Disinfection byproduct relationships and speciation in chlorinated nanofiltered waters

The formation and speciation of disinfection byproducts (DBPs) resulting from chlorination of nanofilter permeates obtained from various source water locations and membrane types are examined. Specific ultraviolet absorbance and bromide utilization are shown to decrease following nanofiltration. Both dissolved organic carbon (DOC) concentration and ultraviolet absorbance at 254 nm were found to correlate strongly with trihalomethane (THM), haloacetic acid (HAA), and total organic halide (TOX) concentrations in chlorinated nanofilter permeates, suggesting that they can be employed as surrogates for DBPs in nanofiltered waters. Because smooth curves were obtained for individual THM and HAA species as well as bromine and chlorine incorporation into THMs and HAAs as a function of Br-/DOC molar ratio, it is likely that mole fractions of these DBPs are more strongly influenced by chlorination conditions, Br-, and DOC concentrations than NOM source and membrane type. Mole fractions of mono-, di-, and trihalogenated HAAs were found to be independent of Br-/DOC. Even at a very low Br-/DOC of 2.9microM/mM, the mixed bromochloro- and tribromoacetic acids constituted 20% of total HAAs on a molar basis. This increased to approximately 50% as Br-/DOC increased to approximately 25microM/mM or more, proving that a large fraction of HAAs may not be covered under existing federal regulations. Total THM and HAA9 concentrations decreased in permeate waters with increasing Br-/DOC suggesting that nanofilter permeates are limited with respect to DBP precursors.     

Trade-offs in disinfection byproduct formation associated with precursor preoxidation for control of N-nitrosodimethylamine formation

Chloramines in drinking water may form N-nitrosodimethylamine (NDMA). Various primary disinfectants can deactivate NDMA precursors prior to chloramination. However, they promote the formation of other byproducts. This study compared the reduction in NDMA formation due to chlorine, ozone, chlorine dioxide, and UV over oxidant exposures relevant to Giardia control coupled with postchloramination under conditions relevant to drinking water practice. Ten waters impacted by treated wastewater, poly(diallyldimethylammonium chloride) (polyDADMAC) polymer, or anion exchange resin were examined. Ozone reduced NDMA formation by 50% at exposures as low as 0.4 mg×min/L. A similar reduction in NDMA formation by chlorination required ～60 mg×min/L exposure. However, for some waters, chlorination actually increased NDMA formation at lower exposures. Chlorine dioxide typically had limited efficacy regarding NDMA precursor destruction; moreover, it increased NDMA formation in some cases. UV decreased NDMA formation by ～30% at fluences >500 mJ/cm(2), levels relevant to advanced oxidation. For the selected pretreatment oxidant exposures, concentrations of regulated trihalomethanes, haloacetic acids, bromate, and chlorite typically remained below current regulatory levels. Chloropicrin and trichloroacetaldehyde formation were increased by preozonation or medium pressure UV followed by postchloramination. Among preoxidants, ozone achieved the greatest reduction in NDMA formation at the lowest oxidant exposure associated with each disinfectant. Accordingly, preozonation may inhibit NDMA formation with minimal risk of promotion of other byproducts. Bromide >500 μg/L generally increased NDMA formation during chloramination. Higher temperatures increased NDMA precursor destruction by preoxidants but also increased NDMA formation during postchloramination. The net effect of these opposing trends on NDMA formation was water-specific.     

Flavor formation of tilapia byproduct hydrolysates in Maillard reaction

The Maillard reaction (MR) of tilapia byproduct protein hydrolysates was investigated for the use of byproduct protein as a food ingredient and to mask its fishy odor and bitter flavor. The flavor differences in tilapia byproduct hydrolysates before and after the MR were analyzed to explore the key flavor precursor peptides and amino acids involved in MR. The results suggested that eight key volatile substances, including 2,5-dimethylpyrazine, 2-pentylfuran, hexanal, octanal, nonanal, (E)-2-decenal, decanal, and 1-octen-3-ol contributed most to the MR products group (ROAV > 1). Ten volatile compounds, including 1-octen-3-ol, hexanal, 2-pentylfuran, 2,5-dimethylpyrazine, methyl decanoate, and 2-octylfuran, were the flavor markers that distinguished the different samples (VIP > 1). The four most consumed peptides were VAPEEHPTL, GPIGPRGPAG, KSADDIKKAF, and VWEGQNIVK. Umami peptides and bitter free amino acids (FAAs) were the key flavor precursor peptide and FAAs, respectively. Overall, the hydrolysates of tilapia byproducts with flavor improved by MR are a promising strategy for the production of flavorings.     

