Great Lakes ecosystem are reviewed. Researchers infer from data on eight species that the effects in offspring are the result of exposure to chlorinated chemicals by adults and passed to the offspring via maternal transfer. Policy implications are discussed. (CW)

Sodium hypochlorite-, chlorine dioxide- and peracetic acid-induced genotoxicity detected by the Comet assay and Saccharomyces cerevisiae D7 tests.

PubMed

Buschini, Annamaria; Carboni, Pamela; Furlini, Mariangela; Poli, Paola; Rossi, Carlo

2004-03-01

Mutagenicity of drinking water is due not only to industrial, agricultural and urban pollution but also to chlorine disinfection by-products. Furthermore, residual disinfection is used to provide a partial safeguard against low level contamination and bacterial re-growth within the distribution system. The aims of this study were to further evaluate the genotoxic potential of the world wide used disinfectants sodium hypochlorite and chlorine dioxide in human leukocytes by the Comet assay and in Saccharomyces cerevisiae strain D7 (mitotic gene conversion, point mutation and mitochondrial DNA mutability, with and without endogenous metabolic activation) and to compare their effects with those of peracetic acid, proposed as an alternative disinfectant. All three disinfectants are weakly genotoxic in human leukocytes (lowest effective dose 0.2 p.p.m. for chlorine dioxide, 0.5 p.p.m. for sodium hypochlorite and peracetic acid). The results in S.cerevisiae show a genotoxic response on the end-points considered with an effect only at doses higher (5- to 10-fold) than the concentration normally used for water disinfection; sodium hypochlorite and peracetic acid are able to induce genotoxic effects without endogenous metabolic activation (in stationary phase cells) whereas chlorine dioxide is effective in growing cells. The Comet assay was more sensitive than the yeast tests, with effective doses in the range normally used for water disinfection processes. The biological effectiveness of the three disinfectants on S.cerevisiae proved to be strictly dependent on cell-specific physiological/biochemical conditions. All the compounds appear to act on the DNA and peracetic acid shows effectiveness similar to sodium hypochlorite and chlorine dioxide.

Oxidation of formic acid by oxyanions of chlorine and its implications to the Viking Labeled Release experiment

NASA Astrophysics Data System (ADS)

Martinez, P.; Navarro-gonzalez, R.

2013-05-01

The Viking Landers that arrived on Mars in 1976 carried out three biological experiments designed to investigate if there was microbial life. These were the Gas-Exchange, Pyrolitic Release and Labeled Release experiments. The three experiments yielded positive responses but the Labeled Release experiment had a kinetic response indicative of microbial activity. The experiment consisted of adding a broth of nutrients (formic acid, glycolic acid, glycine, D- and L-alanine and D- and L-lactic acid uniformly marked with 14C) to martian soil samples. The results were surprising; the nutrients were consumed releasing radioactive gases in a manner that is compatible by terrestrial microorganisms. The existence of Martian life was contradicted by soil chemical analysis that indicated the absence of organic compounds above the detection limits of parts per billion (ppb). Instead the positive response of the Labeled Release Experiment was attributed to the existence of peroxides and/or superoxides in the Martian soils that destroyed the nutrients upon contact. Recently, the Phoenix mission that landed in the Martian Arctic in 2008 revealed the presence of a highly oxidized form of the element chlorine in the soil: perchlorate. Perchlorate is thought to have formed in the Martian atmosphere by the oxidation of chloride from volcanic sources with ozone. Therefore perchlorate is formed by the stepwise oxidation of hypochlorite, chlorite and chlorate. These oxyanions of chlorine are powerful oxidizers that may exist in the Martian soil and may have reacted with the nutrients of the Labeled Release Experiment. This paper aims to better understand these results by designing experiments to determine the kinetics of decomposition of formic acid to carbon dioxide with different oxidized forms of chlorine by headspace technique in gas chromatography coupled to mass spectrometry (GC / MS). Previous studies done in the laboratory showed that only hypochlorite quantitatively reacted with the formate, this is why we conducted experiments at 20 ° C, 30 ° C and 40 ° C at times 0, 0.1, 0.5, 1, 3 , 5, 10, 20, 30, 40 and 60 min. The resulting kinetics were similar to those obtained by the LR experiment, however the speeds at which reacted in the laboratory were very rapid, almost instantaneous, a comparison of the acquired by the Viking was kinetics days. This may be because in the laboratory we do not used soil samples, Viking used Mars regolith Martian, like a complex matrix that may affect the reaction rate. We conclude that the response obtained by the LR experiment is possibly due to the presence of oxyanions of chlorine, hypochlorite specific which is increased by the dismutations chlorine species in solution, all in combination with other components very likely soil nutrients reacted with isotopically labeled. This project is still ongoing, open a new hypothesis of whether there is microbial life on Mars, since, if the Labeled Release experiment found no biological activity, may have been a chemical oxidation of organic nutrients for sodium hypochlorite .

Electrochemical oxidation of bio-refractory dye in a simulated textile industry effluent using DSA electrodes in a filter-press type FM01-LC reactor.

PubMed

Rodríguez, Francisca A; Mateo, María N; Aceves, Juan M; Rivero, Eligio P; González, Ignacio

2013-01-01

This work presents a study on degradation of indigo carmine dye in a filter-press type FM01-LC reactor using Sb2O5-doped Ti/IrO2-SnO2 dimensionally stable anode (DSA) electrodes. Micro- and macroelectrolysis studies were carried out using solutions of 0.8 mM indigo carmine in 0.05 M NaCl, which resemble blue denim laundry industrial wastewater. Microelectrolysis results show the behaviour of DSA electrodes in comparison with the behaviour of boron-doped diamond (BDD) electrodes. In general, dye degradation reactions are carried out indirectly through active chlorine generated on DSA, whereas in the case of BDD electrodes more oxidizing species are formed, mainly OH radicals, on the electrode surface. The well-characterized geometry, flow pattern and mass transport of the FM01-LC reactor used in macroelectrolysis experiments allowed the evaluation of the effect of hydrodynamic conditions on the chlorine-mediated degradation rate. Four values of Reynolds number (Re) (93, 371, 464 and 557) at four current densities (50, 100, 150 and 200 A/m2) were tested. The results show that the degradation rate is independent of Re at low current density (50 A/m2) but becomes dependent on the Re at high current density (200 A/m2). This behaviour shows the central role of mass transport and the reactor parameters and design. The low energy consumption (2.02 and 9.04 kWh/m3 for complete discolouration and chemical oxygen demand elimination at 50 A/m2, respectively) and the low cost of DSA electrodes compared to BDD make DSA electrodes promising for practical application in treating industrial textile effluents. In the present study, chlorinated organic compounds were not detected.

Comparative Study on Oxidative Treatments of NAPL Containing Chlorinated Ethanes and Ethenes using Hydrogen Peroxide and Persulfate in Soils

EPA Science Inventory

The goal of this study was to assess the oxidation of NAPL in soil, 30% of which were composed of chlorinated ethanes and ethenes, using catalyzed hydrogen peroxide (CHP), activated persulfate (AP), and H2O2–persulfate (HP) co-amendment systems. Citrate, a buffer and iron ligand,...

Reduction of disinfection by-product precursors in reservoir water by coagulation and ultrafiltration.

PubMed

Wang, Feng; Gao, Baoyu; Ma, Defang; Yue, Qinyan; Li, Ruihua; Wang, Qianwen

2016-11-01

In this study, reservoir water intended for drinking water supply was treated by (i) ultrafiltration (UF) (ii) coagulation (CW) (iii) coagulation combined with ultrafiltration (CW-UF). To probe the influences of three treatment processes on disinfection byproduct (DBP) precursors in source water, the changes of dissolved organic matter (DOM) amounts and physicochemical properties, and disinfection byproduct (DBP) formation characteristics during chlorine disinfection were investigated. Both carbonaceous DBP (C-DBP) and nitrogenous DBP (N-DBP) formation and speciation were analyzed. The influence of chlorine dose, contact time on DBP formation and speciation were also studied to optimize the disinfection conditions to minimize the DBP formation. Compared with UF and CW alone, CW-UF improved the dissolved organic carbon (DOC) removal from about 20 % to 59 %. The three-dimensional excitation and emission matrix (3DEEM) fluorescence spectroscopy analysis showed that CW-UF had high removal efficiency in microbial products (Region IV), fulvic acid-like (Region III) and humic acid-like (Region V). The total C-DBP was determined by the formation of trihalomethanes and trichloromethane was the most abundant species (40 %). The most abundant N-DBP species was dichloroacetonitrile (32.5 %), followed by trichloroactetonitrile. CW-UF effectively reduced the risk of DBPs in drinking water supply by reducing 30.8 % and 16.9 % DBPs formation potential compared with UF and CW alone. Increasing contact time improved the yields of both C-DBPs and N-DBPs. Chlorine dosage had slight influence on DBP yield in this study.

Modelling the Impacts of Long-term Changes in Ozone Depleting Substances on Stratospheric Composition

NASA Astrophysics Data System (ADS)

Chipperfield, M.; Feng, W.; Dhomse, S.; Hossaini, R.

2016-12-01

Long-lived ozone-depleting substances (ODSs), such as chlorofluorocarbons, halons and other gases, are controlled by the Montreal Protocol. Consequently, their atmospheric abundance has started to decline. This has led to a decrease in the overall loading of inorganic chlorine and bromine in the stratosphere and our expectation of recovery of the ozone layer. While observations of atmospheric composition are largely consistent with this picture, there remain some quantitative issues, which are investigated here using multi-decadal simulations of a three-dimensional chemical transport model. For example, atmospheric carbon tetrachloride has been decreasing at a slower rate than expected based on lifetime estimates and known emissions. We use the 3-D model to investigate the impact of uncertainties in the loss process. Also, increases in uncontrolled anthropogenic very short-lived species (VSLS), such as CH2Cl2, may offset some of the decline in chlorine from long-lived species, thereby delaying ozone recovery. We will quantify this impact using the 3-D model. Overall, we will use the model to test the agreement between observed changes in the near-surface abundance of ODSs and changes to stratospheric chlorine and bromine. For example, past studies have noted that variability in stratospheric dynamics (i.e. age of stratospheric air) can complicate the detection of composition trends. Finally, we will use the model to quantify the expected extent of ozone recovery from the combined effect of ODS decreases by late 2016.

Effects of intermittent chlorination on rainbow trout and yellow perch

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brooks, A.S.; Seegert, G.L.

1977-05-01

Rainbow trout, Salmo gairdneri, and yellow perch, Perca flavescens, were exposed to residual chlorine for single 30-minute and triple 5-minute doses. Tests were conducted at 10, 15, and 20 C with both species plus 25 and 30 C for the perch. Single exposure 30-minute LC50 values for the perch ranged from 0.70 mg/liter at 30 C to 8.0 mg/liter at 10 C. Triple 5-minute exposure LC50 values for the perch were 22.6 and 9.0 mg/liter at 10 and 20 C, respectively. Rainbow trout 30-minute LC50 values were 0.99 and 0.94 mg/liter at 10 and 15 C, respectively. Two groups ofmore » trout tested at 20 C yielded 30-minute LC50 values of 0.60 and 0.43 mg/liter. Triple exposure 5-minute LC50 values for the trout were 2.87 mg/liter at 10 C and 1.65 mg/liter at 20 C. Mortality occurred immediately after exposure to chlorine in the 30-minute perch tests at 10 and 15 C, but was delayed 2 to 12 hours at the higher temperatures. This pattern was reversed in the 5-minute triple exposure tests. Rainbow trout exhibited rapid mortality in all tests except the 10 C triple exposure series where mortality was delayed 12 to 24 hours. For both species, concentrations resulting in no mortality were approximately one-half the LC50 value.« less

Induction of Escherichia coli into a VBNC state through chlorination/chloramination and differences in characteristics of the bacterium between states.

PubMed

Chen, Sheng; Li, Xi; Wang, Yahong; Zeng, Jie; Ye, Chengsong; Li, Xianping; Guo, Lizheng; Zhang, Shenghua; Yu, Xin

2018-05-30

Many pathogens can enter into a viable but nonculturable (VBNC) state in response to harsh environmental stresses. Bacteria in this state can retain certain features of viable cells, such as cellular integrity, metabolic activity, or virulence and may present health risks associated with drinking water. In this study, we investigated the ability of chlorination and chloramination, which are widely used methods to disinfect drinking water, to induce Escherichia coli into a VBNC state. After treatment with chlorine and chloramine at concentrations of 1, 2, 3, and 4 mg/L, the counts of culturable E. coli cells decreased from 10 6  CFU/mL to 0 CFU/mL at 5-60 min post treatment. Meanwhile, viable cell counts were still approximately 10 3 -10 5  cells/mL. These viable E. coli cells may be induced into a VBNC state by chlorination and chloramination. Scanning electron microscopy and laser confocal microscopy showed that some bacteria maintained cellular integrity, but the average length of VBNC cells was less than that of culturable cells. Respiratory activity of VBNC cells decreased approximately 50% relative to that of culturable cells. We also used heavy water (D 2 O) combined with Raman microspectroscopy to show that E. coli in a VBNC state retained metabolic activity involving water (e.g. condensation reactions) at the single-cell level. Furthermore, soxR, gadA, and katG genes remained highly expressed, suggesting that VBNC cells were physiologically active. Finally, resuscitation of VBNC cells induced by chlorine in Luria-Bertani (LB) broth was identified by calculating the generation time. Results of this study will facilitate a better understanding of the health risks associated with VBNC bacteria and the development of more effective strategies for drinking water disinfection. Copyright © 2018. Published by Elsevier Ltd.

