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PubMed2003

Development of a Ct equation for the inactivation of Cryptosporidium oocysts with chlorine dioxide.

Cryptosporidium parvum, a protozoan parasite, has been implicated in a number of waterborne disease outbreaks and is difficult to inactivate using free chlorine. It appears, however, to be inactivated more easily by other oxidants such as chlorine dioxide or ozone. A major element of the EPA (US EPA) strategy for controlling C. parvum (oocysts) in drinking water is the possible use of Ct (concentration of disinfectant in mg/L times time in minutes) values. To support this strategy a Ct equation, based on first-order kinetics, is proposed to provide guidance to drinking water utilities for the application of chlorine dioxide for controlling C. parvum oocysts. The equation is based on standard statistical techniques using available bench scale data. It can predict mean inactivation levels as well as a statistically conservative upper bound Ct value. This upper bound could be used to insure an appropriate safety factor for the protection of public health.

Animals↗
PubMed2003

Pretreatment for membrane water treatment systems: a laboratory study.

The goal of the work was to determine if biological treatment of water containing soil-derived humic substances has the potential for reducing the fouling of membranes used in water treatment. Laboratory scale biological filters containing biologically active carbon or iron oxide coated sand were fed humic-laden water with or without prechlorination. This stream was split, with half being further treated by microfiltration. Treated water was assessed for total organic carbon removal and biofouling potential using a glass bead assay and membrane assay for total cell counts, fouling layer thickness, and flux reduction. A combination of these assays provided more insight than any single measurement. Compared to untreated control water, biological treatment was capable of reducing downstream fouling of membrane systems. For example, fouling layer thickness was reduced by half after biological treatment, and cell counts were reduced four- to five-fold. Biological treatment coupled with microfiltration provided the best reduction of fouling, while prechlorination did not appear to impact the process. These results suggest that biological treatment may be valuable in reducing membrane fouling while reducing the amount of disinfectants used in pretreatment.

Biofilms↗
PubMed2003

Optimal methods for quenching H2O2 residuals prior to UFC testing.

In this paper, the quenching of hydrogen peroxide by catalase, sodium hypochlorite, sodium thiosulfate and sodium sulfite, prior to UFC testing, was investigated. Sodium hypochlorite, sodium thiosulfate and sodium sulfite were found to be unsuitable for quenching H2O2 residuals because the procedures are time-consuming and complicated in that they require potentially multiple measurements of the peroxide and chlorine residuals. In contrast, quenching of peroxide with catalase is a simple procedure. Catalase doses of less than 0.2 mg/L were found to have no impact on DBP (TTHM, HAA and aldehyde) formation in the UFC test, and the time that was needed to quench 100 mg/L peroxide (room temperature, pH 8.3) was less than 10 min. In addition, peroxide was found to react with DPD reagents that are used to measure chlorine residuals, a phenomenon that may lead to falsely high chlorine residuals in the UFC test.

Catalase↗
PubMed2003

An ATP-based method for monitoring the microbiological drinking water quality in a distribution network.

The titration of adenosine triphosphate (ATP) by bioluminescence permits rapid evaluation of the quantity of viable micro-organisms present in a water sample. During two sampling campaigns, Société Anonyme de Gestion des Eaux de Paris (SAGEP) tested a new extraction and titration system of bacterial ATP in the Paris drinking water distribution network. As far as the entire set of results of analyses of water in the network is concerned there is a linear relationship between log [ATP] and log(HPC-R2A/ml). Furthermore, as regards the drinking water originating from treatment of surface waters, some of the results obtained indicate a slight change as regards the Paris network in the microbiological quality. This is certainly linked to the distance travelled from the production location as well as to a reservoir effect observed on a site. Conversely, no change is apparent with regard to waters of underground origin. Lastly, despite changes in temperature and chlorine residual, no significant influence has been observed, essentially because of the very low density of culturable bacteria.

Adenosine Triphosphate↗
PubMed2003

A Bayesian method of estimating kinetic parameters for the inactivation of Cryptosporidium parvum oocysts with chlorine dioxide and ozone.

The main objective of this paper is to use Bayesian methods to estimate the kinetic parameters for the inactivation kinetics of Cryptosporidium parvum oocysts with chlorine dioxide or ozone which are characterized by the delayed Chick-Watson model, i.e., a lag phase or shoulder followed by pseudo-first-order rate of inactivation. As the length of the lag phase (CT(lag)) is not known, Bayesian statistics provides a more accurate approach than traditional statistical methods to fitting the delayed Chick-Watson kinetics. Markov Chain Monte Carlo method is used to estimate CT(lag) and first-order rate constant values. This method is also used to estimate the minimum CT requirement (with safety factor) for 99% inactivation of C. parvum oocysts.

