Monochloramine loss in the presence of humic acid

Free chlorine has been used extensively as a primary and secondary disinfectant for potable water. Where it is difficult to maintain a free chlorine residual or when disinfection by-products (DBPs) are of concern, monochloramine has been used to provide a stable disinfectant residual in distributions systems. Reactions of disinfectants, free chlorine or monochloramine, with natural organic matter (NOM) consequently result in the formation of DBPs such as trihalomethanes and haloacetic acids. However, few studies have focused on the fate and kinetics of monochloramine loss in the presence of reactive constituents such as NOM. Monochloramine is inherently unstable and decays even without reactive constituents present via a mechanism known as autodecomposition. Therefore, to predict monochloramine concentrations in the presence of NOM is clearly associated with the ability to adequately model autodecomposition. This study presents the results of a semi-mechanisiic model capable of predicting the loss of monochloramine in the presence of humic material in the pH range of 6.55-8.33. The model accounts for both fast and a slow monochloramine demand to explain the loss of monochloramine over the pH range of this study. The formation of dichloroacetic acid was also predicted due to the ability of the model to differentiate monochloramine reaction pathways in the presence NOM. The results shown here demonstrate the ability of a semi-mechanistic model to predict monochloramine residuals and DBP formation in the presence of humic material.     

Optimizing booster chlorination in water distribution networks: a water quality index approach

The optimization of chlorine dosage and the number of booster locations is an important aspect of water quality management in distribution networks. Booster chlorination helps to maintain uniformity and adequacy of free residual chlorine concentration, essential for safeguarding against microbiological contamination. Higher chlorine dosages increase free residual chlorine concentration but generate harmful by-products, in addition to taste and odor complaints. It is possible to address these microbial, chemical, and aesthetic water quality issues through free residual chlorine concentration. Estimating a water quality index (WQI) based on regulatory chlorine thresholds for microbial, chemical, and aesthetics criteria can help engineers make intelligent decisions. An innovative scheme for maintaining adequate residual chlorine with optimal chlorine dosages and numbers of booster locations was established based on a proposed WQI. The City of Kelowna (BC, Canada) water distribution network served to demonstrate the application of the proposed scheme. Temporal free residual chlorine concentration predicted with EPANET software was used to estimate the WQI, later coupled with an optimization scheme. Preliminary temporal and spatial analyses identified critical zones (relatively poor water quality) in the distribution network. The model may also prove useful for small or rural communities where free residual chlorine is considered as the only water quality criterion.     

N-nitrosodimethylamine and trihalomethane formation and minimisation in Southeast Queensland drinking water

This study assesses the prevalence of disinfection by-product (DBP) precursors in some Southeast Queensland drinking water sources by conducting formation potential experiments for the four regulated trihalomethanes (THMs), and the potent carcinogen, N-nitrosodimethylamine (NDMA). NDMA formation potentials were consistently low (<5-21 ng/L), and total THM (tTHM) formation potentials were consistently below the Australian Drinking Water Guideline (250 μg/L). NDMA concentration of finished drinking waters was also monitored and found to be <5 ng/L in all cases. The effect of coagulation and advanced oxidation on the formation of NDMA and THMs is also reported. UV/H(2)O(2) pre-treatment was effective in producing water with very low THMs concentrations, and UV irradiation was an effective method for NDMA degradation. H(2)O(2) was not required for the observed NDMA degradation to occur. Coagulation using alum, ferric chloride or poly(diallyldimethylammonium chloride) (polyDADMAC) was ineffective in removing DBPs precursors from the source water studied, irrespective of the low dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) attained. Rather, coagulation with polyDADMAC caused an increase in NDMA formation potential upon chloramination, and all coagulants led to an increased tTHM formation potential upon chlorination due to the high bromide concentration of the source water studied.     