Kinetics and mechanistic aspects of As(III) oxidation by aqueous chlorine, chloramines, and ozone: relevance to drinking water treatment

Kinetics and mechanisms of As(III) oxidation by free available chlorine (FAC-the sum of HOCl and OCl-), ozone (O3), and monochloramine (NH2Cl) were investigated in buffered reagent solutions. Each reaction was found to be first order in oxidant and in As(III), with 1:1 stoichiometry. FAC-As(III) and O3-As(III) reactions were extremely fast, with pH-dependent, apparent second-order rate constants, k'app, of 2.6 (+/- 0.1) x 10(5) M(-1) s(-1) and 1.5 (+/- 0.1) x 10(6) M(-1) s(-1) at pH 7, whereas the NH2Cl-As(III) reaction was relatively slow (k'app = 4.3 (+/- 1.7) x 10(-1) M(-1) s(-1) at pH 7). Experiments conducted in real water samples spiked with 50 microg/L As(III) (6.7 x 10(-7) M) showed that a 0.1 mg/L Cl2 (1.4 x 10-6 M) dose as FAC was sufficient to achieve depletion of As(III) to <1 microg/L As(III) within 10 s of oxidant addition to waters containing negligible NH3 concentrations and DOC concentrations <2 mg-C/L. Even in a water containing 1 mg-N/L (7.1 x 10(-5) M) as NH3, >75% As(III) oxidation could be achieved within 10 s of dosing 1-2 mg/L Cl2 (1.4-2.8 x 10(-5) M) as FAC. As(III) residuals remaining in NH3-containing waters 10 s after dosing FAC were slowly oxidized (t1/2 > or = 4 h) in the presence of NH2Cl formed by the FAC-NH3 reaction. Ozonation was sufficient to yield >99% depletion of 50 microg/L As(III) within 10 s of dosing 0.25 mg/L O3 (5.2 x 10(-6) M) to real waters containing <2 mg-C/L of DOC, while 0.8 mg/L O3 (1.7 x 10(-5) M) was sufficientfor a water containing 5.4 mg-C/L of DOC. NH3 had negligible effect on the efficiency of As(III) oxidation by O3, due to the slow kinetics of the O3-NH3 reaction at circumneutral pH. Time-resolved measurements of As(III) loss during chlorination and ozonation of real waters were accurately modeled using the rate constants determined in this investigation.     

Electrochemistry of free chlorine and monochloramine and its relevance to the presence of Pb in drinking water

The commonly used disinfectants in drinking water are free chlorine (in the form of HOCl/OCl-) and monochloramine (NH2Cl). While free chlorine reacts with natural organic matter in water to produce chlorinated hydrocarbon byproducts, there is also concern that NH2Cl may react with Pbto produce soluble Pb(II) products--leading to elevated Pb levels in drinking water. In this study, electrochemical methods are used to compare the thermodynamics and kinetics of the reduction of these two disinfectants. The standard reduction potential for NH2Cl/Cl- was estimated to be +1.45 V in acidic media and +0.74 V in alkaline media versus NHE using thermodynamic cycles. The kinetics of electroreduction of the two disinfectants was studied using an Au rotating disk electrode. The exchange current densities estimated from Koutecky-Levich plots were 8.2 x 10(-5) and 4.1 x 10(-5) A/cm2, and by low overpotential experiments were 7.5 +/- 0.3 x 10(-5) and 3.7 +/- 0.4 x 10(-5) A/cm2 for free chlorine and NH2Cl, respectively. The rate constantforthe electrochemical reduction of free chlorine at equilibrium is approximately twice as large as that for the reduction of NH2Cl. Equilibrium potential measurements show that free chlorine will oxidize Pb to PbO2 above pH 1.7, whereas NH2Cl will oxidize Pb to PbO2 only above about pH 9.5, if the total dissolved inorganic carbon (DIC) is 18 ppm. Hence, NH2Cl is not capable of producing a passivating PbO2 layer on Pb, and could lead to elevated levels of dissolved Pb in drinking water.     