Animals↗
PubMed2003

Derivation of acute ecological risk criteria for chlorite in freshwater ecosystems.

Chlorine dioxide has been proposed as an alternative to chlorine because it is a powerful disinfection agent that does not react with ammonia or chlorinated organics to form chloramines or trihalomethanes. The major reduction product formed when chlorine dioxide is added to water is the chlorite ion. Chlorite has been shown to be less toxic than free or combined chlorine. However, previous studies with eight freshwater families produced a US Environmental Protection Agency (USEPA) acute water quality criteria (WQC) lower than the WQC for chlorine. In the current study, an additional 12 families were added to the toxicological database to determine ecological risk criteria (ERC) using both the standard USEPA WQC methodology and the USEPA Office of Pesticide Programs (OPP) probabilistic approach. Chlorite LC50 values for the 20 family database ranged from 0.27 mg/L for the Daphnidae to 208.76 mg/L for the Salmonidae. The Daphnidae were by far the most sensitive family tested, with an LC50 44 times lower than the next most sensitive family tested, the Hyalellidae (LC50=1.19 mg/L) and 214 times lower than the most sensitive fish family tested, the Ictaluridae (LC50=5.79 mg/L). The Criteria Maximum Concentration calculated using the USEPA WQC methodology was 0.025 mg/L while the 95% ERC calculated using the USEPA OPP probabilistic methodology was 0.135 mg/L. The USEPA OPP probabilistic approach yields a criterion more consistent with the overall species sensitivity distribution and is not overly skewed by the low Daphnidae LC50 as is the USEPA WQC approach.

Animals↗
PubMed2000

The formation and control of disinfection by-products using chlorine dioxide.

In this study, chlorine dioxide (ClO2) was used as an alternative disinfectant with vanillic acid, p-hydroxybenzoic acid, and humic acid as the organic precursors in a natural aquatic environment. The primary disinfection by-products (DBPs) formed were trihalomethanes (THMs) and haloacetic acids (HAAs). Under neutral conditions (pH = 7) for vanillic acid, more total haloacetic acids (THAAs) than total trihalomethanes (TTHMs) were found, with a substantial increase during the later stages of the reaction. In the case of p-hydroxybenzoic acid, the amount of THAAs produced was minimal. Raising the concentration of ClO2 was not favorable for the control of THAAs in low concentrations of vanillic acid. ClO2 could reduce the total amount of TTHMs and THAAs for higher concentration of vanillic acid. It was found that the humic acid treatment dosage was not significant. Under alkaline conditions (pH = 9), the control of TTHMs and THAAs for the treatment of vanillic acid was better and more economical, however, an appreciable amount of inorganic by-products were observed. Under the same alkaline condition, the control of THAA for the treatment of p-hydroxybenzoic acid was not beneficial and for the treatment of humic acid was not significant.

Chlorine Compounds↗
PubMed2001

The influence of level and chlorine source on the formation of mono- to octa-chlorinated dibenzo-p-dioxins, dibenzofurans and coplanar polychlorinated biphenyls during combustion of an artificial municipal waste.

The formation of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and the three coplanar polychlorinated biphenyls (pPCBs) was studied during labscale fludized bed combustion of eight artificial municipal solid waste (MSW) fuel mixtures. The level of chlorine as well as the chlorine source varies within the different fuel mixtures. Four different chlorine sources were studied, viz, an inorgnaic (NaCl) and three organic sources, pure PVC plastic and two products (floor and cable) and the total chlorine level varies between 0.28% and 1.1%. The experiments were performed in a 5 kW laboratory scale fluidized bed reactor. A correlation between the total chlorine in the fuel and the formation of the hepta- and octa-chlorinated PCDD/F homologues was found. However, the most important variable for changes in the PCDDs/Fs and pPCBs formation was disturbance in the combustion condition and not the variation in chlorine content of the fuel. Furthermore, no differences in formation between the chlorine sources could be seen.

Air Pollutants↗
PubMed2001

Feasibility of using metals to remediate water containing TCE.

The feasibility of treating underground water contaminated by a chlorinated organic compound with bimetallics Fe/ Ni, Zn/Ni and Zn single metal was studied. Column tests to simulate a reactive permeable wall in a funnel-and-gate system were used. Research results indicated that bimetallic Fe0/Ni0 and Zn0/Ni0 all had a very strong degraded power to trichloroethylene (TCE) at concentration up to 25 mg/l under different flow rates (27 cm/day-20 m/day). Furthermore, the concentrations of TCE and various ions in the treated effluent were nearly lower than the values specified in related standards for drinking water in Taiwan. These results showed that this technique could be effectively and safely used as an underground water remediation process.