Oxidation of Cr(III) to Cr(VI) during chlorination of drinking water

Drinking water treatment typically uses strong oxidants such as chlorine which are capable of converting Cr(III) to Cr(VI). The rates and extent of Cr(III) oxidation by chlorine are not well established. Cr(III) oxidation experiments were therefore conducted in distilled deionized water and New York City tap water dosed initially with Cr(III) and supplemented with sodium hypochlorite to increase free chlorine residual. Reaction progress was monitored using capillary electrophoresis which quenched reactions and allowed for quantification of Cr(VI). Three different forms of Cr(III) were used as reactants: a Cr(III) nitrate salt, Cr(III)-EDTA, and Cr(III) hydroxide. Rates of Cr(VI) production for all three forms of Cr(III) were rapid, on the order of hours. However, oxidation rates slowed and a plateau in Cr(VI) concentrations was reached. This resulted in less than 100% conversion of Cr(III) to Cr(VI) even at relatively high chlorine doses (10 to 100 mg L(-1) as Cl(2)). The loss of free chlorine due to a non-Cr chlorine demand, the precipitation of Cr(III) to Cr(OH)(3)(s), and the partial oxidation of Cr(III) to intermediate oxidation states (i.e. Cr(IV) and Cr(V)) were examined and eliminated as possible explanations for this behavior. Consumption of chlorine via reaction with intermediate oxidation states of Cr is therefore offered as a possible explanation for the plateau in Cr(VI) concentrations.     

Predictive model for chloroform during disinfection of water for consumption,city of Montevideo

The objective of this study was to predict chloroform formation resulting from the process of disinfecting water, particularly trihalomethane which is most frequently produced. A statistical model was used which included repeated measurements of water parameters used for monitoring water quality at 51 sites covering the municipal water system of Montevideo. Samples were taken considering different seasons from June 2009 to July 2011 in Montevideo. Total samples (n?=?330) were analytically studied using the headspace-gas chromatography method coupled with mass spectrometry. Chloroform was the dependent variable and the covariables were pH, temperature, free chlorine, and total chlorine. A Tobit analysis with an unstructured correlation matrix was performed, and a significant interaction was found between pH and free chlorine for the prediction of chloroform formation. We concluded that parameters for the continuous control of water quality for consumption can be used to predict the levels of chloroform that may be present. Given the large measurement to variability found in the repeated measurements, the use of averages that include more than one season is not recommended to determine the degree of compliance with acceptable levels established by norms.     

Evaluation of a novel hollow fiber membrane technique for collection of 1,1-dimethylhydrazine in air

The purpose of this study was to develop a novel one-step method for the time-weighted average determination of 1,1-dimethylhydrazine (UDMH) in the air followed by spectrophotometric detection. For this reason, 0.1% hydrochloric acid as the absorbent was used in hollow fiber (HF) membrane for sampling of UDMH from an atmospheric standard chamber. Response surface methodology (RSM) with central composite design (CCD) was used to optimize the sampling parameters, such as flow rate and sampling time. Moreover, several analytical parameters including breakthrough (BT) volume, storage time, and carryover effect of the proposed HF were investigated. The results showed that optimal sampling rate was 9.90 mL/min. In order to validate the proposed method, it was compared with the National Institute for Occupational Safety and Health (NIOSH) 3515 method, which showed good compatibility between the two methods. Intra- and inter-day repeatability values of the HF method were in the range 0.082–0.1 and 0.091–0.12, respectively, and the limits of detection (LODs) and limits of quantitation (LOQs) were 0.002 and 0.006 ng/mL, respectively. The storage time of the proposed HF was 7 days at 2 °C. These results demonstrated that the one-step HF membrane offered a high sensitivity for sampling of UDMH in air.     

A laboratory investigation of the effectiveness of various skin and surface decontaminants for aliphatic polyisocyanates

Isocyanates may cause contact dermatitis and respiratory sensitization leading to asthma. Dermal exposure to aliphatic isocyanates in auto body shops is very common. However, little is known about the effectiveness of available commercial products used for decontaminating aliphatic polyisocyanates. This experimental study evaluated the decontamination effectiveness of aliphatic polyisocyanates for several skin and surface decontaminants available for use in the auto body industry. The efficiency of two major decontamination mechanisms, namely (i) consumption of free isocyanate groups via chemical reactions with active hydrogen components of the decontaminant and (ii) physical removal processes such as dissolution were studied separately for each decontaminant. Considerable differences were observed among surface decontaminants in their rate of isocyanate consumption, of which those containing free amine groups performed the best. Overall, Pine-Sol(R) MEA containing monoethanolamine was the most efficient surface decontaminant, operating primarily via chemical reaction with the isocyanate group. Polypropylene glycol (PPG) had the highest physical removal efficiency and the lowest reaction rate with isocyanates. All tested skin decontaminants performed similarly, accomplishing decontamination primarily via physical processes and removing 70-80% of isocyanates in one wiping. Limitations of these skin decontaminants are discussed and alternatives presented. In vitro testing using animal skins and in vivo testing with field workers are being conducted to further assess the efficiency and identify related determinants.     

