Effect of NOM characteristics on brominated organics formation by ozonation

In this study, organic fractions, namely, humic acid, fulvic acid, hydrophobic base and neutral, and hydrophilic acid, base, and -neutral, were extracted from source water. First, the characteristics of the organic fractions, such as carboxylic acidity, phenolic acidity, ultraviolet absorbance, and aromatic content, were analyzed. Further, a systematic study was carried out to the by-products obtained when organic fractions, to which various amounts of bromide had been added, were oxidized with ozone. Samples after ozonation were analyzed for several brominated organics. The results indicate that the characteristics of the aquatic organic matter, including carboxylic/phenolic acidity, aromatic/aliphatic content, and ultraviolet absorbance, appear to affect the formation of halogenated organics. In general, hydrophobic organics having higher phenolic acidity, aromatic content, and ultraviolet absorbance have higher ozone consumption and produce higher concentrations of brominated organics than hydrophilic organics. It was also found that humic acid demonstrated the highest bromoform (CHBr(3)), dibromoacetic acid (DBAA), and 2,4-dibromophenol (2,4-DBP) formation, whereas hydrophilic neutral produced less CHBr(3) and 2,4-DBP than the rest of the organic fractions but produced the highest amount of dibromoacetone (DBAC) and dibromoacetonitrile (DBAN).     

新型生物膜光纤传感器测定溴化物的研究

用新型生物膜作载体制成的光纤传感器对工业废水中的溴化物进行了测定,溴化物的线性范围为８×１０－７ｍｏｌ／Ｌ～２×１０－５ｍｏｌ／Ｌ;相对标准偏差为０８％;响应时间为２～３ｍｉｎ。     

Leaching of atrazine, metolachlor and diuron in the field in relation to their injection depth into a silt loam soil

A field experiment was conducted on a Calcaric Cambisol soil to study the consequences of the penetration depth and properties of pesticides on the risk of subsequent leaching. Three pesticides with different mobility characteristics and bromide were injected at 30 cm (where soil organic matter (OM) was 2%) and 80 cm (soil OM 0.5%) on irrigated plots without a crop. The migration of injected solutes was assessed for two years by sampling the soil solution using six porous cups installed at 50 and 150 cm depth and by relating solute contents to drainage water flux estimated by the STICS model (Simulateur mulTIdisciplinaire pour les Cultures Standard). Pesticides injected at 30 cm were strongly retained so that no metolachlor or diuron was detected at 50 and 150 cm. The ratio of atrazine peak concentration in the soil solution to concentration in the injected solution (C/C₀) was 1 × 10⁻³ and 0.2 × 10⁻³, respectively, at 50 and 150 cm. When injected at 80 cm, (C/C₀) of atrazine, metolachlor and diuron were 10 × 10⁻³, 1 × 10⁻³ and 0.3 × 10⁻³ at 150 cm, respectively; 1/(C/C₀) was correlated with K_oc values reported from databases. The ratio of drainage volume to the amount of water at field capacity in the soil layer between the injection point at 30 cm and the water sampling level (V/V₀) at 50 and 150 cm was 0.6 and 0.9, respectively, for bromide and 1.6 and 1.0 for atrazine. V/V₀ of the injected solutes at 80 cm was for bromide, atrazine, metolachlor and diuron 0.6, 0.9, 1.2 and 1.7, respectively; pesticide V/V₀ was correlated with K_oc. The retardation factor was a good indicator of migration risk, but tended to overestimate retardation of molecules with high K_oc. Atrazine desorption represented an additional leaching risk as a source of prolonged low contamination. The large variability in soil solution of bromide and pesticide concentrations in the horizontal plane was attributed to flow paths and clods in the tilled soil layer. This heterogeneity was assumed to channel water fluxes into restricted areas and thereby increase the risk of groundwater contamination. The methodology used in the field proves to provide consistent results.     

A DFT study of the reactions of O3 with Hg° or Br

In the mid 1980s the study of ozone reactivity gained a significant interest with the discoveries of the stratospheric ozone hole (Farman et al., 1985) and of the ozone depletion events in the polar boundary layer (Oltmans et al., 1989). In the stratosphere, the mechanism involves heterogeneous reactions on polar stratospheric clouds that lead to chlorine activation (Solomon et al., 1986). In contrast, tropospheric ozone depletion occurring during polar springtime rather involves reactive bromine species. They are released during a series of photochemical and heterogeneous reactions often called the bromine explosion (see the review of Simpson et al., 2007). In this reaction sequence, an essential step is the generation of photolyzable Br₂, the precursor of two Br atoms, via the multiphasic reaction (1):

(1)

HOBr + Br⁻ + H⁺ → H₂O + Br₂

The production of reactive HOBr could occur with the oxidation of BrO by HO₂.     