Reaction of benzophenone UV filters in the presence of aqueous chlorine: kinetics and chloroform formation.

PubMed

Duirk, Stephen E; Bridenstine, David R; Leslie, Daniel C

2013-02-01

The transformation of two benzophenone UV filters (Oxybenzone and Dioxybenzone) was examined over the pH range 6-11 in the presence of excess aqueous chlorine. Under these conditions, both UV filters were rapidly transformed by aqueous chlorine just above circumneutral pH while transformation rates were significantly lower near the extremes of the pH range investigated. Observed first-order rate coefficients (k(obs)) were obtained at each pH for aqueous chlorine concentrations ranging from 10 to 75 μM. The k(obs) were used to determine the apparent second-order rate coefficient (k(app)) at each pH investigated as well as determine the reaction order of aqueous chlorine with each UV filter. The reaction of aqueous chlorine with either UV filter was found to be an overall second-order reaction, first-order with respect to each reactant. Assuming elemental stoichiometry described the reaction between aqueous chlorine and each UV filter, models were developed to determine intrinsic rate coefficients (k(int)) from the k(app) as a function of pH for both UV filters. The rate coefficients for the reaction of HOCl with 3-methoxyphenol moieties of oxybenzone (OXY) and dioxybenzone (DiOXY) were k(1,OxY) = 306 ± 81 M⁻¹s⁻¹ and k(1,DiOxY) = 154 ± 76 M⁻¹s⁻¹, respectively. The k(int) for the reaction of aqueous chlorine with the 3-methoxyphenolate forms were orders of magnitude greater than the un-ionized species, k(2,OxY) = 1.03(±0.52) × 10⁶ M⁻¹s⁻¹ and k(2_1,DiOxY) = 4.14(±0.68) × 10⁵ M⁻¹s⁻¹. Also, k(int) for the reaction of aqueous chlorine with the DiOXY ortho-substituted phenolate moiety was k(2_2,DiOxY) = 2.17(±0.30) × 10³ M⁻¹s⁻¹. Finally, chloroform formation potential for OXY and DiOXY was assessed over the pH range 6-10. While chloroform formation decreased as pH increased for OXY, chloroform formation increased as pH increased from 6 to 10 for DiOXY. Ultimate molar yields of chloroform per mole of UV filter were pH dependent; however, chloroform to UV filter molar yields at pH 8 were 0.221 CHCl₃/OXY and 0.212 CHCl₃/DiOXY. Copyright © 2012 Elsevier Ltd. All rights reserved.

Biodegradation of bis(1-chloro-2-propyl) ether via initial ether scission and subsequent dehalogenation by Rhodococcus sp. strain DTB.

PubMed

Moreno Horn, Marcus; Garbe, Leif-Alexander; Tressl, Roland; Adrian, Lorenz; Görisch, Helmut

2003-04-01

Rhodococcus sp. strain DTB (DSM 44534) grows on bis(1-chloro-2-propyl) ether (DDE) as sole source of carbon and energy. The non-chlorinated diisopropyl ether and bis(1-hydroxy-2-propyl) ether, however, did not serve as substrates. In ether degradation experiments with dense cell suspensions, 1-chloro-2-propanol and chloroacetone were formed, which indicated that scission of the ether bond is the first step while dehalogenation of the chlorinated C(3)-compounds occurs at a later stage of the degradation pathway. Inhibition of ether scission by methimazole suggested that the first step in degradation is catalyzed by a flavin-dependent enzyme activity. The non-chlorinated compounds 1,2-propanediol, hydroxyacetone, lactate, pyruvate, 1-propanol, propanal, and propionate also supported growth, which suggested that the intermediates 1,2-propanediol and hydroxyacetone are converted to pyruvate or to propionate, which can be channeled into the citric acid cycle by a number of routes. Total release of chloride and growth-yield experiments with DDE and non-chlorinated C(3)-compounds suggested complete biodegradation of the chlorinated ether.

Enhanced photocatalytic activity of degrading short chain chlorinated paraffins over reduced graphene oxide/CoFe2O4/Ag nanocomposite.

PubMed

Chen, Xin; Zhao, Qidong; Li, Xinyong; Wang, Dong

2016-10-01

Short chain chlorinated paraffins have recently attracted great attention because of their environmental persistence and biological toxicity as an important organic pollutant. In this work, reduced graphene oxide/CoFe2O4/Ag (RGO/CoFe2O4/Ag) nanocomposite was prepared and employed for photocatalytic degradation of short chain chlorinated paraffins. The process of photocatalytic degradation of short chain chlorinated paraffins over RGO/CoFe2O4/Ag under visible light (λ>400nm) was investigated by in situ Fourier transform infrared spectroscopy and the related mechanisms were proposed. An apparent degradation ratio of 91.9% over RGO/CoFe2O4/Ag could be obtained under visible light illumination of 12h, while only about 21.7% was obtained with commercial P25 TiO2 under the same experimental conditions, which demonstrates that the RGO/CoFe2O4/Ag nanocomposite is a potential candidate for effective photocatalytic removal of short chain chlorinated paraffins. Copyright © 2016 Elsevier Inc. All rights reserved.

A Spore Counting Method and Cell Culture Model for Chlorine Disinfection Studies of Encephalitozoon syn. Septata intestinalis

PubMed Central

Wolk, D. M.; Johnson, C. H.; Rice, E. W.; Marshall, M. M.; Grahn, K. F.; Plummer, C. B.; Sterling, C. R.

2000-01-01

The microsporidia have recently been recognized as a group of pathogens that have potential for waterborne transmission; however, little is known about the effects of routine disinfection on microsporidian spore viability. In this study, in vitro growth of Encephalitozoon syn. Septata intestinalis, a microsporidium found in the human gut, was used as a model to assess the effect of chlorine on the infectivity and viability of microsporidian spores. Spore inoculum concentrations were determined by using spectrophotometric measurements (percent transmittance at 625 nm) and by traditional hemacytometer counting. To determine quantitative dose-response data for spore infectivity, we optimized a rabbit kidney cell culture system in 24-well plates, which facilitated calculation of a 50% tissue culture infective dose (TCID50) and a minimal infective dose (MID) for E. intestinalis. The TCID50 is a quantitative measure of infectivity and growth and is the number of organisms that must be present to infect 50% of the cell culture wells tested. The MID is as a measure of a system's permissiveness to infection and a measure of spore infectivity. A standardized MID and a standardized TCID50 have not been reported previously for any microsporidian species. Both types of doses are reported in this paper, and the values were used to evaluate the effects of chlorine disinfection on the in vitro growth of microsporidia. Spores were treated with chlorine at concentrations of 0, 1, 2, 5, and 10 mg/liter. The exposure times ranged from 0 to 80 min at 25°C and pH 7. MID data for E. intestinalis were compared before and after chlorine disinfection. A 3-log reduction (99.9% inhibition) in the E. intestinalis MID was observed at a chlorine concentration of 2 mg/liter after a minimum exposure time of 16 min. The log10 reduction results based on percent transmittance-derived spore counts were equivalent to the results based on hemacytometer-derived spore counts. Our data suggest that chlorine treatment may be an effective water treatment for E. intestinalis and that spectrophotometric methods may be substituted for labor-intensive hemacytometer methods when spores are counted in laboratory-based chlorine disinfection studies. PMID:10742198

Novel chlorinated dibenzofurans isolated from the cellular slime mold, Polysphondylium filamentosum, and their biological activities.

PubMed

Kikuchi, Haruhisa; Kubohara, Yuzuru; Nguyen, Van Hai; Katou, Yasuhiro; Oshima, Yoshiteru

2013-08-01

Cellular slime molds are expected to have the huge potential for producing secondary metabolites including polyketides, and we have studied the diversity of secondary metabolites of cellular slime molds for their potential utilization as new biological resources for natural product chemistry. From the methanol extract of fruiting bodies of Polysphondylium filamentosum, we obtained new chlorinated benzofurans Pf-1 (4) and Pf-2 (5) which display multiple biological activities; these include stalk cell differentiation-inducing activity in the well-studied cellular slime mold, Dictyostelium discoideum, and inhibitory activities on cell proliferation in mammalian cells and gene expression in Drosophila melanogaster. Copyright © 2013 Elsevier Ltd. All rights reserved.

Environmental occurrence and distribution of short chain chlorinated paraffins in sediments and soils from the Liaohe River Basin, P. R. China.

PubMed

Gao, Yuan; Zhang, Haijun; Su, Fan; Tian, Yuzeng; Chen, Jiping

2012-04-03

Chlorinated paraffins (CPs) are industrially produced in large quantities in the Liaohe River Basin. Their discharge inevitably causes environmental contamination. However, very limited information is available on their environmental levels and distributions in this typical industrial region. In this study, short chain CPs (SCCPs) were analyzed in sediments, paddy soils, and upland soils from the Liaohe River Basin, with concentrations ranging from 39.8 to 480.3 ng/g dry weight. A decreasing trend in SCCP concentrations was found with increasing distance from the cities, suggesting that local industrial activity was the major source of SCCP contamination. A preliminary sediment inventory of SCCPs indicated approximately 30.82 tonnes of SCCPs residual in the sediments from the Liaohe River. The average discharge of SCCPs was estimated to be about 74.4 mg/tonne industrial wastewater. The congener group profiles showed that the relative abundances of shorter chain and lower chlorinated CP congeners (C(10)-CPs with 5 or 6 chlorine atoms) in soils in rural areas were higher than in sites near cities, which demonstrated that long-range atmospheric transportation could be the major transport pathway. Environmental degradation of SCCPs might occur, where higher chlorinated congeners could dechlorinate to form the lower chlorinated congeners.

High-performance Ti/Sb-SnO(2)/Pb(3)O(4) electrodes for chlorine evolution: preparation and characteristics.

PubMed

Shao, Dan; Yan, Wei; Cao, Lu; Li, Xiaoliang; Xu, Hao

2014-02-28

Chlorine evolution via electrochemical approach has wide application prospects in drinking water disinfection and wastewater treatment fields. Dimensional stable anodes used for chlorine evolution should have high stability and adequate chlorine evolution efficiency. Thus a novel and cost-effective Ti/Sb-SnO(2)/Pb(3)O(4)electrode was developed. The physicochemical and electrochemical properties as well as the chlorine evolution performances of the electrodes were investigated. The electrocatalytic activity and deactivation course of the electrodes were also explored. Results showed that this novel electrode had strong chlorine evolution ability with high current efficiency ranging from 87.3% to 93.4% depending on the operational conditions. The accelerated service life of Ti/Sb-SnO(2)/Pb(3)O(4) electrode could reach 180 h at a current density of 10,000 A m(-2) in 0.5 molL(-1) H(2)SO(4). During the electrolysis process, it was found that the conversion of Pb(3)O(4) into β-PbO(2) happened gradually on the electrode surface, which not only inhibited the leakage of hazardous Pb(2+) ion but also increased the anti-corrosion capacity of the electrode effectively. Copyright © 2014 Elsevier B.V. All rights reserved.

Influence of trophic conditions on exopolysaccharide production: bacterial biofilm susceptibility to chlorine and monochloramine.

PubMed

Samrakandi, M M; Roques, C; Michel, G

1997-08-01

This study examines the controversial efficacy of chlorine and monochloramine against biofilms that differ in their extracellular polysaccharide (EPS) content. The results point out a net variability of bacterial biofilm susceptibility according to the nutrients present. Chlorine and monochloramine showed an equal biocidal activity on lactose medium-grown E. coli ATCC 10536 and glycerol-ammonium nitrate medium-grown nonmucoid Pseudomonas aeruginosa biofilms. In contrast, the effect of monochloramine is greater compared with that of chlorine on E. coli and mucoid P. aeruginosa biofilms grown in sucrose and glycerol-ammonium nitrate media, respectively. In these culture conditions, treatment with 25 mg monochloramine/L for 2 h reduced culturable cells by 4.5 logs (99.997%) for E. coli and about 3 logs (99.87%) for mucoid P. aeruginosa while the similar treatment with chlorine reduced culturable cells in these biofilms by 2.2 logs (99.4%) and 1 log (10%), respectively. The decrease of chlorine disinfection efficacy on sucrose and glycerol-ammonium nitrate medium-grown biofilms is postulated to be linked to the higher polysaccharide production observed in these media. It seems likely that monochloramine produces a high leakage of material absorbing at 260 nm from sucrose medium-grown E. coli biofilm, which could indicate its better penetration into biofilms.

Inactivation of biofilm bacteria.