水杨酸法检测水质氨氮的改进方法

该氨氮检测方法是对水杨酸分光光度法的改进,通过将50 g/L的水杨酸改为150 g/L的水杨酸钠,将有效氯为3. 5 g/L的次氯酸钠溶液改为5 g/L的二氯异氰尿酸钠溶液,增加了检测试剂的稳定性和贮存时间,同时将氨氮测定上限从1 mg/L提高至2. 5 mg/L,并将显色时间从60 min优化为30 min,使得此方法更为便捷。该方法的氨氮标准曲线线性关系良好,相关系数为0. 999 6,准确性和精密度高,加标回收率良好,适用于不同类型水质中氨氮的检测。     

高氯离子废水化学需氧量分析方法的研究

提出一种测定高氯离子废水 COD的新方法。其消解条件与现行国标法基本相同 ,消解过程产生的氯气用Na OH吸收并测定出氯离子的 COD校正值。由表观 COD值减去氯离子的 COD校正值 ,即为水样的真实 COD值。标样的相对误差在 -1.5 %～ 5 %之间 ,RSD%≤ 5 .5 %。高氯废水的 RSD%≤ 8.0 %。     

Modeling the Formation of Chlorination By-Products During Enhanced Coagulation

Because of increasing need to balance health risks for pathogen control and disinfection by-products (DBP) formation in drinking water supplies, water utilities are forced to closely examine and optimize their disinfection practices. This research was designed to investigate the effects of independent variables of dissolved organic carbon (DOC), ferric chloride dosage, chlorine dose, and reaction time on trihalomethanes (THMs) formation in Terkos Lake Water (TLW) of Istanbul City. A statistically-based empirical model was developed for predicting THM formation during enhanced coagulation. The R ² and F value of model were 0.762 and 460, respectively. The model was found to be statistically significant for all four variables, and model predictions appear to be most accurate for this study. A multiple linear model exhibited the best fit of data. It was observed that THM formation depended primarily on DOC removal. Model calibration, testing and validation were accomplished by using independent data set.     

水中微量偏二甲基肼检测方法的研究和应用

偏二甲基肌是川作火箭推进剂燃料，有较大的毒性，也是环境污染物。它的水中最大允许浓度为０．０６ｍｇ／Ｌ。本研究建立了一种水中微量偏二甲基肼的检测方法，采用钼酸铵作为试剂的比色测定法，方法简便、准确、灵敏度高，可川于现场检测。本文还报道了应用本法测定了水中微量肼和甲基肼的稳定性的结果。     

Determining the agricultural ammonia immission using bark bio-monitoring: comparison with passive sampler measurements

Bark samples of spruce, pine and oak trees were collected at two sites in southern Bavaria which are characterized by high agricultural ammonia emissions. The samples were taken using a recently developed bark sampling device which removes a defined layer of the bark. The bark was then analysed for ammonium concentration in order to reflect the environmental ammonia immission. The measured bark concentrations decreased with rising distance between the sample trees and the ammonia source. This applied (i) to measurements inside a closed forest stand ranging from forest edge with high immission to forest interior with much lower immission, and (ii) to the open field where single-standing trees were sampled. Comparing the ammonium concentrations among the three different tree species revealed significant correlations. Thus, it could be shown that old spruce trees are as usable for bark bio-monitoring as the traditionally used pine and oak trees. The ammonium concentrations of the bark were significantly correlated to measurements taken by ammonia passive samplers at the same locations. These results indicate that bark samples may be used for a standardised monitoring of airborne ammonia load. A major advantage of the technique is the determination of the long-term accumulative ammonia load using a single measurement.     