食品及水体中碘形态分析研究进展

碘是人体必需的一种微量元素。但是由于碘在自然环境中的分布不均匀,不同地区人群的碘摄入会产生缺乏或过量的现象,进而引起一系列的疾病。我国是世界上碘缺乏最严重的国家之一,因此实施食品及相关水体中碘含量的监测是一项长期的基本任务。然而碘在自然环境中的存在形式复杂,不同形态碘的生物有效性及毒性差异很大,因此开展不同形态碘含量的监测对于科学、准确评估人群的碘摄入具有重要意义。本文总结了近十多年来碘形态分析技术的发展,比较了各种前处理技术及分离分析技术的优缺点及适用范围,以期为相关科研工作者开展进一步的工作提供参考。     

Comparison of the chlorine inactivation of Yersinia enterocolitica in chlorine demand and demand-free systems

Inactivation of Yersinia enterocolitica by chlorine (0.6 to 20 ppm) was investigated in distilled water and in tryptic soy broth (TSB, 0.015%) at different temperatures (4, 20, and 40 degrees C). In distilled water, chlorine inactivation of Y. enterocolitica was enhanced by increasing the temperature from 4 to 20 degrees C, and survival curves were described by a model that assumed first-order kinetics followed by tailing in which the microbial concentration remained constant. The presence of TSB increased chlorine resistance of Y. enterocolitica, and survival curves were concave downward. These survival curves were described by a model based on the Weibull distribution. Chlorine decay in distilled water was independent of temperature and of the initial concentration of available chlorine and was modeled by first-order reaction kinetics. Chlorine decay in TSB was independent of the initial chlorine concentration but depended on the treatment temperature and was modeled by the addition of two first-order decay equations. The increased resistance of Y. enterocolitica to chlorine in TSB was not due only to the chlorine demand by the TSB components. These components protected Y. enterocolitica cells from the antimicrobial effect of chlorine.     

Atmospheric chlorine chemistry in southeast Texas: impacts on ozone formation and control

Recent evidence has demonstrated that chlorine radical chemistry can enhance tropospheric hydrocarbon oxidation and has the potential to enhance ozone formation in urban atmospheres. To assess these effects quantitatively, an August-September 2000 photochemical episode in southeast Texas was simulated using the comprehensive air quality model, with extensions (CAMx). During this episode, ambient measurements of a unique marker of atmospheric chlorine chemistry, 1-chloro-3-methyl-3butene-2-one (CMBO), were made and model performance was assessed by comparing modeled and observed CMBO mixing ratios. The model predicted ambient CMBO mixing ratios within the uncertainty limits associated with the emissions inventory, so the model was used to assess the impacts of chlorine chemistry on ozone formation. Based on the current emissions inventory, chlorine emissions have the potential to enhance 1-h-averaged ozone mixing ratios by 70 ppb, in very localized areas, during morning hours. Over wider areas, and at times of day when peak ozone concentrations are observed, the impacts of chlorine emissions on ozone concentrations are typically less than 10 ppb. Chlorine emissions also influenced changes in ozone concentrations due to hydrocarbon and NOx emission controls.     