PubMed Central

LeChevallier, M W; Cawthon, C D; Lee, R G

1988-01-01

The current project was developed to examine inactivation of biofilm bacteria and to characterize the interaction of biocides with pipe surfaces. Unattached bacteria were quite susceptible to the variety of disinfectants tested. Viable bacterial counts were reduced 99% by exposure to 0.08 mg of hypochlorous acid (pH 7.0) per liter (1 to 2 degrees C) for 1 min. For monochloramine, 94 mg/liter was required to kill 99% of the bacteria within 1 min. These results were consistent with those found by other investigators. Biofilm bacteria grown on the surfaces of granular activated carbon particles, metal coupons, or glass microscope slides were 150 to more than 3,000 times more resistant to hypochlorous acid (free chlorine, pH 7.0) than were unattached cells. In contrast, resistance of biofilm bacteria to monochloramine disinfection ranged from 2- to 100-fold more than that of unattached cells. The results suggested that, relative to inactivation of unattached bacteria, monochloramine was better able to penetrate and kill biofilm bacteria than free chlorine. For free chlorine, the data indicated that transport of the disinfectant into the biofilm was a major rate-limiting factor. Because of this phenomenon, increasing the level of free chlorine did not increase disinfection efficiency. Experiments where equal weights of disinfectants were used suggested that the greater penetrating power of monochloramine compensated for its limited disinfection activity. These studies showed that monochloramine was as effective as free chlorine for inactivation of biofilm bacteria. The research provides important insights into strategies for control of biofilm bacteria. Images PMID:2849380

Products identified at an alternative disinfection pilot plant.

PubMed Central

Lykins, B W; Koffskey, W

1986-01-01

Many drinking water utilities have recently changed or are seriously considering changing their disinfection practice from chlorine to some alternative treatment process. However, most of these utilities are changing their disinfectants without evaluating chemical impacts. Therefore, a research cooperative agreement was developed with Jefferson Parish, LA, to evaluate four parallel streams treated with four different disinfectants (chlorine, monochloramine, chlorine dioxide, and ozone.) These streams, along with a fifth parallel stream, which was not treated with a disinfectant (control), were passed through both sand and granular activated carbon (GAC). Ozonation reduced the total organic carbon (TOC) and total organic halide (TOX) concentration by 0.3 mg/L and 10 micrograms/L, respectively. The average concentration of TOC for the other disinfectants was comparable to that associated with the nondisinfected stream (3.3 mg/L). The average instantaneous TOX concentration for chlorine dioxide, chloramine, and chlorine disinfection after 30 min contact time increased by 60, 92, and 238 micrograms/L, respectively, from a nondisinfected concentration of 25 micrograms/L. The volatile organics most affected by disinfection (chlorination) were the trihalomethanes. No significant change in concentration was noted after disinfection for the other volatile organics evaluated, such as 1,2-dichlorethane, dichloromethane, trichloroethylene, 1,1,2-trichloroethane, and carbon tetrachloride. Ozonation produced an average concentration reduction of 11 to 84% for most of the nonvolatiles evaluated. Conversely, a concentration increase of 43 to 100% was noted, after chlorination, for some of the nonvolatile organics. PMID:3816717

Type of disinfectant in drinking water and patterns of mortality in Massachusetts.

PubMed Central

Zierler, S; Danley, R A; Feingold, L

1986-01-01

Chlorination has been the major strategy for disinfection of drinking water in the United States. Concern about the potential health effects of the reaction by-products of chlorine has prompted use of alternative strategies. One such method is chloramination, a treatment process that does not appear to have carcinogenic by-products, but may have less potent biocidal activity than chlorination. We examined the patterns of mortality of residents in Massachusetts who died between 1969 and 1983 and lived in communities using drinking water that was disinfected either by chlorine or chloramine. Comparison of type of disinfectant among 51,645 cases of deaths due to selected cancer sites and 214,988 controls who died from cardiovascular, cerebrovascular, or pulmonary disease, or from lymphatic cancer showed small variation in the patterns of mortality. Bladder cancer was moderately associated with residence at death in a chlorinated community (mortality odds ratio = 1.7, 95% confidence interval = 1.3-2.2) in a logistic regression analysis using controls who died from lymphatic cancer. A slight excess of deaths from pneumonia and influenza was observed in communities whose residents drank chloraminated water compared to residents from chlorinated communities, as well as to all Massachusetts residents (standardized mortality ratio = 118, 95% confidence interval = 116-120 for chloraminated communities, and standardized mortality ratio = 98, 95% confidence interval = 95-100 for chlorinated communities). These results are intended to be preliminary and crude descriptions of the relationship under study.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:3816730

Products identified at an alternative disinfection pilot plant

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lykins, B.W. Jr.; Koffskey, W.

1986-11-01

Many drinking water utilities have recently changed or are seriously considering changing their disinfection practice from chlorine to some alternative treatment process. However, most of these utilities are changing their disinfectants without evaluating chemical impacts. Therefore, a research cooperative agreement was developed with Jefferson Parish, LA, to evaluate four parallel streams treated with four different disinfectants (chlorine, monochloramine, chlorine dioxide, and ozone.) These streams, along with a fifth parallel stream, which was not treated with a disinfectant (control), were passed through both sand and granular activated carbon (GAC). Ozonation reduced the total organic carbon (TOC) and total organic halide (TOX)more » concentration by 0.3 mg/L and 10 micrograms/L, respectively. The average concentration of TOC for the other disinfectants was comparable to that associated with the nondisinfected stream (3.3 mg/L). The average instantaneous TOX concentration for chlorine dioxide, chloramine, and chlorine disinfection after 30 min contact time increased by 60, 92, and 238 micrograms/L, respectively, from a nondisinfected concentration of 25 micrograms/L. The volatile organics most affected by disinfection (chlorination) were the trihalomethanes. No significant change in concentration was noted after disinfection for the other volatile organics evaluated, such as 1,2-dichlorethane, dichloromethane, trichloroethylene, 1,1,2-trichloroethane, and carbon tetrachloride. Ozonation produced an average concentration reduction of 11 to 84% for most of the nonvolatiles evaluated. Conversely, a concentration increase of 43 to 100% was noted, after chlorination, for some of the nonvolatile organics.« less

Disinfection of swine wastewater using chlorine, ultraviolet light and ozone.

PubMed

Macauley, John J; Qiang, Zhimin; Adams, Craig D; Surampalli, Rao; Mormile, Melanie R

2006-06-01

Veterinary antibiotics are widely used at concentrated animal feeding operations (CAFOs) to prevent disease and promote growth of livestock. However, the majority of antibiotics are excreted from animals in urine, feces, and manure. Consequently, the lagoons used to store these wastes can act as reservoirs of antibiotics and antibiotic-resistant bacteria. There is currently no regulation or control of these systems to prevent the spread of these bacteria and their genes for antibiotic resistance into other environments. This study was conducted to determine the disinfection potential of chlorine, ultraviolet light and ozone against swine lagoon bacteria. Results indicate that a chlorine dose of 30 mg/L could achieve a 2.2-3.4 log bacteria reduction in lagoon samples. However, increasing the dose of chlorine did not significantly enhance the disinfection activity due to the presence of chlorine-resistant bacteria. The chlorine resistant bacteria were identified to be closely related to Bacillus subtilis and Bacillus licheniformis. A significant percentage of lagoon bacteria were not susceptible to the four selected antibiotics: chlortetracycline, lincomycin, sulfamethazine and tetracycline (TET). However, the presence of both chlorine and TET could inactivate all bacteria in one lagoon sample. The disinfection potential of UV irradiation and ozone was also examined. Ultraviolet light was an effective bacterial disinfectant, but was unlikely to be economically viable due to its high energy requirements. At an ozone dose of 100 mg/L, the bacteria inactivation efficiency could reach 3.3-3.9 log.

Lethality of chlorine, chlorine dioxide, and a commercial fruit and vegetable sanitizer to vegetative cells and spores of Bacillus cereus and spores of Bacillus thuringiensis.

PubMed

Beuchat, Larry R; Pettigrew, Charles A; Tremblay, Mario E; Roselle, Brian J; Scouten, Alan J

2004-08-01

Chlorine, ClO2, and a commercial raw fruit and vegetable sanitizer were evaluated for their effectiveness in killing vegetative cells and spores of Bacillus cereus and spores of Bacillus thuringiensis. The ultimate goal was to use one or both species as a potential surrogate(s) for Bacillus anthracis in studies that focus on determining the efficacy of sanitizers in killing the pathogen on food contact surfaces and foods. Treatment with alkaline (pH 10.5 to 11.0) ClO2 (200 microg/ml) produced by electrochemical technologies reduced populations of a five-strain mixture of vegetative cells and a five-strain mixture of spores of B. cereus by more than 5.4 and more than 6.4 log CFU/ml respectively, within 5 min. This finding compares with respective reductions of 4.5 and 1.8 log CFU/ml resulting from treatment with 200 microg/ml of chlorine. Treatment with a 1.5% acidified (pH 3.0) solution of Fit powder product was less effective, causing 2.5- and 0.4-log CFU/ml reductions in the number of B. cereus cells and spores, respectively. Treatment with alkaline ClO2 (85 microg/ml), acidified (pH 3.4) ClO2 (85 microg/ml), and a mixture of ClO2 (85 microg/ml) and Fit powder product (0.5%) (pH 3.5) caused reductions in vegetative cell/spore populations of more than 5.3/5.6, 5.3/5.7, and 5.3/6.0 log CFU/ml, respectively. Treatment of B. cereus and B. thuringiensis spores in a medium (3.4 mg/ml of organic and inorganic solids) in which cells had grown and produced spores with an equal volume of alkaline (pH 12.1) ClO2 (400 microg/ml) for 30 min reduced populations by 4.6 and 5.2 log CFU/ml, respectively, indicating high lethality in the presence of materials other than spores that would potentially react with and neutralize the sporicidal activity of ClO2.

Quantification of bisphenol A, 353-nonylphenol and their chlorinated derivatives in drinking water treatment plants.

PubMed

Dupuis, Antoine; Migeot, Virginie; Cariot, Axelle; Albouy-Llaty, Marion; Legube, Bernard; Rabouan, Sylvie

2012-11-01

Bisphenol A (BPA) and nonylphenols (NP) are of major concern to public health due to their high potential for human exposure and to their demonstrated toxicity (endocrine disruptor effect). A limited number of studies have shown that BPA and NP are present in drinking water. The chlorinated derivatives that may be formed during the chlorination step in drinking water treatment plants (DWTP) exhibit a higher level of estrogenic activity than their parent compounds. The aim of this study was to investigate BPA, 353NP, and their chlorinated derivative concentrations using an accurate and reproducible method of quantification. This method was applied to both surface and treated water samples from eight French DWTPs producing from surface water. Solid-phase extraction followed by liquid chromatography-tandem mass spectrometry was developed in order to quantify target compounds from water samples. The limits of detection ranged from 0.3 to 2.3 ng/L for BPA and chlorinated BPA and from 1.4 to 63.0 ng/L for 353NP and chlorinated 353NP. BPA and 353NP were found in most analyzed water samples, at a level ranging from 2.0 to 29.7 ng/L and from 0 to 124.9 ng/L, respectively. In most of DWTPs a decrease of BPA and 353NP was observed between surface water and treated water (36.6 to 78.9 % and 2.2 to 100.0 % for BPA and 353NP, respectively). Neither chlorinated BPA nor chlorinated 353NP was detected. Even though BPA and 353NP have been largely removed in the DWTPs studied, they have not been completely eliminated, and drinking water may consequently remain a source of human exposure.

Inactivation of human norovirus using chemical sanitizers.

PubMed

Kingsley, David H; Vincent, Emily M; Meade, Gloria K; Watson, Clytrice L; Fan, Xuetong

2014-02-03

The porcine gastric mucin binding magnetic bead (PGM-MB) assay was used to evaluate the ability of chlorine, chlorine dioxide, peroxyacetic acid, hydrogen peroxide, and trisodium phosphate to inactivate human norovirus within 10% stool filtrate. One-minute free chlorine treatments at concentrations of 33 and 189 ppm reduced virus binding in the PGM-MB assay by 1.48 and 4.14 log₁₀, respectively, suggesting that chlorine is an efficient sanitizer for inactivation of human norovirus (HuNoV). Five minute treatments with 5% trisodium phosphate (pH~12) reduced HuNoV binding by 1.6 log₁₀, suggesting that TSP, or some other high pH buffer, could be used to treat food and food contact surfaces to reduce HuNoV. One minute treatments with 350 ppm chlorine dioxide dissolved in water did not reduce PGM-MB binding, suggesting that the sanitizer may not be suitable for HuNoV inactivation in liquid form. However a 60-min treatment with 350 ppm chlorine dioxide did reduce human norovirus by 2.8 log₁₀, indicating that chlorine dioxide had some, albeit limited, activity against HuNoV. Results also suggest that peroxyacetic acid has limited effectiveness against human norovirus, since 1-min treatments with up to 195 ppm reduced human norovirus binding by <1 log₁₀. Hydrogen peroxide (4%) treatment of up to 60 min resulted in minimal binding reduction (~0.1 log₁₀) suggesting that H₂O₂ is not a good liquid sanitizer for HuNoV. Overall this study suggests that HuNoV is remarkably resistant to several commonly used disinfectants and advocates for the use of chlorine (sodium hypochlorite) as a HuNoV disinfectant wherever possible. Copyright © 2013. Published by Elsevier B.V.

