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Relationship of chlorine decay and THMs formation to NOM size.

Because of increasing concern about balancing health risks for pathogen control and disinfection by-product (DBP) formation in water supplies, utilities are forced to closely examine and optimize their disinfection practices. A better understanding of the relationship between the molecular weights of the natural organic matter (NOM), chlorine decay kinetics and THMs formation can help the utilities to minimize the DBP concentrations, providing healthier and microbially safer water. The authors present data on chlorine decay kinetics and total trihalomethanes (TTHM) formation kinetics and modeling with different molecular weights NOM fractions of Mississippi River water. TTHM modeling results indicated that the TTHM formation in fractionated NOM was a function of chlorine consumption. TTHM yield coefficients ranged from 31 to 42 microg-TTHM/mg-Cl2. As the molecular weight of the fractions decreased, TTHM yield coefficients increased.

Chlorine Compounds↗

Simultaneous capture of metal, sulfur and chlorine by sorbents during fluidized bed incineration.

Metal capture experiments were carried out in an atmospheric fluidized bed incinerator to investigate the effect of sulfur and chlorine on metal capture efficiency and the potential for simultaneous capture of metal, sulfur and chlorine by sorbents. In addition to experimental investigation, the effect of sulfur and chlorine on the metal capture process was also theoretically investigated through performing equilibrium calculations based on the minimization of system free energy. The observed results have indicated that, in general, the existence of sulfur and chlorine enhances the efficiency of metal capture especially at low to medium combustion temperatures. The capture mechanisms appear to include particulate scrubbing and chemisorption depending on the type of sorbents. Among the three sorbents tested, calcined limestone is capable of capturing all the three air pollutants simultaneously. The results also indicate that a mixture of the three sorbents, in general, captures more metals than a single sorbent during the process. In addition, the existence of sulfur and chlorine apparently enhances the metal capture process.

Adsorption↗

A comparative adsorption/biosorption study of mono-chlorinated phenols onto various sorbents.

The potential use of dried activated sludge and fly ash as a substitute for granular activated carbon for removing mono-chlorinated phenols (o-chlorophenol and p-chlorophenol) was examined. The pollutant binding capacity of the adsorbent/biosorbent was shown to be a function of substituted group, initial pH and initial mono-chlorinated phenol concentration. The working sorption pH value was determined as 1.0 and the equilibrium uptake increased with increasing initial mono-chlorinated phenol concentration up to 500 mg dm(-3) for all the mono-chlorinated phenol-sorbent systems. The suitability of the Freundlich, Langmuir and Redlich-Peterson adsorption models to the equilibrium data were investigated for each mono-chlorinated phenol-sorbent system. The results showed that the equilibrium data for all the mono-chlorinated phenol-sorbent systems fitted the Redlich-Peterson model best within the concentration range studied.

Adsorption↗

Destruction of cyanide waste solutions using chlorine dioxide, ozone and titania sol.

Increasingly, there are severe environmental controls in the mining industry. Because of lack of technological advances, waste management practices are severely limited. Most of the wastes in the milling industrial effluents are known to contain cyanides and it is recognized that after extraction and recovery of precious metals, substantial amounts of cyanide are delivered to tailings ponds. The toxicity of cyanide creates serious environmental problems. In this paper we describe several methods for the treatment of cyanide solutions. These include: (1) cyanide destruction by oxidation with chlorine dioxide (ClO(2)) in a Gas-Sparged Hydrocyclone (GSH) reactor; (2) destruction of cyanide by ozone (O(3)) using a stirred batch reactor, and finally, (3) the photolysis of cyanide with UV light in presence of titania sol. In all cases excellent performance were observed as measured by the extent and of the destruction.

Chlorine Compounds↗

Properties and application of a partially purified alkaline xylanase from an alkalophilic fungus Aspergillus nidulans KK-99.

An alkalophilic Aspergillus nidulans KK-99 produced an alkaline, thermostable xylanase (40 IU/ml) in a basal medium supplemented with wheat bran (2% w/v) and KNO3 (at 0.15% N) pH 10.0 and 37 degrees C. The partially purified xylanase was optimally active at pH 8.0 and 55 degrees C. The xylanase was stable in a broad pH range of 4.0-9.5 for 1 h at 55 degrees C, retaining more than 80% of its activity. The enzyme exhibited greater binding affinity for xylan from hardwood than from softwood. The xylanase activity was stimulated (+25%) by Na+ and Fe2+ and was strongly inhibited (maximum by 70%) by Tween-20, 40, 60, SDS, acetic anhydride, phenylmethane sulphonyl fluoride, Triton-X-100. The xylanase dose of 1.0 IU/g dry weight pulp gave optimum bleach boosting of Kraft pulp at pH 8.0 and temperature 55 degrees C for 3 h reaction time.