Shelf-life of minimally processed lettuce and cabbage treated with gaseous chlorine dioxide and cysteine

Gaseous ClO2 was evaluated for effectiveness in prolonging the shelf-life of minimally processed (MP) lettuce and MP cabbage, previously immersed in a cysteine solution in order to inhibit browning occurring during ClO2 treatment. Each vegetable was shredded, washed, and separated in two portions, one to be treated with ClO2 gas and the other to remain untreated as reference sample. The batch to be treated with ClO2 gas was immersed for 1 min in a 0.5% solution of HCl.L-cysteine monohydrate. Then both batches were spun dried. MP vegetables were decontaminated in a cabinet at 90-91% relative humidity and 22-25 degrees C up to 10 min, including 30 s of ClO2 injection into the cabinet. The ClO2 concentration rose to 1.74 mg/L (MP lettuce) and 1.29 mg/L (MP cabbage). Then samples were stored under modified atmosphere at 7 degrees C for shelf-life studies. Changes in O2 and CO2 headspace concentrations, microbiological quality (aerobic plate count (APC), psychrotrophs, lactic acid bacteria, and yeasts), sensory quality, and pH were followed during storage. The respiration rate of the minimally processed vegetables was significantly increased by the ClO2 gas treatment only in the case of MP cabbage (P<0.05). The gas treatment reduced initially APC and psychrotroph count of MP lettuce and APC, psychrotroph counts, yeast counts and pH of MP cabbage (P<0.05). ClO2 treatment did not cause initially any significant (P<0.05) sensorial alteration, except for a weak off-odour in MP lettuce. Interestingly, no browning was observed after treating, which can be accounted to the use of L-cysteine. Although an initial microbiological reduction was observed due to ClO2 gas treatment, APC and psychrotroph counts reached in the samples treated with ClO2 higher levels than in those non-treated with ClO2 before the third day of the shelf-life study. Untreated and treated samples of MP lettuce were sensorial unacceptable due to bad overall visual quality after 4 days, while treated and untreated MP cabbage remained sensorial acceptable during the 9 days of the study. L-cysteine reduced (P<0.05) the decontamination efficacy of ClO2 when applied to MP cabbage but not in the case of MP lettuce. Gaseous ClO2 failed to prolong the shelf-life of MP lettuce and MP cabbage, the reason for the enhanced growth of microorganisms in decontaminated samples should be investigated. Nonetheless, our results prove that it is possible to inhibit browning caused by ClO2.     

Volatile disinfection byproduct formation resulting from chlorination of organic-nitrogen precursors in swimming pools

Clinical studies have documented the promotion of respiratory ailments (e.g., asthma) among swimmers, especially in indoor swimming pools. Most studies of this behavior have identified trichloramine (NCl3) as the causative agent for these respiratory ailments; however, the analytical methods employed in these studies were not suited for identification or quantification of other volatile disinfection byproducts (DPBs) that could also contribute to this process. To address this issue, volatile DBP formation resulting from the chlorination of four model compounds (creatinine, urea, L-histidine, and L-arginine) was investigated over a range of chlorine/precursor (Cl/P) molar ratios. Trichloramine was observed to result from chlorination of all four model organic-nitrogen compounds. In addition to trichloramine, dichloromethylamine (CH3NCl2) was detected in the chlorination of creatinine, while cyanogen chloride (CNCl) and dichoroacetonitrile (CNCHCl2) were identified in the chlorination of L-histidine. Roughly 0.1 mg/L (as Cl2) NCl3, 0.01 mg/L CNCHCl2, and 0.01 mg/L CH3NCl2 were also observed in actual swimming pool water samples. DPD/FAS titration and MIMS (membrane introduction mass spectrometry) were both employed to measure residual chlorine and DBPs. The combined application of these methods allowed for identification of sources of interference in the conventional method (DPD/FAS), as well as structural information about the volatile DBPs that formed. The analysis by MIMS clearly indicates that volatile DBP formation in swimming pools is not limited to inorganic chloramines and haloforms. Additional experimentation allowed for the identification of possible reaction pathways to describe the formation of these DBPs from the precursor compounds used in this study.     