Lindane degradation by electrooxidation process: Effect of electrode materials on oxidation and mineralization kinetics.

PubMed

Dominguez, Carmen M; Oturan, Nihal; Romero, Arturo; Santos, Aurora; Oturan, Mehmet A

2018-05-15

This study focuses on the effect of electrode materials on abatement of lindane (an organochlorine pesticide) by electrooxidation process. Comparative performances of different anodic (platinum (Pt), dimensionally stable anode (DSA) and boron-doped diamond (BDD)) and cathodic (carbon sponge (CS), carbon felt (CF) and stainless steel (SS)) materials on lindane electrooxidation and mineralization were investigated. Special attention was paid to determine the role of chlorine active species during the electrooxidation process. The results showed that better performances were obtained when using a BDD anode and CF cathode cell. The influence of the current density was assessed to optimize the oxidation of lindane and the mineralization of its aqueous solution. A quick (10 min) and complete oxidation of 10 mg L -1 lindane solution and relatively high mineralization degree (80% TOC removal) at 4 h electrolysis were achieved at 8.33 mA cm -2 current density. Lindane was quickly oxidized by in-situ generated hydroxyl radicals, (M( • OH)), formed from oxidation of water on the anode (M) surface following pseudo first-order reaction kinetics. Formation of chlorinated and hydroxylated intermediates and carboxylic acids during the treatment were identified and a plausible mineralization pathway of lindane by hydroxyl radicals was proposed. Copyright © 2018 Elsevier Ltd. All rights reserved.

Chlorination of bromide-containing waters: enhanced bromate formation in the presence of synthetic metal oxides and deposits formed in drinking water distribution systems.

PubMed

Liu, Chao; von Gunten, Urs; Croué, Jean-Philippe

2013-09-15

Bromate formation from the reaction between chlorine and bromide in homogeneous solution is a slow process. The present study investigated metal oxides enhanced bromate formation during chlorination of bromide-containing waters. Selected metal oxides enhanced the decay of hypobromous acid (HOBr), a requisite intermediate during the oxidation of bromide to bromate, via (i) disproportionation to bromate in the presence of nickel oxide (NiO) and cupric oxide (CuO), (ii) oxidation of a metal to a higher valence state in the presence of cuprous oxide (Cu2O) and (iii) oxygen formation by NiO and CuO. Goethite (α-FeOOH) did not enhance either of these pathways. Non-charged species of metal oxides seem to be responsible for the catalytic disproportionation which shows its highest rate in the pH range near the pKa of HOBr. Due to the ability to catalyze HOBr disproportionation, bromate was formed during chlorination of bromide-containing waters in the presence of CuO and NiO, whereas no bromate was detected in the presence of Cu2O and α-FeOOH for analogous conditions. The inhibition ability of coexisting anions on bromate formation at pH 8.6 follows the sequence of phosphate > sulfate > bicarbonate/carbonate. A black deposit in a water pipe harvested from a drinking water distribution system exerted significant residual oxidant decay and bromate formation during chlorination of bromide-containing waters. Energy dispersive spectroscopy (EDS) analyses showed that the black deposit contained copper (14%, atomic percentage) and nickel (1.8%, atomic percentage). Cupric oxide was further confirmed by X-ray diffraction (XRD). These results indicate that bromate formation may be of concern during chlorination of bromide-containing waters in distribution systems containing CuO and/or NiO. Copyright © 2013 Elsevier Ltd. All rights reserved.

Formation of iodo-trihalomethanes (I-THMs) during disinfection with chlorine or chloramine: Impact of UV/H2O2 pre-oxidation.

PubMed

Zhang, Jie; Liu, Jing; He, Chuan-Shu; Qian, Chen; Mu, Yang

2018-06-04

Ultraviolet/hydrogen peroxide (UV/H 2 O 2 ) pre-oxidation has the potential to induce reactions with dissolved organic matter (DOM) and alter the generation of disinfection byproducts (DBPs). This study evaluated the influence of UV/H 2 O 2 pretreatment on the formation of iodo-trihalomethanes (I-THMs) during disinfection with chlorine or chloramine. The changes of precursors, I - and Br - , after UV/H 2 O 2 pretreatment were investigated, and then, the formation and speciation of I-THMs during chlorination or chloramination after pre-oxidation were explored. Additionally, the effects of UV doses and H 2 O 2 concentrations on the formation and speciation of I-THMs were studied. It was found that UV/H 2 O 2 pretreatment could change larger molecular weight (MW) DOM to smaller MW species, which had less aromatic organic compounds and fluorescence substances. Additionally, insignificant transformations of I - and Br - were observed after UV/H 2 O 2 treatment. Compared to direct disinfection, UV/H 2 O 2 pretreatment resulted in 23.0 ± 3.5% reduction in I-THMs formation during post-chlorination while an enhancement was observed during post-chloramination at a UV dose of 460 mJ/cm 2 and 20 mg/L H 2 O 2 . Moreover, total I-THM concentration increased from 43.7 ± 2.4 to 97.6 ± 14.9 nM with the increase of UV doses from 0 to 1400 mJ/cm 2 during the post-chlorination process, while reduced when the UV fluence was >460 mJ/cm 2 during the post-chloramination. Additionally, the generation of I-THMs during both post-chlorination and post-chloramination was positively related to the H 2 O 2 levels from 0 to 20 mg/L in the UV/H 2 O 2 pretreatment. Copyright © 2018 Elsevier B.V. All rights reserved.

Estrogen-related receptor gamma disruption of source water and drinking water treatment processes extracts.

PubMed

Li, Na; Jiang, Weiwei; Rao, Kaifeng; Ma, Mei; Wang, Zijian; Kumaran, Satyanarayanan Senthik

2011-01-01

Environmental chemicals in drinking water can impact human health through nuclear receptors. Additionally, estrogen-related receptors (ERRs) are vulnerable to endocrine-disrupting effects. To date, however, ERR disruption of drinking water potency has not been reported. We used ERRgamma two-hybrid yeast assay to screen ERRgamma disrupting activities in a drinking water treatment plant (DWTP) located in north China and in source water from a reservoir, focusing on agonistic, antagonistic, and inverse agonistic activity to 4-hydroxytamoxifen (4-OHT). Water treatment processes in the DWTP consisted of pre-chlorination, coagulation, coal and sand filtration, activated carbon filtration, and secondary chlorination processes. Samples were extracted by solid phase extraction. Results showed that ERRgamma antagonistic activities were found in all sample extracts, but agonistic and inverse agonistic activity to 4-OHT was not found. When calibrated with the toxic equivalent of 4-OHT, antagonistic effluent effects ranged from 3.4 to 33.1 microg/L. In the treatment processes, secondary chlorination was effective in removing ERRgamma antagonists, but the coagulation process led to significantly increased ERRgamma antagonistic activity. The drinking water treatment processes removed 73.5% of ERRgamma antagonists. To our knowledge, the occurrence of ERRgamma disruption activities on source and drinking water in vitro had not been reported previously. It is vital, therefore, to increase our understanding of ERRy disrupting activities in drinking water.

Electron Spectroscopy for Chemical Analysis (ESCA) study of atmospheric particles

NASA Technical Reports Server (NTRS)

Dillard, J. G.; Seals, R. D.; Wightman, J. P.

1979-01-01

The results of analyses by ESCA (Electron Spectroscopy for Chemical Analysis) on several Nuclepore filters which were exposed during air pollution studies are presented along with correlative measurements by Neutron Activation Analysis and Scanning Electron Microscopy. Samples were exposed during air pollution studies at Norfolk, Virginia and the NASA Kennedy Space Center (KSC). It was demonstrated that with the ESCA technique it was possible to identify the chemical (bonding) state of elements contained in the atmospheric particulate matter collected on Nuclepore filters. Sulfur, nitrogen, mercury, chlorine, alkali, and alkaline earth metal species were identified in the Norfolk samples. ESCA binding energy data for aluminum indicated that three chemically different types of aluminum are present in the launch and background samples from NASA-KSC.

Acute changes in serum immune markers due to swimming in a chlorinated pool.

PubMed

Vlaanderen, Jelle; van Veldhoven, Karin; Font-Ribera, Laia; Villanueva, Cristina M; Chadeau-Hyam, Marc; Portengen, Lützen; Grimalt, Joan O; Zwiener, Christian; Heederik, Dick; Zhang, Xiangru; Vineis, Paolo; Kogevinas, Manolis; Vermeulen, Roel

2017-08-01

Exposure to disinfectants and disinfection byproducts (DBPs) due to swimming in chlorinated water has been associated with allergic and respiratory health effects, including asthma. Biological mechanisms contributing to these associations are largely unknown. We hypothesized a potential pathway involving modulation of the immune system. We assessed levels of immune markers (CCL11, CCL22, CXCL10, CRP, EGF, GCSF, IL-8, IL-17, IL-1RA, MPO, VEGF, Periostin) in serum collected from 30 women and 29 men before and after 40min of swimming in a chlorinated pool. Exposure to DBPs was assessed by measuring bromodichloromethane, bromoform, chloroform, and dibromochloromethane in exhaled breath before and after swimming. Covariate data including information on physical activity was available through questionnaires and measurements. We assessed the association between indicators of swimming in a chlorinated pool and changes in serum immune marker concentrations using linear regression with bivariate normal distributions and adjusted for multiple comparisons by applying the Benjamini-Hochberg procedure. We observed a significant decrease in serum concentrations of IL-8 (-12.53%; q=2.00e-03), CCL22 (-7.28%; q=4.00e-04), CCL11 (-7.15%; q=9.48e-02), CRP (-7.06%; q=4.68e-05), and CXCL10 (-13.03%; q=6.34e-14) and a significant increase in IL-1RA (20.16%; q=4.18e-06) from before to after swimming. Associations with quantitative measurements of DBPs or physical activity were similar in direction and strength. Most of the observed associations became non-significant when we adjusted the effects of exposure to DBPs for physical activity or vice-versa. Our study indicates that swimming in a chlorinated pool induces perturbations of the immune response through acute alterations of patterns of cytokine and chemokine secretion. The observed effects could not be uniquely attributed to either exposure to DBPs or physical activity. Evidence in the literature suggests that observed decreases in immune markers are possibly due to an immunosuppressive effect of DBPs, while the increase in IL-1RA might be due to physical activity. Copyright © 2017 Elsevier Ltd. All rights reserved.

Annual Report to Congress, Fiscal Year 1997. A Report by The Council of the Strategic Environmental Research and Development Program

DTIC Science & Technology

1998-03-01

Discovery of Novel Enzymatic Reactions and Determination of Biodegradation Mechanisms and Pathways. b. Phytoremediation of Explosives Contaminated...Groundwater using Wetlands and Aquatic Plants. c. Phytoremediation of Munitions Contaminated Soils. d. Enhanced TNT Biodegradation Through Genetic Manipulation...Microbial Communities Active in the Enhanced Aerobic Treatment of Chlorinated Ethenes. c. Phytoremediation of Shallow Chlorinated Solvent Plumes

A computer simulation of the afterburning processes occurring within solid rocket motor plumes in the troposphere

NASA Technical Reports Server (NTRS)

Gomberg, R. I.; Stewart, R. B.

1976-01-01

As part of a continuing study of the environmental effects of solid rocket motor (SRM) operations in the troposphere, a numerical model was used to simulate the afterburning processes occurring in solid rocket motor plumes and to predict the quantities of potentially harmful chemical species which are created. The calculations include the effects of finite-rate chemistry and turbulent mixing. It is found that the amount of NO produced is much less than the amount of HCl present in the plume, that chlorine will appear predominantly in the form of HCl although some molecular chlorine is present, and that combustion is complete as is evident from the predominance of carbon dioxide over carbon monoxide.

Coplanar polychlorinated biphenyl congeners in shark livers from the north-western African Atlantic ocean

DOE Office of Scientific and Technical Information (OSTI.GOV)

Serrano, R.; Fernandez, M.A.; Hernandez, L.M.

1997-01-01

Polychlorinated biphenyls have been widely used by industry throughout the world since 1930. Although their use has been banned in many countries since the late 1970s, they still represent an important class of priority pollutants due to their persistence. Most open uses of these chemicals have been severely curtailed in industrialized nations, but a considerable fraction of past productions is probably still cycling in the ecosphere. In recent years, attention has been focused on the toxicity of PCBs, especially of those congeners showing similar toxicity as the polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDFs). It has been shown that PCB congeners`more » toxicity largely depends on the chlorine substitution pattern. The most toxic PCB cogeners are those with two para chlorines, at least two meta chlorines and 0-2 ortho chlorines. These so-called {open_quotes}coplanar{close_quotes} (non- mono- and di-ortho) PCB cogeners are able to obtain planar conformation. Recently, toxic equivalence factors have been assigned to coplanar PCBs. Thus determination of individual PCB cogeners is important for evaluating the toxic potentials of PCB residues in, for example, wildlife. This paper presents preliminary results of a study looking at levels of PCB congeners, including coplanar ones, in the liver of six shark species, collected in the North African Atlantic Ocean. 15 refs., 2 figs., 2 tabs.« less

Inorganic Chlorine Partitioning in the Summer Lower Stratosphere: Modeled and Measured [ClONO2/HCl] During POLARIS

NASA Technical Reports Server (NTRS)

Voss, P. B.; Stimpfle, R. M.; Cohen, R. C.; Hanisco, T. F.; Bonne, G. P.; Perkins, K. K.; Lanzendorf, E. J.; Anderson, J. G.; Salawitch, R. J.