Environmental Pollution↗
PubMed2001

The organic precursors affecting the formation of disinfection by-products with chlorine dioxide.

The object of this research was to study the formation of disinfection by-products by using chlorine dioxide (ClO2) as a disinfectant reacting with different properties of organic substance in natural aquatic environment. The adsorbent resin (XAD-4, XAD-7) was used to divide the organic matters in raw water into three groups. The influence of the function groups on structure, reaction tendency, and formation of disinfection by-products generated by the reaction of these organic substances with chlorine dioxide was explored. The experimental results show that the three different organic groups formed using adsorbent resin were hydrophobic substance, hydrophilic acid, and non-acid hydrophilics in proportions of 43%, 41%, and 16%, respectively. Within the raw water in our study, the hydrophilic substance had a higher distribution proportion than that described in general articles and journals, which indicates that this water was contaminated with pollution from human beings. The exploration of the reactivity of the three different organic substances with chlorine dioxide shows that the unit consumption of disinfection agent per unit organic matters (represented by ClO2/DOC) is in the following sequence hydrophobic substance > hydrophilic substance > non-acid hydrophilics. It indicated that larger molecular organic precursors had larger consumption of disinfectant. We also discovered that after the reaction of the three different organic substances with chlorine dioxide, the largest amount of disinfection by-products were generated by the non-acid hydrophilics.

Adsorption↗
PubMedDate not supplied

Congener-specific detection of dioxins using jet-REMPI.

Although 210 chemically different polychlorinated dibenzo-p-dioxin and dibenzofuran congeners can be produced during combustion, it is currently believed that fewer than 20 are toxic enough to warrant monitoring. SRI is developing a continuous emissions monitor to study the emission levels of these most toxic dioxins, leading eventually to an improved understanding of the formation of these molecules and to improved means of monitoring and control. We report here the first results of performing congener-specific detection for two dichloro dibenzo-p-dioxins present in low ppt concentrations in a mixture using the supersonic jet/resonantly enhanced multiphoton ionization time-of-flight mass spectrometer technique. In addition, we present preliminary data on the detection of chlorinated aromatic compounds using a two-color REMPI scheme with the same instrument.

Benzofurans↗
PubMedDate not supplied

Solvent extraction and tandem dechlorination for decontamination of soil.

The United States Environmental Protection Agency (US EPA) guidelines allow removal of polychlorinated biphenyls (PCBs) from soils via solvent extraction. This option holds promise for removal of other recalcitrant organic contaminants as well. A study was undertaken to evaluate the effectiveness of solvent extraction with two tandem degradation techniques. The degradation techniques were chemical dehalogenation with immobilized reagents and gamma-ray irradiation. The integrated approach was evaluated with contaminated soils from wood treatment and electric power substation sites. Evaluations were carried out on a bench scale in the laboratory and on a semi-pilot scale at a contaminated site. Binary solvent mixture of alkanes and alcohols yielded the highest extraction efficiencies. Extraction efficiencies in excess of 90% were obtained for PCBs, polychlorinated dibenzo-p-dioxins (PCDDs) and polynuclear aromatic hydrocarbons (PAHs). Extracted PCBs were rapidly degraded through chemical dehalogenation or with high doses of the gamma-ray irradiation. The residual organics in the solvent mixture were removed with activated carbon, and the solvent was recycled for subsequent soil extractions. Contaminants adsorbed on the activated carbon were destroyed with a counter flow oxidation process.

Carbon↗
PubMedDate not supplied

Dioxin cycling in aquatic sediments: the Passaic River Estuary.

The contribution of dechlorination reactions to the transformation of dioxins in river sediments was evaluated under a range of geochemical conditions mimicking freshwater, estuarine and marine environments, and interpreted in the light of recent evidence for their accumulation at the air-water interface. The yield of dechlorinated products increased with salinity, but never exceeded 20% of the initial dioxins present. Among the homologue groups in saline conditions, diCDDs were dominant at 32-47 mol% (8-16 nM). The production of 2,3,7,8-TCDD increased with decreasing salinity and in the presence of dissolved organic matter, exhibiting a maximum ratio (2,3,7,8-TCDD:non-2,3,7,8-TCDD) of 0.5. These differences in patterns may be related to the dominant microbial respiratory processes responsible for carbon turnover under the imposed conditions, and are strongly affected by the presence of organic matter. Based on these results, a conceptual dechlorination and carbon turnover model is proposed to help explain the likely reactivity of dioxins in the Passaic River Estuary.

Carbon↗
PubMed2001

Factors on the formation of disinfection by-products MX, DCA and TCA by chlorination of fulvic acid from lake sediments.