Reduction of SO2 Emissions by Ammonia Gas During Staged Combustion

To reduce SO2 emissions, ammonia gas was injected into a coal-fired fluidized-bed combustor under staged commbustion condition. The combustor was 2 m high with a 30 cm static bed height and a freeboard height of 170 cm. The ammonia gas was injected at 52 cm and 65 cm above the distributor, which had a temperature of ca. 700 °C, by an uncooled stainless-steel tube injector. The experiments investigated the effects of ammonia gas injection on sulphur dioxide emissions at staged conditions, varying the: (i) excess air level, (ii) secondary air ratio, (iii) fluidizing velocity, (iv) ammonia injection position, and (v) the ammonia : sulphur dioxide molar ratio.A maximum reduction of 66% in SO2 emissions was found at 40% excess air, 65 : 35 staging, 1.5 m/s fluidizing velocity, 65 cm injection height, and an NH3 : SO2 molar ratio of 1.2. The onset of SO2 reduction occurred at an NH3 : SO2 ratio of 0.5. The fluidizing velocity, excess air, level of staging, and ammonia injection height all have a significant influence on SO2 reduction.It is difficult to determine how the SO2 reduction varies with the operating conditions when ammonia is injected in the high temperature zone of the combustor. As sulphur oxides-ammonia reactions are low temperature reactions, the findings confirm the occurrence of reactions above the freeboard or near the exit to the cyclone.     

饮水中挥发性卤代烃成因研究

对影响饮水生成挥发性卤代烃的各种因素进行了研究.发现源水腐殖质等有机物的存在和加氯消毒处理是产生挥发性卤代烃的主要原因,而氯化消毒的温度、时间、源水pH值对其生成有重要影响.     

测定游离氯和总氯样品保存方法研究

建立了游离氯和总氯样品保存方法。用氢氧化钠溶液作为固定剂,现场固定含有游离氯和总氯的水样,使水样pH>12。结果表明,样品经4℃低温避光保存,5 d内测定,测量结果没有显著变化,方法检出限(以Cl2计)为0.004mg/L,加标回收率为96.7%～104%。     

The impact of a rice based diet on urinary arsenic

Rice is elevated in arsenic (As) compared to other staple grains. The Bangladeshi community living in the United Kingdom (UK) has a ca. 30-fold higher consumption of rice than white Caucasians. In order to assess the impact of this difference in rice consumption, urinary arsenicals of 49 volunteers in the UK (Bangladeshi n = 37; white Caucasians n = 12) were monitored along with dietary habits. Total urinary arsenic (As(t)) and speciation analysis for dimethylarsinic acid (DMA), monomethylarsonic acid (MA) and inorganic arsenic (iAs) was conducted. Although no significant difference was found for As(t) (median: Bangladeshis 28.4 μg L(-1)) and white Caucasians (20.6 μg L(-1)), the sum of medians of DMA, MA and iAs for the Bangladeshi group was found to be over 3-fold higher (17.9 μg L(-1)) than for the Caucasians (3.50 μg L(-1)). Urinary DMA was significantly higher (p < 0.001) in the UK Bangladeshis (median: 16.9 μg DMA L(-1)) than in the white Caucasians (3.16 μg DMA L(-1)) as well as iAs (p < 0.001) with a median of 0.630 μg iAs L(-1) for Bangladeshi and 0.250 μg iAs L(-1) for Caucasians. Cationic compounds were significantly lower in the Bangladeshis (2.93 μg L(-1)) than in Caucasians (14.9 μg L(-1)). The higher DMA and iAs levels in the Bangladeshis are mainly the result of higher rice consumption: arsenic is speciated in rice as both iAs and DMA, and iAs can be metabolized, through MA, to DMA by humans. This study shows that a higher dietary intake of DMA alters the DMA/MA ratio in urine. Consequently, DMA/MA ratio as an indication of methylation capacity in populations consuming large quantities of rice should be applied with caution since variation in the quantity and type of rice eaten may alter this ratio.     

Assessing regulatory violations of disinfection by-products in water distribution networks using a non-compliance potential index

Inactivating pathogens is essential to eradicate waterborne diseases. However, disinfection forms undesirable disinfection by-products (DBPs) in the presence of natural organic matter. Many regulations and guidelines exist to limit DBP exposure for eliminating possible health impacts such as bladder cancer, reproductive effects, and child development effects. In this paper, an index named non-compliance potential (NCP) index is proposed to evaluate regulatory violations by DBPs. The index can serve to evaluate water quality in distribution networks using the Bayesian Belief Network (BBN). BBN is a graphical model to represent contributing variables and their probabilistic relationships. Total trihalomethanes (TTHM), haloacetic acids (HAA5), and free residual chlorine (FRC) are selected as the variables to predict the NCP index. A methodology has been proposed to implement the index using either monitored data, empirical model results (e.g., multiple linear regression), and disinfectant kinetics through EPANET simulations. The index’s usefulness is demonstrated through two case studies on municipal distribution systems using both full-scale monitoring and modeled data. The proposed approach can be implemented for data-sparse conditions, making it especially useful for smaller municipal drinking water systems.     