2001-01-01

We examine inorganic chlorine (Cly) partitioning in the summer lower stratosphere using in situ ER-2 aircraft observations made during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) campaign. New steady state and numerical models estimate [ClONO2]/[HCl] using currently accepted photochemistry. These models are tightly constrained by observations with OH (parameterized as a function of solar zenith angle) substituting for modeled HO2 chemistry. We find that inorganic chlorine photochemistry alone overestimates observed [ClONO2]/[HCl] by approximately 55-60% at mid and high latitudes. On the basis of POLARIS studies of the inorganic chlorine budget, [ClO]/[ClONO2], and an intercomparison with balloon observations, the most direct explanation for the model-measurement discrepancy in Cly partitioning is an error in the reactions, rate constants, and measured species concentrations linking HCl and ClO (simulated [ClO]/[HCl] too high) in combination with a possible systematic error in the ER-2 ClONO2 measurement (too low). The high precision of our simulation (+/-15% 1-sigma for [ClONO2]/[HCl], which is compared with observations) increases confidence in the observations, photolysis calculations, and laboratory rate constants. These results, along with other findings, should lead to improvements in both the accuracy and precision of stratospheric photochemical models.

Revealing hidden spectral information of chlorine and sulfur in data of a mobile Laser-induced Breakdown Spectroscopy system using chemometrics

NASA Astrophysics Data System (ADS)

Gottlieb, C.; Millar, S.; Günther, T.; Wilsch, G.

2017-06-01

For the damage assessment of reinforced concrete structures the quantified ingress profiles of harmful species like chlorides, sulfates and alkali need to be determined. In order to provide on-site analysis of concrete a fast and reliable method is necessary. Low transition probabilities as well as the high ionization energies for chlorine and sulfur in the near-infrared range makes the detection of Cl I and S I in low concentrations a difficult task. For the on-site analysis a mobile LIBS-system (λ = 1064 nm, Epulse ≤ 3 mJ, τ = 1.5 ns) with an automated scanner has been developed at BAM. Weak chlorine and sulfur signal intensities do not allow classical univariate analysis for process data derived from the mobile system. In order to improve the analytical performance multivariate analysis like PLS-R will be presented in this work. A comparison to standard univariate analysis will be carried out and results covering important parameters like detection and quantification limits (LOD, LOQ) as well as processing variances will be discussed (Allegrini and Olivieri, 2014 [1]; Ostra et al., 2008 [2]). It will be shown that for the first time a low cost mobile system is capable of providing reproducible chlorine and sulfur analysis on concrete by using a low sensitive system in combination with multivariate evaluation.

Sequential Combination of Electro-Fenton and Electrochemical Chlorination Processes for the Treatment of Anaerobically-Digested Food Wastewater.

PubMed

Shin, Yong-Uk; Yoo, Ha-Young; Kim, Seonghun; Chung, Kyung-Mi; Park, Yong-Gyun; Hwang, Kwang-Hyun; Hong, Seok Won; Park, Hyunwoong; Cho, Kangwoo; Lee, Jaesang

2017-09-19

A two-stage sequential electro-Fenton (E-Fenton) oxidation followed by electrochemical chlorination (EC) was demonstrated to concomitantly treat high concentrations of organic carbon and ammonium nitrogen (NH 4 + -N) in real anaerobically digested food wastewater (ADFW). The anodic Fenton process caused the rapid mineralization of phenol as a model substrate through the production of hydroxyl radical as the main oxidant. The electrochemical oxidation of NH 4 + by a dimensionally stable anode (DSA) resulted in temporal concentration profiles of combined and free chlorine species that were analogous to those during the conventional breakpoint chlorination of NH 4 + . Together with the minimal production of nitrate, this confirmed that the conversion of NH 4 + to nitrogen gas was electrochemically achievable. The monitoring of treatment performance with varying key parameters (e.g., current density, H 2 O 2 feeding rate, pH, NaCl loading, and DSA type) led to the optimization of two component systems. The comparative evaluation of two sequentially combined systems (i.e., the E-Fenton-EC system versus the EC-E-Fenton system) using the mixture of phenol and NH 4 + under the predetermined optimal conditions suggested the superiority of the E-Fenton-EC system in terms of treatment efficiency and energy consumption. Finally, the sequential E-Fenton-EC process effectively mineralized organic carbon and decomposed NH 4 + -N in the real ADFW without external supply of NaCl.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morita, M.

Chlorinated benzenes are composed of twelve chemical species: one mono-, three di-, three tri-, three tetra-, one penta-, and one hexachlorobenzene. Most of these are not only important intermediates for various kinds of chemicals but are also extensively employed for various applications singly or in combination. For example, 1,4-dichlorobenzene is used chiefly against termites in soil; trichlorobenzenes are used as solvents for pesticides and also as heat transfer agents with PCBs; the mixture of trichlorobenzene and tetrachlorobenzene is applied in controlling shellfish predators; and hexachlorobenzene is applied to wheat as a fungicide in some countries and as an additive tomore » rubber products. The annual production (1973) of monochlorobenzene, 1,2-dichlorobenzene, and 1,4-dichlorobenzene in Japan was about 23,000, 9000, and 20,000, tons, respectively. Production volumes of other chlorinated benzenes are not well known but are assumed to be smaller than those of the above three compounds. The total annual production of chlorinated benzenes far surpasses the peak production of PCBs (7000 tons/year) which are known as a ubiquitous pollutant in this country. Since chlorinated benzenes have a chemical structure and properties similar to those of PCBs and PCTs, it seemed necessary to direct our attention to environmental contamination by these materials. The present paper describes only the occurrence and the fate of these materials. Toxicity and biological impact are not referred to here.« less

Haloactamides versus halomethanes formation and toxicity in chloraminated drinking water.

PubMed

Yang, Fan; Zhang, Jing; Chu, Wenhai; Yin, Daqiang; Templeton, Michael R

2014-06-15

In this study we quantified the concentrations of nine haloacetamides (HAcAms) and nine halomethanes (HMs) in the final waters of five drinking water treatment plants (DWTPs) that use either chlorination or chloramination for disinfection and evaluated the toxicity of dichloroacetamide (DCAcAm) and dichloromethane (DCM) in normal rat kidney (NRK) cells using four in vitro toxicity assays. All the DWTPs final waters contained primarily di-HAcAms, followed by tri- and mono-HAcAms, and DCAcAm was the most abundant species of the 9 HAcAms, regardless of chlorination or chloramination being applied. In the final waters of DWTPs using chlorination, tri-HMs (trihalomethanes, THMs) accounted for the majority of HMs, whereas chloramination resulted in more di-HMs (especially DCM) than THMs. All four in vitro toxicity assays indicated that the NRK cell chronic cytotoxicity and acute genotoxicity of DCAcAm were substantially higher than that of DCM. In view of observed occurrence concentrations and quantified toxicity levels, the findings of this study suggest that DCAcAm represents a higher toxicity risk than DCM in chloraminated drinking waters. Copyright © 2014 Elsevier B.V. All rights reserved.

Report on concentrations, lifetimes, and trends of CFCs, halons, and related species

NASA Technical Reports Server (NTRS)

Kaye, J. A. (Editor); Penkett, S. A. (Editor); Ormond, F. M. (Editor); Fraser, P.; Fisher, D.; Bloomfield, P.; Sander, S. P.; Ko, M. K. W.

1994-01-01

The atmospheric lifetimes of molecules containing chlorine and bromine are the dominant parameters influencing their ability to promote enhanced ozone destruction in the stratosphere. The purpose of this report is to assess the present state of knowledge of the lifetimes of halocarbons using two complementary approaches. First, a time series of measurements of gas concentrations is used together with information on their emissions histories and a computational model of atmospheric circulation and chemistry to infer lifetimes through a mass balance approach. Second, an atmospheric chemical-dynamical model is used with detailed information on the chemistry and spectroscopy of the molecules of interest to calculate lifetimes. The lifetimes determined by these two methods are then compared. Attention is focused most closely on fully halogenated chlorine- and bromine-containing molecules, primarily the chlorofluorocarbons, and the halons, because of their ability to deliver chlorine and bromine to the stratosphere. Some attention will be given to those molecules containing hydrogen, which are subject to removal in the troposphere primarily by reaction with OH and by other processes.

Halocarbons in the stratosphere

NASA Astrophysics Data System (ADS)

Fabian, P.; Borchers, R.

1981-12-01

The possible impact of chlorine compounds on the Earth's ozone layer has caused concern. Profiles of the anthropogenic halocarbons F-11 (CFC13) and F-12 (CF2Cl2) have already been measured in the stratosphere1-4. Measurements of the vertical distribution of methyl chloride (CH3Cl), the most important natural chlorine-bearing species confirm that chlorine of anthropogenic origin now predominates the stratosphere5,6. More halogen radicals are added through decomposition of various other halocarbons, most of them released by man. We report here the first measurements of vertical profiles of F-13 (CF3Cl), F-14 (CF4), F-113 (C2F3Cl3), F-114 (C2F4Cl2), F-115 (C2F5Cl), F-116 (C2F6), and F-13 B(CF3Br) resulting from gas chromatography-mass spectrometer (GC-MS) analysis of air samples collected cryogenically between 10 and 33 km, at 44° N. Some data for F-22 (CHF2C1), methyl bromide (CH3Br) and methyl chloroform (CH3CC13) also presented are subject to confirmation.

8-Chloroadenine: a novel product formed from hypochlorous acid-induced damage to calf thymus DNA.

PubMed

Matthew Whiteman Andrew Jenner Barry Halliwell

1999-01-01

Hypochlorous acid (HOCl) is formed by the action of the enzyme myeloperoxidase on hydrogen peroxide and chloride ions. It has been shown to be highly bactericidal and cytotoxic by a variety of mechanisms, one of which, may be the modification of DNA. Previously we have demonstrated by GC-MS analysis that exposure of calf thymus DNA to HOCl causes extensive pyrimidine modification, including 5-chlorocytosine formation. Using GC-MS analysis, we now demonstrate the formation of an additional chlorinated base product, 8-Cl adenine. The addition of 50 μM HOCl was sufficient to produce a significant increase in this product. The reaction of HOCl with adenine in calf thymus DNA was shown to be rapid with the reaction complete after 1 min. pH-dependence studies suggest HOCl rather than its conjugate base (OCl-) to be responsible for 8-Cl adenine formation. Other commercially available chlorinated base products, 6-Cl guanine or 2-Cl adenine were not detected. Therefore, 8-Cl adenine might prove a useful biomarker for studying the role of reactive chlorine species (RCS) during inflammatory processes.

Ab initio calculations and kinetic modeling of thermal conversion of methyl chloride: implications for gasification of biomass.

PubMed

Singla, Mallika; Rasmussen, Morten Lund; Hashemi, Hamid; Wu, Hao; Glarborg, Peter; Pelucchi, Matteo; Faravelli, Tiziano; Marshall, Paul

2018-04-25

Limitations in current hot gas cleaning methods for chlorine species from biomass gasification may be a challenge for end use such as gas turbines, engines, and fuel cells, all requiring very low levels of chlorine. During devolatilization of biomass, chlorine is released partly as methyl chloride. In the present work, the thermal conversion of CH3Cl under gasification conditions was investigated. A detailed chemical kinetic model for pyrolysis and oxidation of methyl chloride was developed and validated against selected experimental data from the literature. Key reactions of CH2Cl with O2 and C2H4 for which data are scarce were studied by ab initio methods. The model was used to analyze the fate of methyl chloride in gasification processes. The results indicate that CH3Cl emissions will be negligible for most gasification technologies, but could be a concern for fluidized bed gasifiers, in particular in low-temperature gasification. The present work illustrates how ab initio theory and chemical kinetic modeling can help to resolve emission issues for thermal processes in industrial scale.

Removal of the cyanotoxin anatoxin-a by drinking water treatment processes: a review.

PubMed

Vlad, Silvia; Anderson, William B; Peldszus, Sigrid; Huck, Peter M

2014-12-01

Anatoxin-a (ANTX-a) is a potent alkaloid neurotoxin, produced by several species of cyanobacteria and detected throughout the world. The presence of cyanotoxins, including ANTX-a, in drinking water sources is a potential risk to public health. This article presents a thorough examination of the cumulative body of research on the use of drinking water treatment technologies for extracellular ANTX-a removal, focusing on providing an analysis of the specific operating parameters required for effective treatment and on compiling a series of best-practice recommendations for owners and operators of systems impacted by this cyanotoxin. Of the oxidants used in drinking water treatment, chlorine-based processes (chlorine, chloramines and chlorine dioxide) have been shown to be ineffective for ANTX-a treatment, while ozone, advanced oxidation processes and permanganate can be successful. High-pressure membrane filtration (nanofiltration and reverse osmosis) is likely effective, while adsorption and biofiltration may be effective but further investigation into the implementation of these processes is necessary. Given the lack of full-scale verification, a multiple-barrier approach is recommended, employing a combination of chemical and non-chemical processes.