Comparison of calcium lactate with chlorine as a washing treatment for fresh‐cut lettuce and carrots: quality and nutritional parameters

The efficacies of calcium lactate and chlorine washing treatments of fresh‐cut lettuce and carrots were compared during storage at 4 °C over 10 days. The gas composition of packages, colour, enzyme activity, texture, sensory attributes, microflora and levels of ascorbic acid and carotenoids were evaluated at 1, 3, 7 and 10 days. Calcium lactate treatment was not significantly different to chlorine treatment (p < 0.05) in terms of maintaining colour, texture and acceptability of fresh‐cut lettuce and carrots during the entire storage period. The washing treatments did not affect levels of ascorbic acid of fresh‐cut lettuce or carrots. Carotenoid levels were higher in calcium lactate‐treated carrots than chlorine‐treated samples at the end of storage. Mesophilic, psychrotrophic and lactic acid bacteria counts were not significantly different between treatments for both vegetables. Copyright © 2005 Society of Chemical Industry     

News: Study finds no correlation between chlorine incineration and dioxin formation

Technology.     

Muscle glycogen: Comparison of iodine binding and enzyme digestion assays and application to meat samples

A rapid assay for tissue glycogen is described. Bovine liver and muscle glycogen were solubilized with perchloric acid (7-10%) and incubated with an iodine (I(2)-KI) solution containing saturated CaCl(2). The optical density of the amber-brown color was determined at 460 nm. Color development was immediate, stable for up to 2 h, and was linear with respect to glycogen concentrations up to 600 μg glycogen/ml. The iodine assay was applied to fresh, frozen, and aged bovine muscle samples and was compared to enzymic (amyloglucosidase) digestion of glycogen followed by glucose determination. The correlation between the iodine and enzyme methods was linear over the range of 0-1400 g glycogen/g tissue (corr = 0·875; P < 0·01; n = 172). The iodine binding assay can be employed with confidence as an indicator of tissue [glycogen] and is faster and more reliable than the enzyme assay. Comparison of the iodine enzyme assays on aged meat samples revealed marked decreases in muscle glycogen during the first 48 h post slaughter. The decreases were identical whether determined by iodine binding or enzyme assay. Regardless of assay method, post-mortem concentrations of glycogen in bovine sternomandibularis muscle were more variable than in longissimus dorsi samples.     

Halonitroalkanes, halonitriles, haloamides, and N-nitrosamines: a critical review of nitrogenous disinfection byproduct formation pathways

Interest in the formation of nitrogenous disinfection byproducts (N-DBPs) has increased because toxicological research has indicated that they are often more genotoxic, cytotoxic, or carcinogenic than many of the carbonaceous disinfection byproducts (C-DBPs) that have been a focus for previous research. Moreover, population growth has forced utilities to exploit source waters impaired by wastewater effluents or algal blooms. Both waters feature higher levels of organic nitrogen, that might serve as N-DBP precursors. Utilities are exploring new disinfectant combinations to reduce the formation of regulated trihalomethanes and haloacetic acids. As some of these new combinations may promote N-DBP formation, characterization of N-DBP formation pathways is needed. Formation pathways for halonitroalkanes, halonitriles, haloamides, and N-nitrosamines associated with chlorine, ozone, chlorine dioxide, UV, and chloramine disinfection are critically reviewed. Several important themes emerge from the review. First, the formation pathways of the N-DBP families are partially linked because most of the pathways involve similar amine precursors. Second, it is unlikely that a disinfection scheme that is free of byproduct formation will be discovered. Disinfectant combinations should be optimized to reduce the overall exposure to toxic byproducts. Third, the understanding of formation pathways should be employed to devise methods of applying disinfectants that minimize byproduct formation while accomplishing pathogen reduction goals. Fourth, the well-characterized nature of the monomers constituting the biopolymers that likely dominate the organic nitrogen precursor pool should be exploited to predict the formation of byproducts likely to form at high yields.     

Development and interpretation of disinfection byproduct formation models using the Information Collection Rule database

Multiple linear regression models were used to examine relationships between water quality, treatment, and disinfection byproduct (DBP) formation in Information Collection Rule field data. Finished water models were specified using a cross-validation approach based on data for 225 free chlorine treatment plants. Turbidity, bromide, temperature, alkalinity, total organic carbon, ultraviolet absorbance at 254 nm, pH, chlorine residual, chlorine consumed, and chlorine contact time were employed as independent variables. Important trends within the trihalomethane, dihaloacetic acid, and trihaloacetic acid classes were observed. Bromide was a significant predictor for all DBP species and its influence changed in sign and magnitude with the extent of bromine substitution. A similar pattern followed by alkalinity suggested it plays an important role as an indicator of natural organic matter hydrophobicity and reactivity. Chlorine consumed and organic precursor variables were significant predictors in almost all DBP species models, exhibiting trends opposite to those for alkalinity and bromide. Temperature was the most significant variable in chloroform and chloral hydrate models and its significance declined with increasing bromine substitution within the trihalomethane class. pH had a strong positive influence on chloroform formation, a negative influence on trihaloacetic acid formation, and no influence on dihaloacetic acid formation.     