Acetic Anhydrides↗

The development and testing of a dermal exposure system for pharmacokinetic studies of administered and ambient water contaminants.

INTRODUCTION: In order to investigate the pharmacokinetics of water-borne chemicals while eliminating exposures by other routes, a dermal exposure system was developed to expose the hand and forearm of human subjects. METHODS: The goal was, primarily, to study the dermal pharmacokinetics of methyl tertiary butyl ether (MTBE), a water contaminant, and, secondarily, the ambient disinfection byproducts (DBPs). MTBE is used as a fuel oxygenate and DBPs result from chlorination of drinking water. The DBPs measured in the water and blood of the subjects were chloroform, bromodichloromethane, and dibromochloromethane. The dermal exposure system was constructed of inert and impervious materials. The interface between the glass and Teflon exposure tank and the subject was custom-made of clear Tedlar (polyvinylfluoride) so that the depth of the arm in the media could be monitored. RESULTS: Sampling of the water concentration of the test chemical, MTBE, demonstrated stability over the duration of the exposure. A temperature loss of about 1.5 degrees C occurred over the course of the 1-h exposure. Blood concentrations taken from 14 human subjects before, during, and after the 1-h exposure demonstrated that measurable MTBE and DBPs were absorbed. DISCUSSION: This system has the advantages of maintaining contaminant concentration and exposing an anatomically distinct body region, and the convenience of blood sampling.

Administration, Cutaneous↗

Laser Raman and IR spectra and force fields for 2,4-dichlorobenzonitrile.

Raman spectrum of 2,4-dichlorobenzonitrile (2,4-DCBN) in powder form has been recorded in the region 50-4000 cm(-1) on a Jasco K-500 Raman spectrophotometer using the 488.0 nm radiation from an argon laser. FTIR spectra in the region 200-4000 cm(-1) have been recorded in KBr pellet and nujol mull on a Nicolet DX spectrometer. Using the observed Raman and IR frequencies, normal co-ordinate analysis has been carried out to support the vibrational analysis and to determine the planar and non-planar force fields.

Chlorine Compounds↗

Vibrational frequencies and structure of B4Cl4: an ab intio quantum chemical study.

The normal mode frequencies and corresponding vibrational assignments of B4Cl4 are examined theoretically using the Gaussian 98 set of quantum chemistry codes. All normal modes were successfully assigned to one of three types of motion predicted by a group theoretical analysis (B-B stretch, B-Cl stretch, B-Cl bend) utilizing the Td symmetry of the molecule. The vibrational modes of the naturally isotopically substituted (1-(10)B, 2-(10)B, 3-(10)B and 4-(10)B) forms of B4Cl4 were also calculated and compared against experimental data. A complex pattern of frequency shifts and splittings is revealed.

Boron↗

Vibrational frequencies and structural determination of trichloroboroxine.

The normal mode frequencies and corresponding vibrational assignments of trichloroboroxine (B3O3Cl3) in D3h symmetry are examined theoretically using the Gaussian 98 set of quantum chemistry codes. All normal modes were successfully assigned to one of five types of motion (B-Cl stretch, B-O stretch, B-Cl bend, O-B-O bend, and B(OOCl) umbrella motion) predicted by a group theoretical analysis. By comparing the vibrational frequencies with IR and Raman spectra available in the literature, a set of scaling factors is derived. Molecular orbitals and bonding are examined.

Boron Compounds↗

Water ecology of Legionella and protozoan: environmental and public health perspectives.

Ecological studies on Legionella spp. are essential to better understand their sources in the natural environments, the mechanism of their entry into man-made water systems and the factors enabling their survival and growth in aquatic habitats. Legionella spp. exhibits peculiar and multiple strategies to adapt to stressful environment conditions which normally impair other germ survival. These strategies include the ability to enter in a viable but non-cultivable (VBNC) state, to multiply intracellularly within a variety of protozoa, such as amoebae, to survive as free organisms within biofilms and to be enhanced/inhibited by the presence of other aquatic bacteria. The host-parasite interaction has been shown to be central in the pathogenesis and ecology of L. pneumophila. The bacterial-protozoan interaction contributes to the amplification of Legionella population in water systems, represents a shelter against unfavourable environmental conditions, acts as a reservoir of infection and contributes to virulence by priming the pathogen to infect human cells. Legionella is able to survive as free organism for long periods within biofilms which are widespread in man-made water systems. Biofilm provides shelter and nutrients, exhibits a remarkable resistance to biocide compounds and chlorination, thus representing ecological niches for legionella persistence in such environments. Further knowledge on biofilm-associated legionellae may lead to effective control measures to prevent legionellosis. Lastly, new perspectives in controlling legionella contamination can arise from investigations on aquatic bacteria able to inhibit legionella growth in natural and artificial water systems.