Ozonation and H2O2/UV treatment of clofibric acid in water: a kinetic investigation.

PubMed

Andreozzi, Roberto; Caprio, Vincenzo; Marotta, Raffaele; Radovnikovic, Anita

2003-10-31

The presence of pharmaceuticals or their active metabolites in surface and ground waters has been recently reported as mainly due to an incomplete removal of these pollutants in sewage treatment plants (STP). Advanced oxidation processes may represent a suitable tool to reduce environmental release of these species by enhancing the global efficiency of reduction of pharmaceuticals in the municipal sewage plant effluents. The present work aims at assessing the kinetics of abatement from aqueous solutions of clofibric acid (a metabolite of the blood lipid regulator clofibrate) which has been found in surface, ground and drinking waters. Ozonation and hydrogen peroxide photolysis are capable of fast removal of this species in aqueous solution, with an almost complete conversion of the organic chlorine content into chloride ions for the investigated reaction conditions. A validation of assessed kinetics at clofibric acid concentrations as low as those found in STP effluents is presented for both systems.

New Metabolites and Bioactive Chlorinated Benzophenone Derivatives Produced by a Marine-Derived Fungus Pestalotiopsis heterocornis

PubMed Central

Lei, Hui; Lin, Xiuping; Han, Li; Ma, Jian; Ma, Qingjuan; Zhong, Jialiang; Liu, Yonghong; Sun, Tiemin; Wang, Jinhui; Huang, Xueshi

2017-01-01

Four new compounds, including two isocoumarins, pestaloisocoumarins A and B (1, 2), one sesquiterpenoid degradation, isopolisin B (4), and one furan derivative, pestalotiol A (5), together with one known isocoumarin, gamahorin (3), and three chlorinated benzophenone derivatives, pestalachloride B (6), pestalachloride E (7) and a mixture of pestalalactone atropisomers (8a/8b), were isolated from a culture of the fungus Pestalotiopsis heterocornis associated with sponge Phakellia fusca. These new chemical structures were established using NMR and MS spectroscopic data, as well as single-crystal X-ray crystallographic analysis and CD Cotton effects. All of the isolated compounds were evaluated for their antimicrobial and cytotoxic activities. Isocoumarins 1–3, showed antibacterial activities against Gram-positive bacteria Staphylococcus aureus and Bacillus subtilis with MIC values ranging from 25 to 100 μg/mL and weak antifungal activities. Chlorinated benzophenone derivatives 6–8 exhibited antibacterial activities against S. aureus and B. subtilis with MIC values ranging from 3.0 to 50 μg/mL and cytotoxicities against four human cancer cell lines with IC50 values of 6.8–87.8 μM. PMID:28335391

The Emission and Chemistry of Reactive Nitrogen Species in the Plume of an Athena II Rocket

NASA Astrophysics Data System (ADS)

Popp, P. J.; Gao, R. S.; Neuman, J. A.; Northway, M. J.; Holecek, J. C.; Fahey, D. W.; Wiedinmyer, C.; Brock, C. A.; Ridley, B. A.; Walega, J. G.; Grahek, F. E.; Wilson, J. C.; Reeves, J. M.; Toohey, D. W.; Avallone, L. M.; Thornton, B. F.; Gates, A. M.; Ross, M. N.; Zittel, P. F.

2001-12-01

In situ measurements of total reactive nitrogen (NOy), nitric acid (HNO3), and particles were conducted in the plume of an Athena II rocket launched from Vandenberg AFB on September 24, 1999. These measurements were obtained onboard the NASA WB-57F high-altitude research aircraft as part of the Atmospheric Chemistry of Combustion Emissions near the Tropopause (ACCENT) mission. The calculated NOy emission index, determined from measurements made during the first 3 of 6 plume intercepts, was 2.1\\pm1.0 g NO2/kg propellant, consistent with far-field rocket plume model calculations. Although nitric oxide (NO) is thought to be the primary NOy species formed in the Athena solid rocket motor (SRM) and by hot afterburning in the plume, measurements in the plume as soon as 4 minutes after emission indicate that HNO3 is the dominant NOy species. In the chlorine-rich plume, NO is converted to chlorine nitrate (ClONO2) which reacts with water on emitted alumina particles to form HNO3. The data suggest HNO3 remains absorbed on alumina particles. With the potential increase in launch vehicle traffic in the coming decades, accurate modeling of the global impact of current and future rocket fleets will require the use of emission indices validated by observations.

Methods for microbiological quality assessment in drinking water: a comparative study.

PubMed

Helmi, K; Barthod, F; Méheut, G; Henry, A; Poty, F; Laurent, F; Charni-Ben-Tabassi, N

2015-03-01

The present study aimed to compare several methods for quantifying and discriminating between the different physiological states of a bacterial population present in drinking water. Flow cytometry (FCM), solid-phase cytometry (SPC), epifluorescence microscopy (MSP) and culture method performances were assessed by comparing the results obtained for different water samples. These samples, including chlorinated and non-chlorinated water, were collected in a drinking water treatment plant. Total bacteria were quantified by using SYBR Green II (for FCM) and 4',6'-diamino-2-phenylindole (DAPI) (for MSP), viable and non-viable bacteria were distinguished by using SYBR Green II and propidium iodide dual staining (for FCM), and active cells were distinguished by using CTC (for MSP) and Chemchrome V6 (for FCM and SPC). In our conditions, counts using microscopy and FCM were significantly correlated regarding total bacteria and active cells. Conversely, counts were not significantly similar using solid-phase and FCM for active bacteria. Moreover, the R2A medium showed that bacterial culturability could be recovered after chlorination. This study highlights that FCM appears to be a useful and powerful technique for drinking water production monitoring.

Analysis of the structure and the FT-IR and Raman spectra of 2-(4-nitrophenyl)-4H-3,1-benzoxazin-4-one. Comparisons with the chlorinated and methylated derivatives

NASA Astrophysics Data System (ADS)

Castillo, María V.; Rudyk, Roxana A.; Davies, Lilian; Brandán, Silvia Antonia

2017-07-01

In this work, the structural, topological and vibrational properties of the monomer and three dimers of the 2-(4-nitrophenyl)-4H-3,1-benzoxazin-4-one (NPB) derivative were studied combining the experimental FTIR and FT-Raman spectra in the solid phase with DFT calculations. Here, Natural Bond Orbital (NBO), Atoms in Molecules (AIM) and HOMO and LUMO calculations were performed by using the hybrid B3LYP/6-31G*and B3LYP/6-311++G** methods in order to compute those properties and to predict their reactivities. The comparisons with the properties reported for the chlorinated (Cl-PB) and methylated (CH3-PB) derivatives at the same levels of theory can be clearly justified by the activating (CH3) and deactivating (NO2 and Cl) characteristics of the different groups linked to oxaxin rings. The NBO and AIM studies evidence the following stability orders: Cl-PB > NO2-PB > CH3-PB in very good concordance with the f(νC23-X26) force constants values. The frontier orbitals analyses reveal that the Cl-PB and NO2-PB derivatives have good stabilities and high chemical hardness while CH3-PB has a higher chemical reactivity. On the other hand, the complete vibrational assignments for monomer and dimers species of NPB were presented. The presence of the IR bands at 1574 and 1037 cm-1 and, of the Raman bands at 1571 and 1038 cm-1 support clearly the presence of the different dimeric species proposed for NPB.

Inactivation of marine heterotrophic bacteria in ballast water by an Electrochemical Advanced Oxidation Process.

PubMed

Moreno-Andrés, Javier; Ambauen, Noëmi; Vadstein, Olav; Hallé, Cynthia; Acevedo-Merino, Asunción; Nebot, Enrique; Meyn, Thomas

2018-05-03

Seawater treatment is increasingly required due to industrial activities that use substantial volumes of seawater in their processes. The shipping industry and the associated management of a ship's ballast water are currently considered a global challenge for the seas. Related to that, the suitability of an Electrochemical Advanced Oxidation Process (EAOP) with Boron Doped Diamond (BDD) electrodes has been assessed on a laboratory scale for the disinfection of seawater. This technology can produce both reactive oxygen species and chlorine species (especially in seawater) that are responsible for inactivation. The EAOP was applied in a continuous-flow regime with real seawater. Natural marine heterotrophic bacteria (MHB) were used as an indicator of disinfection efficiency. A biphasic inactivation kinetic model was fitted on experimental points, achieving 4-Log reductions at 0.019 Ah L -1 . By assessing regrowth after treatment, results suggest that higher bacterial damages result from the EAOP when it is compared to chlorination. Furthermore, several issues lacking fundamental understanding were investigated such as recolonization capacity or bacterial community dynamics. It was concluded that, despite disinfection processes being effective, there is not only a possibility for regrowth after treatment but also a change on bacterial population diversity produced by the treatment. Finally, energy consumption was estimated and indicated that 0.264 kWh·m -3 are needed for 4.8-Log reductions of MHB; otherwise, with 0.035 kWh·m -3 , less disinfection efficiency can be obtained (2.2-Log red). However, with a residual oxidant in the solution, total inactivation can be achieved in three days. Copyright © 2018 Elsevier Ltd. All rights reserved.

Chlorophyll-Derivative Modulation of Rhodopsin Signaling Properties through Evolutionarily Conserved Interaction Pathways

PubMed Central

Woods, Kristina N.; Pfeffer, Jürgen; Klein-Seetharaman, Judith

2017-01-01

Retinal is the light-absorbing chromophore that is responsible for the activation of visual pigments and light-driven ion pumps. Evolutionary changes in the intermolecular interactions of the retinal with specific amino acids allow for adaptation of the spectral characteristics, referred to as spectral tuning. However, it has been proposed that a specific species of dragon fish has bypassed the adaptive evolutionary process of spectral tuning and replaced it with a single evolutionary event: photosensitization of rhodopsin by chlorophyll derivatives. Here, by using a combination of experimental measurements and computational modeling to probe retinal-receptor interactions in rhodopsin, we show how the binding of the chlorophyll derivative, chlorin-e6 (Ce6) in the intracellular domain (ICD) of the receptor allosterically excites G-protein coupled receptor class A (GPCR-A) conserved long-range correlated fluctuations that connect distant parts of the receptor. These long-range correlated motions are associated with regulating the dynamics and intermolecular interactions of specific amino acids in the retinal ligand-binding pocket that have been associated with shifts in the absorbance peak maximum (λmax) and hence, spectral sensitivity of the visual system. Moreover, the binding of Ce6 affects the overall global properties of the receptor. Specifically, we find that Ce6-induced dynamics alter the thermal stability of rhodopsin by adjusting hydrogen-bonding interactions near the receptor active-site that consequently also influences the intrinsic conformational equilibrium of the receptor. Due to the conservation of the ICD residues amongst different receptors in this class and the fact that all GPCR-A receptors share a common mechanism of activation, it is possible that the allosteric associations excited in rhodopsin with Ce6 binding are a common feature in all class A GPCRs. PMID:29312953

Direct electrochemical oxidation of ammonia on graphite as a treatment option for stored source-separated urine.

PubMed

Zöllig, Hanspeter; Fritzsche, Cristina; Morgenroth, Eberhard; Udert, Kai M

2015-02-01

Electrolysis can be a viable technology for ammonia removal from source-separated urine. Compared to biological nitrogen removal, electrolysis is more robust and is highly amenable to automation, which makes it especially attractive for on-site reactors. In electrolytic wastewater treatment, ammonia is usually removed by indirect oxidation through active chlorine which is produced in-situ at elevated anode potentials. However, the evolution of chlorine can lead to the formation of chlorate, perchlorate, chlorinated organic by-products and chloramines that are toxic. This study focuses on using direct ammonia oxidation on graphite at low anode potentials in order to overcome the formation of toxic by-products. With the aid of cyclic voltammetry, we demonstrated that graphite is active for direct ammonia oxidation without concomitant chlorine formation if the anode potential is between 1.1 and 1.6 V vs. SHE (standard hydrogen electrode). A comparison of potentiostatic bulk electrolysis experiments in synthetic stored urine with and without chloride confirmed that ammonia was removed exclusively by continuous direct oxidation. Direct oxidation required high pH values (pH > 9) because free ammonia was the actual reactant. In real stored urine (pH = 9.0), an ammonia removal rate of 2.9 ± 0.3 gN·m(-2)·d(-1) was achieved and the specific energy demand was 42 Wh·gN(-1) at an anode potential of 1.31 V vs. SHE. The measurements of chlorate and perchlorate as well as selected chlorinated organic by-products confirmed that no chlorinated by-products were formed in real urine. Electrode corrosion through graphite exfoliation was prevented and the surface was not poisoned by intermediate oxidation products. We conclude that direct ammonia oxidation on graphite electrodes is a treatment option for source-separated urine with three major advantages: The formation of chlorinated by-products is prevented, less energy is consumed than in indirect ammonia oxidation and readily available and cheap graphite can be used as the electrode material. Copyright © 2014 Elsevier Ltd. All rights reserved.