[3-Chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone] (MX) and chlorinated acetic acids such as dichlorinated acetic acid (DCA) and trichlorinated acetic acid (TCA) have always been the focus of disinfection by-products (DBPs) studies. In order to find out the influences of reaction time, TOC, chlorine dose, pH and temperature on the formation of MX, DCA and TCA, we extracted fulvic acid (FA) from the sediment of Tai Lake, and conducted simulated chlorination of samples rich in FA. Results showed positive relationship between TOC and the yields of MX, DCA and TCA. But the influences of pH, chlorine dose, reaction time, and temperature are quite complex. The optimal chlorination condition for the formation of MX is pH = 2, T = 45 degrees C, C/Cl2 = 1/4, t = 12 h. Lower pH, longer time, greater chlorine dose can result in greater yield of both DCA and TCA, and there is a strong linear relationship between the formation of DCA and TCA.

Acetic Acid↗
PubMed2001

Microbial dechlorination of three PCB congeners in river sediment.

We investigated the potential for the anaerobic degradation of three PCB congeners (2,3,5,6-CB, 2,3,4,5-CB, and 2,3,4,5,6-CB) in sediments collected from five monitoring sites along the Keelung River in northern Taiwan. Optimal conditions for congener dechlorination were 30 degrees C and pH 7.0. Intermediate 2,3,4,5-CB products were identified as 2,3,5-CB, 2,4,5-CB, and 2,5-CB. Intermediate 2,3,4,5,6-CB products were identified as 2,3,5,6-CB, 2,3,6-CB, and 2,5-CB. For 2,3,5,6-CB, intermediate products were identified as 2,3,6-CB and 2,5-CB. Dechlorination rates for PCB congeners were observed as (fastest to slowest): 2, 3, 4-CB > 2, 3, 4, 5-CB > 2, 3, 4, 5, 6-CB > 2, 3, 5, 6-CB > 2, 2', 3, 3', 4, 4'-CB > 2, 2', 4, 4' 6, 6'-CB > 2, 2', 3, 4, 4', 5, 5'-CB > 2, 2', 3, 3', 4, 4', 5, 5'-CB. Rates decreased for mixtures of the eight congeners. Dechlorination rates for the three primary congeners under different reducing conditions occurred in the order of (fastest to slowest): methanogenic condition > sulfate-reducing condition > nitrate-reducing condition. Under methanogenic and sulfate-reducing conditions, dechlorination rates were enhanced by the addition of lactate, pyruvate, or acetate, but delayed by the addition of manganese oxide, or ferric chloride. Under nitrate-reducing condition, dechlorination rates were delayed by the addition of lactate, pyruvate, acetate, manganese oxide or ferric chloride. Treatment with such microbial inhibitors as bromoethanesulfonic acid (BESA) or molybdate revealed that methanogen and sulfate-reducing bacteria were involved in the dechlorination of these three PCB congeners.

Bacteria, Anaerobic↗
PubMed2002

Reductive dechlorination of polychlorinated dibenzo-p-dioxins by zerovalent iron in subcritical water.

A new method for reductive dechlorination of polychlorinated dibenzo-p-dioxins (PCDDs) and remediation of contaminated soils is described that uses zerovalent iron as the dechlorination agent and subcritical water as reaction medium and extractive solvent. It is found that the zerovalent iron can be applied for stepwise dechlorination of octachlorinated dibenzo-p-dioxin (OCDD) on various matrixes in subcritical water. By using iron powder as matrix higher chlorinated congeners were practically completely reduced to less than tetra-substituted homologues. A significant part of residual OCDD, when it was spiked in to soils, and formed less chlorinated congeners are extracted with water in the given conditions. The solubility of OCDD was increased by a 4-6 orders over its solubility at ambient conditions. The new method of contentious-flow extraction is described.

Chlorine Compounds↗
PubMed2002

Analysis of chlorinated paraffins in cutting fluids and sealing materials by carbon skeleton reaction gas chromatography.

Chlorinated paraffins (CPs) pose a major risk in the environment, due to their wide application, to their persistence, to their carcinogenic potential, and in view of the fact, that they cannot be easily identified. Various commercial cutting fluids and sealing materials were analysed for CPs with carbon skeleton reaction gas chromatography (GC) and flame ionization detection. CPs are simultaneously dechlorinated and hydrogenated to the corresponding alkanes with Pd catalyst material in the GC injector. With this method, the carbon chain length of commercial technical CPs was determined. In six of sixteen sealing materials we found five short and one medium chain length polychlorinated paraffins in percentages of 9-16% (w/w). In five cutting fluids we found predominantly medium to long chain length chloroparaffins with percentages of 2.5-31% (w/w), only one fluid contained short chain CPs.

Catalysis↗