Animals↗

Inactivation of human rotavirus, SA11 and other enteric viruses in effluent by disinfectants.

A preparation of infectious human rotavirus, isolated from faeces and resuspended in wastewater effluent, was shown to be inactivated by chlorine, chlorine dioxide, ozone and peracetic acid. Infectivity was assayed in MA 104 cells by the detection of cell-associated viral antigen by immunofluorescence. The inactivation curves were similar to those reported for other enteric viruses. Human rotavirus was at least as resistant as poliovirus, coxsackievirus, echovirus and f2 coliphage and was strikingly less sensitive to inactivation than the simian rotavirus, SA11. The latter was generally the most sensitive of the six tested viruses yet is often taken as being representative of the human rotaviruses.

Chlorine↗

A comparison of the virucidal properties of chlorine, chlorine dioxide, bromine chloride and iodine.

Chlorine dioxide, bromine chloride and iodine were compared with chlorine as virucidal agents. Under optimal conditions all disinfectants were effective at low concentrations, but each disinfectant responded differently to acidity and alkalinity. Disinfection by chlorine was impaired by the presence of ammonia, but the other disinfectants retained much of their potency. Disinfection of poliovirus by iodine resulted in structural changes in the virions as seen by electron micrroscopy, but the other disinfectants were able to inactivate poliovirus without causing any apparent structural changes.

Bromides↗

Sustained high levels of stored drinking water treatment and retention of hand-washing knowledge in rural Kenyan households following a clinic-based intervention.

Nyanza Province, Kenya is characterized by poor water quality and high diarrhoea prevalence. To address these problems, nurses in a maternal and child health clinic in Homa Bay, Kenya were trained in household water chlorination with a locally available, social marketed product, and in six steps of proper hand washing. They were asked to communicate this information to their clients. Interviews immediately following the training by nurses were conducted on 220 clients, of whom 168 (76%) reported being taught both procedures during their clinic visit. After 2 weeks, free chlorine residuals were present in stored drinking water in 67 out of 98 (68%) clients' homes and, 1 year later, in 36 out of 51 (71%) clients' homes. After 2 weeks, all six hand-washing steps were correctly demonstrated by 41 (44%) out of 93 clients, and by 17 out of 51 (34%) 1 year later. This brief, practical intervention shows promise for vulnerable populations.

Adolescent↗

Reductive dechlorination of cis-1,2-dichloroethene and vinyl chloride by "Dehalococcoides ethenogenes".

cis-Dichloroethene (DCE) and vinyl chloride (VC) often accumulate in contaminated aquifers in which tetrachloroethene (PCE) or trichloroethene (TCE) undergo reductive dechlorination. "Dehalococcoides ethenogenes" strain 195 is the first isolate capable of dechlorinating chloroethenes past cis-DCE. Strain 195 could utilize commercially synthesized cis-DCE as an electron acceptor, but doses greater than 0.2 mmol/L were inhibitory, especially to PCE utilization. To test whether the cis-DCE itself was toxic, or whether the toxicity was due to impurities in the commercial preparation (97% nominal purity), we produced cis-DCE biologically from PCE using a Desulfitobacterium sp. culture. The biogenic cis-DCE was readily utilized at high concentrations by strain 195 indicating that cis-DCE was not intrinsically inhibitory. Analysis of the commercially synthesized cis-DCE by GC/mass spectrometry indicated the presence of approximately 0.4% mol/mol chloroform. Chloroform was found to be inhibitory to chloroethene utilization by strain 195 and at least partially accounts for the inhibitory activity of the synthetic cis-DCE. VC, a human carcinogen that accumulates to a large extent in cultures of strain 195, was not utilized as a growth substrate, and cultures inoculated into medium with VC required a growth substrate, such as PCE, for substantial VC dechlorination. However, high concentrations of PCE or TCE inhibited VC dechlorination. Use of a hexadecane phase to keep the aqueous PCE concentration low in cultures allowed simultaneous utilization of PCE and VC. At contaminated sites in which "D. ethenogenes" or similar organisms are present, biogenic cis-DCE should be readily dechlorinated, chloroform as a co-contaminant may be inhibitory, and concentrations of PCE and TCE, except perhaps those near the source zone, should allow substantial VC dechlorination.

Bacteria, Anaerobic↗

Abiotic transformation of perchloroethylene in homogeneous dithionite solution and in suspensions of dithionite-treated clay minerals.