Evidence for Perchlorates and the Origin of Chlorinated Hydrocarbons Detected by SAM at the Rocknest Aeolian Deposit in Gale Crater

NASA Technical Reports Server (NTRS)

Glavin, Daniel P.; Freissinet, Caroline; Miller, Kristen E.; Eigenbrode, Jennifer L.; Brunner, Anna E.; Buch, Arnaud; Sutter, Brad; Archer, P. Douglas, Jr.; Atreya, Sushil K.; Brinckerhoff, William B.;

Detection of griseofulvin in a marine strain of Penicillium waksmanii by ion trap mass spectrometry.

PubMed

Petit, K E; Mondeguer, F; Roquebert, M F; Biard, J F; Pouchus, Y F

2004-07-01

A marine strain of Penicillium waksmanii Zaleski was isolated from a sample of seawater from shellfish-farming area in the Loire estuary (France). The in vitro marine culture showed an important antifungal activity. Bioassay-guided fractionation was used to purify the crude extract. Dereplication by electrospray-ion trap/mass spectrometry (ESI-IT/MS) afforded the identification of the antifungal compound, after a semi-purification consisting of two stages. A comparison of the ionic composition between the active and the non-active fractions allowed the detection of a monocharged ion at m/z 353 containing a chlorine atom, which could be attributed to the antifungal griseofulvin [C17H17ClO6+H]+. Multi-stage fragmentation (MSn) confirmed the identity of the m/z 353 ion of the antifungal fraction as griseofulvin. It is the first description of griseofulvin production by a strain of P. waksmanii and the first chemical study of a strain of this species isolated from marine temperate cold water. Copyright 2004 Elsevier B.V.

Regenerable cobalt oxide loaded magnetosphere catalyst from fly ash for mercury removal in coal combustion flue gas.

PubMed

Yang, Jianping; Zhao, Yongchun; Zhang, Junying; Zheng, Chuguang

2014-12-16

To remove Hg(0) in coal combustion flue gas and eliminate secondary mercury pollution of the spent catalyst, a new regenerable magnetic catalyst based on cobalt oxide loaded magnetospheres from fly ash (Co-MF) was developed. The catalyst, with an optimal loading of 5.8% cobalt species, attained approximately 95% Hg(0) removal efficiency at 150 °C under simulated flue gas atmosphere. O2 could enhance the Hg(0) removal activity of magnetospheres catalyst via the Mars-Maessen mechanism. SO2 displayed an inhibitive effect on Hg(0) removal capacity. NO with lower concentration could promote the Hg(0) removal efficiency. However, when increasing the NO concentration to 300 ppm, a slightly inhibitive effect of NO was observed. In the presence of 10 ppm of HCl, greater than 95.5% Hg(0) removal efficiency was attained, which was attributed to the formation of active chlorine species on the surface. H2O presented a seriously inhibitive effect on Hg(0) removal efficiency. Repeated oxidation-regeneration cycles demonstrated that the spent Co-MF catalyst could be regenerated effectively via thermally treated at 400 °C for 2 h.

Poisoning of wild birds from exposure to anticholinesterase compounds and lead: diagnostic methods and selected cases

USGS Publications Warehouse

Franson, J. Christian; Smith, Milton R.

1999-01-01

Organophosphorus and carbamate compounds have largely replaced chlorinated hydrocarbons for pesticidal use in the United States, and many cases of poisoning resulting from exposure to these anticholinesterase agents have occurred in free-living birds. Although lead shot has been prohibited for waterfowl hunting throughout the United States since 1991, lead poisoning from the ingestion of spent lead shot is still occasionally seen in wild birds, and lead poisoning from the ingestion of fishing sinkers is an emerging issue of concern. A thorough history, a complete necropsy evaluation, and appropriate laboratory analysis of tissues are required to diagnose toxicoses in wild birds, including those caused by anticholinesterase compounds and lead. The interpretation of brain cholinesterase (ChE) activity results depends on the methods of analysis and comparison with expected normal enzyme activities in brain tissue from the same species. Although lead residues in tissues vary among species, many lead poisoned birds have tissue residues that are much higher than the lower threshold commonly accepted for a diagnosis of lead poisoning. We review histories, necropsy findings, and analytical methodologies and results for selected anticholinesterase and lead poisoning cases diagnosed in wild raptors, waterfowl, and loons.

The effect of high-level chlorine carcass drench on the recovery of Salmonella and enumeration of bacteria from broiler carcasses.

PubMed

Bartenfeld, L N; Fletcher, D L; Northcutt, J K; Bourassa, D V; Cox, N A; Buhr, R J

2014-11-01

A study was conducted to determine the bacteriological effect of exposing processed broiler carcasses to a high (10-fold increase) concentration chlorinated drench. During each of 6 replicate trials, eviscerated prechill carcasses were obtained from a commercial processing plant and chlorine-treated carcasses were subjected to a 1-min drench in 500 mL of a 500 mg/kg chlorine solution (sodium hypochlorite). Water-drenched carcasses were treated the same way except water was used in place of chlorinated water drench. Control carcasses were not drenched. All carcasses were then subjected to a whole carcass rinse (WCR) in 450 mL of buffered peptone water, from which 50 mL of the rinsate was removed for enumeration of total aerobic bacteria (APC), Escherichia coli, and total coliforms (TC). The entire carcass was then incubated 24 h at 37°C (whole carcass enrichment, WCE) for recovery of Salmonella. Levels of bacteria recovered from WCR were lower by 0.6 log10 cfu/mL for APC, 0.8 for E. coli, and 0.9 for TC when carcasses were drenched with water compared with undrenched control levels. Similarly, the levels of bacteria recovered from WCR were further lower by 1.0 log10 cfu/mL for APC, 0.5 for E. coli, and 0.5 for TC, when carcasses were drenched with 500 mg/kg of chlorine compared with water. However, there was no significant difference (P > 0.05) in prevalence of Salmonella among the treatments (29% positive for control, 26% positive for water, 38% positive for chlorinated). These results indicate that drenching eviscerated carcasses with water or chlorinated water at 500 mg/kg significantly, but minimally, reduces the numbers of APC, E. coli, and TC bacteria recovered compared with undrenched carcasses. However, neither drenching carcasses with water or high chlorine had an effect on the prevalence of Salmonella that remain with the carcass as determined by WCE. The results of this study confirms the importance of maintaining and replenishing free chlorine for optimal antimicrobial activity, because chlorine at 500 mg/kg was rapidly used within 1 min of exposure to the carcass to <10 mg/kg. ©2014 Poultry Science Association Inc.

THE PUBLIC HEALTH IMPORTANCE OF BIOFILM SLIME IN DRINKING WATER PIPES: CREATING HIDEOUTS FOR THE PATHOGENIC UNDERWORLD OF MICROBIOLOGY

EPA Science Inventory

Biofilms consist of many species of bacteria, protozoa, and other microbes living together on almost any type of moist surface. Within drinking water distribution systems, biofilms grow readily on the inner walls of pipes, even in the presence of chlorine disinfectants. Some mi...

Sea ice-associated diet change increases the levels of chlorinated and brominated contaminants in polar bears.

PubMed

Mckinney, Melissa A; Peacock, Elizabeth; Letcher, Robert J

2009-06-15

Two global environmental issues, climate change and contamination by persistent organic pollutants, represent major concerns for arctic ecosystems. Yet, it is unclear how these two stressors interact in the Arctic. For instance, the influence of climate-associated changes in food web structure on exposure to pollutants within arctic ecosystems is presently unknown. Here, we report on recent changes in feeding ecology (1991-2007) in polar bears (Ursus maritimus) from the western Hudson Bay subpopulation that have resulted in increases in the tissue concentrations of several chlorinated and brominated contaminants. Differences in timing of the annual sea ice breakup explained a significant proportion of the diet variation among years. As expected from climate change predictions, this diet change was consistent with an increase in the consumed proportions of open water-associated seal species compared to ice-associated seal species in years of earlier sea ice breakup. Our results demonstrate that climate change is a modulating influence on contaminants in this polar bear subpopulation and may pose an additional and previously unidentified threat to northern ecosystems through altered exposures to contaminants.

Determination of relative assay response factors for toxic chlorinated and brominated dioxins/furans using an enzyme immunoassay (EIA) and a chemically-activated luciferase gene expression cell bioassay (CALUX).

PubMed

Samara, Fatin; Gullett, Brian K; Harrison, Robert O; Chu, Andrew; Clark, George C

2009-04-01

Determination of toxic activity requires knowledge of both the concentration and toxicity to evaluate the risk for adverse human health and environmental effects. A chemically-activated luciferase gene expression cell bioassay system (CALUX) and an antibody-based method enzyme immunoassay (EIA) were used to detect the dioxin-like response of several polybrominated, polychlorinated, and polybrominated/chlorinated dibenzo-p-dioxins/furans (PBDDs/Fs, PCDDs/Fs, and PBCDDs/Fs, respectively). It has been suggested that the biological activity of the brominated and mixed bromo/chloro compounds is similar to their chlorinated analogues (measured by binding to the Ah receptor). PBDD/F, PCDD/F, and PBCDD/F laboratory standards exhibited biological activity ranging over three orders of magnitude. The highest relative potency (REP) values from CALUX analysis, when compared to 2,3,7,8-TCDD, were 2,3,7,8-TBDD at 0.99 (+/-0.07), 1,2,3,7,8-PeCDD at 0.69, and 2-Br-3,7,8-TriCDD at 0.72 (+/-0.02). Cross-reactivities were calculated using EIA for several PBDDs/Fs and PBCDDs. The highest percent cross-reactivity was found for 2,3,7,8-TBDD at 138 (+/-34%), and 2,3,7-TriBDD at 84 (+/-36%).

Chlorination and chloramination of bisphenol A, bisphenol F, and bisphenol A diglycidyl ether in drinking water.

PubMed

Lane, Rachael F; Adams, Craig D; Randtke, Stephen J; Carter, Ray E

2015-08-01

Bisphenol A (BPA), bisphenol F (BPF), and bisphenol A diglycidyl ether (BADGE) are common components of epoxy coatings used in food packaging and in drinking water distribution systems. Thus, leachates from the epoxy may be exposed to the disinfectants free chlorine (Cl2/HOCl/OCl(-)) and monochloramine (MCA, NH2Cl). Bisphenols are known endocrine disrupting chemicals (EDC) with estrogenic activity. Chlorination by-products have the potential to have reduced or enhanced estrogenic qualities, and are, therefore, of interest. In this work, chlorination reactions for bisphenols and BADGE were explored (via LC/MS/MS) and kinetic modeling (using a pseudo-first order approach) was conducted to predict the fate of these compounds in drinking water. The half-lives of BPA and BPF with 1 mg/L of free chlorine ranged from 3 to 35 min over the pH range from 6 to 11 and the temperature range of 10-25 °C. Half-lives for reactions of BPA and BPF with a nominal MCA concentration of 3.5 mg/L as Cl2 were from 1 to 10 days and were greater at higher pH and lower temperature. Formation of chlorinated bisphenol A by-products was observed during the kinetic studies. BADGE was found unreactive with either oxidant. Copyright © 2015. Published by Elsevier Ltd.

Mobilization of lead and other trace elements following shock chlorination of wells

USGS Publications Warehouse

Seiler, R.L.

2006-01-01

Many owners of domestic wells shock chlorinate their wells to treat for bacterial contamination or control bad odors from sulfides. Analysis of well water with four wells from Fallon, Nevada, showed that following recommended procedures for shock chlorinating wells can cause large, short-lasting increases in trace-element concentrations in ground water, particularly for Cu, Fe, Pb, and Zn. Lead concentrations increased up to 745 fold between samples collected just before the well was shock chlorinated and the first sample collected 22-24??h later; Zn concentrations increased up to 252 fold, Fe concentrations increased up to 114 fold, and Cu concentrations increased up to 29 fold. Lead concentrations returned to near background levels following pumping of about one casing volume, however, in one well an estimated 120??mg of excess Pb were pumped before concentrations returned to prechlorination levels. Total Pb concentrations were much greater than filtered (0.45????m) concentrations, indicating the excess Pb is principally particulate. Recommended procedures for purging treated wells following shock chlorination may be ineffective because a strong NaOCl solution can remain in the casing above the pump even following extended pumping. Only small changes in gross alpha and beta radioactivity occurred following shock chlorination. USEPA has not promulgated drinking-water standards for 210Pb, however, measured 210Pb activities in the study area typically were less than the Canadian Maximum Acceptable Concentration of 100??mBq/L. By consuming well water shortly after shock chlorination the public may inadvertently be exposed to levels of Pb, and possibly 210Pb, that exceed drinking-water standards.

Sources of organochlorine contaminants and mercury in seabirds from the Aleutian archipelago of Alaska: Inferences from spatial and trophic variation

USGS Publications Warehouse

Ricca, Mark A.; Miles, A. Keith; Anthony, Robert G.