Stability of iodine in salt fortified with iodine and iron

BACKGROUND: Determining the stability of iodine in fortified salt can be difficult under certain conditions. Current methods are sometimes unreliable in the presence of iron. OBJECTIVE: To test the new method to more accurately estimate iodine content in double-fortified salt (DFS) fortified with iodine and iron by using orthophosphoric acid instead of sulfuric acid in the titration procedure. METHODS: A double-blind, placebo-controlled study was carried out on DFS and iodized salt produced by the dry-mixing method. DFS and iodized salt were packed and sealed in color-coded, 0.5-kg, low-density polyethylene pouches, and 25 of these pouches were further packed and sealed in color-coded, double-lined, high-density polyethylene bags and transported by road in closed, light-protected containers to the International Council for the Control of Iodine Deficiency Disorders (ICCIDD), Delhi; the National Institute of Nutrition (NIN), Hyderabad; and the Orissa Unit of the National Nutrition Monitoring Bureau (NNMB), Bhubaneswar. The iodine content of DFS and iodized salt stored under normal room conditions in these places was measured by the modified method every month on the same prescribed dates during the first 6 months and also after 15 months. The iodine content of DFS and iodized salt stored under simulated household conditions was also measured in the first 3 months. RESULTS: After the color code was broken at the end of the study, it was found that the DFS and iodized salt stored at Bhubaneswar, Delhi, and Hyderabad retained more or less the same initial iodine content (30-40 ppm) during the first 6 months, and the stability was not affected after 15 months. The proportion of salt samples having more than 30 ppm iodine was 100% in DFS and iodized salt throughout the study period. Daily opening and closing of salt pouches under simulated household conditions did not result in any iodine loss. CONCLUSIONS: The DFS and iodized salt prepared by the dry-mixing method and stored at normal room conditions had excellent iodine stability for more than 1 year.     

Reduction of nitrite levels in fresh lettuces with aqueous chlorine dioxide treatment

Leafy vegetables are the major source of nitrite intake in the human diet, and technological processing to control the nitrite levels is necessary to the harvested vegetables destined for consumption. In this work, the effect of aqueous chlorine dioxide (ClO₂) treatment on the nitrite levels in fresh lettuces during storage was studied. The results showed the appropriate aqueous ClO₂ solutions treatment (30 and 45 mg L^?1, 10 min) could reduce the nitrite levels or retard the peak occurrence in fresh lettuces during storage. The reduction of nitrite levels in fresh lettuces with appropriate ClO₂ treatment can be attributed to two aspects including the inactivation of nitrate reductase directly and the reduction of the bacterial populations. This study will provide a useful method to reduce the nitrite levels in fresh lettuces destined for short storage followed by consumption.     

Comparison of teat dips with differing iodine concentrations in prevention of mastitis infection

Six commercial dairy herds were used to test the relative efficacy of three concentrations of iodine as a teat dip over 12 mo. Concentrations were .1, .25, and 1% iodine with free iodine contents of 3.5, 4.0, and 1.0 ppm. Two concentrations were compared in each herd. The greatest number of new infections (71) occurred in approximately 120 cows whose teats were dipped with the 1% iodine dip, and the fewest (52) occurred in a similar number of cow quarters dipped in .1% iodine; however, differences were not significant. Clinical mastitis was highest in the 1% group. If all clinical mastitis were the result of infection, even if bacteria were not isolated from the pretreatment sample or from samples collected at the start of the study and those quarters were added to the totals, then reduction of new infection with the .1% product would be significant.