The reductive dechlorination of perchloroethylene (PCE) in homogeneous solutions of dithionite and at the surfaces of dithionite-citrate-bicarbonate (DCB) treated ferruginous smectite and Na-montmorillonite was studied. Transformation products of PCE identified in dosed dithionite-treated samples included TCE, DCE, 1,1,2-trichloroethane (TCA), 1,1-dichloroethane (DCA), chloroacetylene, acetylene, ethene, and ethane. The decomposition of dithionite to sulfate yielded both protons and electrons necessary for hydrodechlorination (hydrogenolysis) of PCE. Dithionite treatment of the Fe-poor Na-montmorillonite enhanced reductive dechlorination of PCE relative to dithionite-treated Fe-rich ferruginous smectite, within the range of 11.5-137.8 mM dithionite. For the same dithionite concentration, the kinetics of the heterogeneous reactions of PCE was generally faster than that of the homogeneous reaction, and higher concentrations of TCE were measured in the heterogeneous reactions. Interestingly, increases in the mass of the clay minerals used, the Fe2+ content in the clay mineral structure, or the dithionite concentration used did not necessarily enhance the abiotic transformation of PCE, as would otherwise be predicted. The most efficient reductive dechlorination of PCE was observed with 0.5% clay (m/v) treated with 34.5 mM dithionite buffered at pH 8.5. The solid-state transfer of electrons to surfaces and edges, rather than the redox capacity, limited the dechlorination of PCE by reduced ferruginous smectite and/or suspensions containing a higher clay mass. The greater reactivity of dithionite-reduced montmorillonite than similarly treated ferruginous smectite is attributed to (i) the well-documented layer collapse and aggregation of chemically reduced clays that increases with the clay's iron content, (ii) the location of solid-phase Fe2+ in the reduced clay mineral and whether it is accessible or inaccessible for reaction with PCE at the mineral edges and surfaces where the reactions are thought to occur, and (iii) the greater swellability of montmorillonite versus ferruginous smectite. The faster dechlorination rate of PCE observed with dithionite-reduced Fe-poor montmorillonite than similarly reduced iron-rich ferruginous smectite suggests that the use of dithionite barriers for in-situ treatment of chlorinated solvent plumes should not be limited to aquifers with Fe-rich sediments.

Aluminum Silicates↗

Radiolytic and thermal dechlorination of organic chlorides adsorbed on molecular sieve 13X.

Reductive dechlorination of chlorobenzene (PhCl), trichloroethylene (TCE), tetrachloroethylene (PCE), 1- and 2-chlorobutanes, chloroform, carbon tetrachloride, and 1,1,1- and 1,1,2-trichloroethanes adsorbed on molecular sieve 13X was investigated. The molecular sieve adsorbing the organic chlorides was irradiated with gamma-rays, heated, or allowed to stand at room temperature in a sealed ampule and was then soaked in water. The dechlorination yields were determined from the Cl- concentrations of the supernatant aqueous solutions. It was found that the chlorinated alkanes adsorbed on the molecular sieve are readily dechlorinated on standing at room temperature. The dechlorination at room temperature was limited for TCE and PCE. PhCl was quite stable even at 200 degrees C. gamma-Radiolysis was examined for PhCl, TCE, and PCE at room temperature. The radiation chemical yields of the dechlorination, G(Cl-), were 1.9, 40, and 30 for PhCl, TCE, and PCE, respectively. After 5 h of heating at 200 degrees C, the dechlorination yields for TCE and PCE were 24.5 and 4.3%, respectively. TCE is much more reactive than PCE in the thermal dechlorination, whereas their radiolytic dechlorination yields are comparable. The pH of the supernatant solutions decreased along with the dechlorination.

Adsorption↗

Are PCBs in the Canadian Arctic atmosphere declining? Evidence from 5 years of monitoring.

A long-term database of weekly air concentrations was examined to establish temporal trends of PCBs in the Arctic atmosphere. Several methods were employed to reduce the intra-annual variability allowing the elucidation of longterm trends for a selection of congeners at Alert located in the Canadian Arctic. These methods included temperature normalization (TN), multiple linear regression (MLR), and digital filtration (DF). Estimation of the slope (m) resulting from the linear regression between the natural logarithm of the partial pressure in air versus reciprocal temperature (In P = m/T + b), required for TN and MLR, proved difficult due to the poor correlation with temperature experienced forthe majority of congeners. Values of m were considerably lower than those obtained from temperate studies, implying that regional air-surface exchange plays a minor role in supporting the observed air concentrations in the Arctic. The lighter congeners generally showed very low slopes, and some even showed positive correlation with 1/T. This might be a result of their relatively fast reaction rates with OH radicals following the onset of 24-h sunlight in spring. Use of DF (in combination with TN and MLR) revealed declining trends for several of the lower chlorinated congeners in the high Arctic atmosphere, with estimated first-order half-lives, t1/2, ranging from approximately 3 to 20 yr. Declining trends of the lower congeners probably reflect falling levels in source regions, as a result of long-range transport to this Arctic site. There were no apparent trends for the higher chlorinated congeners (penta-substituted and above), exceptfor PCB 180, in marked contrast to temperate studies, indicating a lag time for decline between the Arctic and source regions.

Air Pollutants↗