2008-01-01

Persistent organochlorine compounds and mercury (Hg) have been detected in numerous coastal organisms of the Aleutian archipelago of Alaska, yet sources of these contaminants are unclear. We collected glaucous-winged gulls, northern fulmars, and tufted puffins along a natural longitudinal gradient across the western and central Aleutian Islands (Buldir, Kiska, Amchitka, Adak), and an additional 8 seabird species representing different foraging and migratory guilds from Buldir Island to evaluate: 1) point source input from former military installations, 2) westward increases in contaminant concentrations suggestive of distant source input, and 3) effects of trophic status (δ15N) and carbon source (δ13C) on contaminant accumulation. Concentrations of Σ polychlorinated biphenyls (PCBs) and most chlorinated pesticides in glaucous-winged gulls consistently exhibited a ‘U’-shaped pattern of high levels at Buldir and the east side of Adak and low levels at Kiska and Amchitka. In contrast, concentrations of Σ PCBs and chlorinated pesticides in northern fulmars and tufted puffins did not differ among islands. Hg concentrations increased westward in glaucous-winged gulls and were highest in northern fulmars from Buldir. Among species collected only at Buldir, Hg was notably elevated in pelagic cormorants, and relatively high Σ PCBs were detected in black-legged kittiwakes. Concentrations of Σ PCBs, dichlorodiphenyldichloroethylene (p,p′ DDE), and Hg were positively correlated with δ15N across all seabird species, indicating biomagnification across trophic levels. The east side of Adak Island (a former military installation) was a likely point source of Σ PCBs and p,p′ DDE, particularly in glaucous-winged gulls. In contrast, elevated levels of these contaminants and Hg, along with PCB congener and chlorinated pesticide compositional patterns detected at Buldir Island indicated exposure from distant sources influenced by a combination of atmospheric–oceanic processes and the migratory movements of seabirds.

Biodistribution of charged 17.1A photoimmunoconjugates in a murine model of hepatic metastasis of colorectal cancer

PubMed Central

Hamblin, M R; Governatore, M Del; Rizvi, I; Hasan, T

2000-01-01

Optimizing photodynamic therapy involves attempting to increase both the absolute tumour content of photosensitizer and the selectivity between tumour and surrounding normal tissue. One reason why photodynamic therapy has not been considered suitable for treatment of metastatic tumours in the liver, is the poor selectivity of conventional photosensitizers for tumour compared to normal liver. This report details an alternative approach to increasing this selectivity by the use of antibody-targeted photosensitizers (or photoimmunoconjugates) to target intrahepatic tumours caused by human colorectal cancer cells in the nude mouse, and explores the role of molecular charge on the tumour-targeting efficiency of macromolecules. The murine monoclonal antibody 17.1A (which recognizes an antigen expressed on HT 29 cells) was used to prepare site-specific photoimmunoconjugates with the photosensitizer chlorine6. The conjugates had either a predominant cationic or anionic charge and were injected i.v. into tumour-bearing mice. Biodistribution 3 or 24 h later was measured by extraction of tissue samples and quantitation of chlorine6 content by fluorescence spectroscopy. The photoimmunoconjugates were compared to the polylysine conjugates in an attempt to define the effect of molecular charge as well as antibody targeting. The anionic 17.1A conjugate delivered more than twice as much photosensitizer to the tumour at 3 h than other species (5 times more than the cationic 17.1A conjugate) and had a tumour:normal liver ratio of 2.5. Tumour-to-liver ratios were greater than one for most compounds at 3 h but declined at 24 h. Tumour-to-skin ratios were high (> 38) for all conjugates but not for free chlorine6. Cationic species had a high uptake in the lungs compared to anionic species. The photoimmunoconjugates show an advantage over literature reports of other photosensitizers, which can result in tumour:normal liver ratios of less than 1. © 2000 Cancer Research Campaign http://www.bjcancer.com PMID:11076666

Detection of bromine monoxide in a volcanic plume.

PubMed

Bobrowski, N; Hönninger, G; Galle, B; Platt, U

2003-05-15

The emission of volcanic gases usually precedes eruptive activity, providing both a warning signal and an indication of the nature of the lava soon to be erupted. Additionally, volcanic emissions are a significant source of gases and particles to the atmosphere, influencing tropospheric and stratospheric trace-gas budgets. Despite some halogen species having been measured in volcanic plumes (mainly HCl and HF), little is known about bromine compounds and, in particular, gas-phase reactive bromine species. Such species are especially important in the stratosphere, as reactive bromine-despite being two orders of magnitude less abundant than chlorine-accounts for about one-third of halogen-catalysed ozone depletion. In the troposphere, bromine-catalysed complete ozone destruction has been observed to occur regularly during spring in the polar boundary layers as well as in the troposphere above the Dead Sea basin. Here we report observations of BrO and SO2 abundances in the plume of the Soufrière Hills volcano (Montserrat) in May 2002 by ground-based multi-axis differential optical absorption spectroscopy. Our estimate of BrO emission leads us to conclude that local ozone depletion and small ozone 'holes' may occur in the vicinity of active volcanoes, and that the amount of bromine emitted from volcanoes might be sufficiently large to play a role not only in the stratosphere, but also in tropospheric chemistry.

Upper-atmosphere Aerosols: Properties and Natural Cycles

NASA Technical Reports Server (NTRS)

Turco, Richard P.

1992-01-01

The middle atmosphere is rich in its variety of particulate matter, which ranges from meteorite debris, to sulfate aerosols, to polar stratospheric ice clouds. Volcanic eruptions strongly perturb the stratospheric sulfate (Junge) layer. High-altitude 'noctilucent' ice clouds condense at the summer mesopause. The properties of these particles, including their composition, sizes, and geographical distribution, are discussed, and their global effects, including chemical, radiative, and climatic roles, are reviewed. Polar stratospheric clouds (PSCs) are composed of water and nitric acid in the form of micron-sized ice crystals. These particles catalyze reactions of chlorine compounds that 'activate' otherwise inert chlorine reservoirs, leading to severe ozone depletions in the southern polar stratosphere during austral spring. PSCs also modify the composition of the polar stratosphere through complex physiocochemical processes, including dehydration and denitrification, and the conversion of reactive nitrogen oxides into nitric acid. If water vapor and nitric acid concentrations are enhanced by high-altitude aircraft activity, the frequency, geographical range, and duration of PSCs might increase accordingly, thus enhancing the destruction of the ozone layer (which would be naturally limited in geographical extent by the same factors that confine the ozone hole to high latitudes in winter). The stratospheric sulfate aerosol layer reflects solar radiation and increases the planetary albedo, thereby cooling the surface and possibly altering the climate. Major volcanic eruptions, which increase the sulfate aerosol burden by a factor of 100 or more, may cause significant global climate anomalies. Sulfate aerosols might also be capable of activating stratospheric chlorine reservoirs on a global scale (unlike PCSs, which represent a localized polar winter phenomenon), although existing evidence suggests relatively minor perturbations in chlorine chemistry. Nevertheless, if atmospheric concentrations of chlorine (associated with anthropogenic use of chlorofluorocarbons) continue to increase by a factor of two or more in future decades, aircraft emissions of sulfur dioxide and water vapor may take on greater significance.

Oxidation of artificial sweetener sucralose by advanced oxidation processes: a review.

PubMed

Sharma, Virender K; Oturan, Mehmet; Kim, Hyunook

2014-01-01

Sucralose, a chlorinated carbohydrate, has shown its increased use as an artificial sweetener and persistently exists in wastewater treatment plant effluents and aquatic environment. This paper aims to review possible degradation of sucralose and related carbohydrates by biological, electrochemical, chemical, and advanced oxidation processes. Biodegradation of sucralose in waterworks did not occur significantly. Electrochemical oxidation of carbohydrates may be applied to seek degradation of sucralose. The kinetics of the oxidation of sucralose and the related carbohydrates by different oxidative species is compared. Free chlorine, ozone, and ferrate did not show any potential to degrade sucralose in water. Advanced oxidation processes, generating highly strong oxidizing agent hydroxyl radicals ((•)OH), have demonstrated effectiveness in transforming sucralose in water. The mechanism of oxidation of sucralose by (•)OH is briefly discussed.

Optimum Disinfection Properties and Commercially Available Disinfectants

DTIC Science & Technology

1989-07-01

organic constituents that display a chlorine demand.) d. Upon addition to water, the agent should dissolve quickly and release its active ingredient(s...trione pH dependence alkaline pH favored Temperature dependence high at low residual Palatability Taste and odor claimed to be lartgly absent Color...CryptosgortdLjM at various temperature and pH levels. 2. A field procedwu for masueing disinfectant residual is ".eded for chlorin dioaide. 3. Stability

Sequential anaerobic/aerobic biodegradation of chloroethenes--aspects of field application.

PubMed

Tiehm, Andreas; Schmidt, Kathrin R

2011-06-01

Because of a range of different industrial activities, sites contaminated with chloroethenes are a world-wide problem. Chloroethenes can be biodegraded by reductive dechlorination under anaerobic conditions as well as by oxidation under aerobic conditions. The tendency of chloroethenes to undergo reductive dechlorination decreases with a decreasing number of chlorine substituents, whereas with less chlorine substituents chloroethenes more easily undergo oxidative degradation. There is currently a growing interest in aerobic metabolic degradation of chloroethenes, which demonstrates advantages compared to cometabolic degradation pathways. Sequential anaerobic/aerobic biodegradation can overcome the disadvantages of reductive dechlorination and leads to complete mineralization of the chlorinated pollutants. This approach shows promise for site remediation in natural settings and in engineered systems. Copyright © 2011 Elsevier Ltd. All rights reserved.

Groups at potentially high risk from chlorine dioxide treated water.

PubMed

Moore, G S; Calabrese, E J; Ho, S C

1980-09-01

Chlorite, a by-product of chlorine dioxide disinfection of water, is a strong oxidant compound that produces markedly exaggerated effects in vitro on red cells of G6PD deficient humans when compared to normal human cells. Levels of methemoglobin are significantly greater and GSH levels significantly lower in the G6PD deficient cells than in normal cells after chlorite exposure. Persons with G6PD deficiency may be 3 to 4 times more likely to develop hemolytic anemia from chlorite exposure as persons with normal activity levels when GSH levels are used as a measure of susceptibility. The proposed use of chlorine dioxide as an alternate disinfectant for drinking water supplies should consider this potential high risk group.

Assessment of potential for natural attenuation of chlorinated ethenes and ethanes in ground water at a petrochemical reclamation site, Harris County, Texas

USGS Publications Warehouse

Huff, Glenn F.; Braun, Christopher L.; Lee, Roger W.

2000-01-01

Redox conditions in the Numerous Sand Channels Zone beneath a petrochemical reclamation site in Harris County, Texas, range from sulfate reducing to methanogenic as indicated by the presence of methane in ground water and the range of molecular hydrogen concentrations. Assessment of the potential for reductive dechlorination using BIOCHLOR as a screening tool indicated conditions favoring anaerobic degradation of chlorinated organic compounds in the Numerous Sand Channels Zone. Evidence supporting reductive dechlorination includes apparently biogenic cis-1,2-dichloroethene; an increased ratio of 1,2-dichloroethane to 1,1,2-trichloroethane downgradient from the assumed contaminant source area; ethene and methane concentrations greater than background concentrations within the area of the contaminant plume; and a positive correlation of the ratio of ethene to vinyl chloride as a function of methane concentrations. The body of evidence presented in this report argues for hydrogenolysis of trichloroethene to cis-1,2-dichloroethene; of 1,1,2-trichloroethane to 1,2-dichloroethane; and of vinyl chloride to ethene within the Numerous Sand Channels Zone. Simulations using BIOCHLOR yielded apparent first-order decay constants for reductive dechlorination in the sequence Tetrachloroethene --> trichloroethene --> cis-1,2-dichloroethene --> vinyl chloride --> ethene within the range of literature values reported for each compound and apparent first-order decay constants for reductive dechlorination in the sequence 1,1,2-trichloroethane --> 1,2-dichloroethane slightly greater than literature values reported for each compound along the upgradient segment of a simulated ground-water flowpath. Except for vinyl chloride, apparent rates of reductive dechlorination for all simulated species show a marked decrease along the downgradient segment of the simulated ground-water flowpath. Evidence for reductive dechlorination of chlorinated ethenes within the Numerous Sand Channels Zone indicates potential for natural attenuation of chlorinated ethenes. Reductive dechlorination of chlorinated ethanes apparently occurs to a lesser extent, indicating relatively less potential for natural attenuation of chlorinated ethanes. Additional data are needed on the concentrations and distribution of chlorinated ethenes and ethanes in individual fine sand intervals of the Numerous Sand Channels Zone. This information, combined with lower minimum reporting levels for future chloroethane analyses, might enable a more complete and quantitative assessment of the potential for natural attenuation at the site.

RESPIRATORY RESPONSE AND INTERNAL TISSUE DOSE OF INHALED CHLORINE IN THE RESPIRATORY TRACT OF F344 RATS: SEX AND SPECIES COMPARISONS

EPA Science Inventory

Inhaled Cl₂ causes irritant effects in the respiratory tract. Females of various toxicological studies show more severe effects than males, notably a decrease in survivability observed in rats of a 2-year bioassay (CIIT, 1993; Wolf et al., 1995, Fundam. Appl. Toxic...