Ascorbic acid reduction of active chlorine prior to determining Ames mutagenicity of chlorinated natural organic matter (NOM)

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 compounds in samples from potable water supplies or laboratory studies of DBP formation. Reduction of oxidizing disinfectants is required since these compounds can kill the bacteria or react with the agar, producing chlorinated byproducts. When mutagens are collected by passing potable water through adsorbing resins, active chlorine compounds react with the resin, producing undesirable mutagenic artifacts. The bioanalytical and chemoanalytical needs of drinking water DBP studies required a suitable reductant. Many of the candidate compounds failed to meet those needs, including 2,4-hexadienoic (sorbic) acid, 2,4-pentanedione (acetylacetone), 2-butenoic (crotonic) acid, 2-butenedioic (maleic and fumaric) acids and buten-2-ol (crotyl alcohol). Candidates were rejected if they (1) reacted too slowly with active chlorine, (2) formed mutagenic byproducts, or (3) interfered in the quantitation of known chlorination DBPs. L-Ascorbic acid reacts rapidly and stoichiometrically with active chlorine and has limited interactions with halogenated DBPs. In this work, we found no interference from L-ascorbic acid or its oxidation product (dehydroascorbic acid) in mutagenicity assays of chlorinated NOM using Salmonella typhimurium TA100, with or without metabolic activation (S9). This was demonstrated for both aqueous solutions of chlorinated NOM and concentrates derived from the involatile, ether-extractable chlorinated byproducts of those solutions.     

Dynamic Cost-Effective Reduction Strategies for Acidification in Europe: An Application to Ireland and the United Kingdom

This paper describes the application of an optimisation model for calculating cost-effective abatement strategies for the reduction of acidification in Europe while taking into account the dynamic character of soil acidification in a number of countries. Environmental constraints are defined in terms of soil quality indicators, e.g., pH, base saturation or the aluminium ion concentration in the soil solution within an optimisation model for transboundary air pollution.We present a case study for Ireland and the United Kingdom. Our results indicate that reduction of sulphur dioxide emission is more cost-effective than that of nitrogen oxides or ammonia. The reduction percentages for sulphur dioxide are highest, for two reasons: (i) marginal sulphur dioxide reduction costs are relatively low compared to marginal reduction costs of nitrogen oxides and ammonia and (ii) sulphur dioxide reduction is more effective in reducing acidification in physical terms than nitrogen oxides or ammonia abatement. Our dynamic analysis shows that a (fast) improvement of soil quality requires high emission reduction levels. These reduction levels are often higher than reduction levels that are typically deduced from the static critical loads approach. Once soil quality targets are reached, in our model, less stringent emission reductions are required to maintain the soil quality at a constant and good target level. Static critical load approaches that ignore dynamic aspects therefore may underestimate the emission reductions needed to achieve predefined soil quality targets.     

Reduction of SO2 emissions by ammonia gas during unstaged combustion

The reduction of SO₂ by the addition of ammonia gas has been studied in a 2 m high fluidized bed combustor having a 30 cm static bed height and a freeboard height of 170 cm. Ammonia gas was injected at 52 cm above the distributor where the temperature is ca. 700° C by an uncooled stainless steel tube injector. Experiments were carried out to investigate the effects of amminia gas injection on sulphur dioxide emissions at unstaged conditions of: (i) excess air level, (ii) NH₃:SO₂ molar ratio, (iii) fluidizing velocity and (iv) bed height.A maximum reduction of 75% in SO₂ emissions was found at 40% excess air, at an NH₃:SO₂ molar ratio of 5.4. The onset of SO₂ reduction occurred at an NH₃:SO₂ ratio of 1.5 However, the most effective ratio was found to be between 3 and 5. Fluidizing velocity and bed height were also found to have significant influence on SO₂ reduction.It is difficult to determine how the SO₂ reduction varied with operating conditions. When ammonia is added in the main combustor zone, the temperature is much higher than that required for the occurrence of sulphur dioxide-ammonia and sulphur trioxide-ammonia reactions. However, this paper points out the significance of ammonia addition in the reduction of sulphur dioxide.