Formation of regulated and unregulated disinfection byproducts during chlorination and chloramination: Roles of dissolved organic matter type, bromide, and iodide

Algal blooms and wastewater effluents can introduce algal organic matter (AOM) and effluent organic matter (EfOM) into surface waters, respectively. In this study, the impact of bromide and iodide on the formation of halogenated disinfection byproducts (DBPs) during chlorination and chloramination from various types of dissolved organic matter (DOM, e.g., natural organic matter (NOM), AOM, and EfOM) were investigated based on the data collected from literature. In general, higher formation of trihalomethanes (THMs) and haloacetic acids (HAAs) was observed in NOM than AOM and EfOM, indicating high reactivities of phenolic moieties with both chlorine and monochloramine. The formation of haloacetaldehydes (HALs), haloacetonitriles (HANs) and haloacetamides (HAMs) was much lower than THMs and HAAs. Increasing initial bromide concentrations increased the formation of THMs, HAAs, HANs, and HAMs, but not HALs. Bromine substitution factor (BSF) values of DBPs formed in chlorination decreased as specific ultraviolet absorbance (SUVA) increased. AOM favored the formation of iodinated THMs (I-THMs) during chloramination using preformed chloramines and chlorination-chloramination processes. Increasing prechlorination time can reduce the I-THM concentrations because of the conversion of iodide to iodate, but this increased the formation of chlorinated and brominated DBPs. In an analogous way, iodine substitution factor (ISF) values of I-THMs formed in chloramination decreased as SUVA values of DOM increased. Compared to chlorination, the formation of noniodinated DBPs is low in chloramination.     

Disinfection byproduct formation from algal organic matters after ozonation or ozone combined with activated carbon treatment with subsequent chlorination

Algal organic matter (AOM), including extracellular organic matter (EOM) and intracellular organic matter (IOM) from algal blooms, is widely accepted as essential precursors of disinfection byproducts (DBPs). This study evaluated the effect of ozonation or ozone combined with activated carbon (O₃-AC) treatment on characteristic alternation and DBP formation with subsequent chlorination of Chlorella sp.. The effects of pH and bromide concentration on DBP formation by ozonation or O₃-AC treatment were also investigated. Results showed that the potential formation of DBPs might be attributed to ozonation, but these DBP precursors could be further removed by activated carbon (AC) treatment. Moreover, the formation of target DBPs was controlled at acidic pH by alleviating the reactions between chlorine and AOM. Besides, the bromide substitution factor (BSF) value of trihalomethanes (THMs) from EOM and IOM remained constant after AC treatment. However, THM precursors could be significantly decreased by AC treatment. The above results indicated that O₃-AC was a feasible treatment method for algal-impacted water.     

离子色谱法测定水中溴离子与碘离子

采用离子色谱法测定水中溴离子与碘离子,选择AS19阴离子交换分离柱、KOH淋洗液自动发生器、抑制型电导检测。溴离子与碘离子分别在14.8 μg/L～100 mg/L与30.4 μg/L～100 mg/L范围内线性良好,检出限分别为3.7 μg/L与7.6 μg/L,环境水样平行测定的RSD分别为0.2%～1.5%与0.3%～1.6%,两个质量浓度水平的加标回收率分别为91.8%～105%与89.5%～93.4%。     

Effects of bromide on the formation of THMs and HAAs

The role of bromide in the formation and speciation of disinfection by-products (DBPs) during chlorination was investigated. The molar ratio of applied chlorine to bromide is an important factor in the formation and speciation of trihalomethanes (THMs) and halogenacetic acids (HAAs). A good relationship exists between the molar fractions of THMs and the bromide incorporation factor. The halogen substitution ability of HOBr and HOCl during the formation of THMs and HAAs can be determined based on probability theory. The formation of HAAs, and their respective concentrations, can also be estimated through use of the developed model.     

Evaluating equilibrium and non-equilibrium transport of bromide and isoproturon in disturbed and undisturbed soil columns

In this study, displacement experiments of isoproturon were conducted in disturbed and undisturbed columns of a silty clay loam soil under similar rainfall intensities. Solute transport occurred under saturated conditions in the undisturbed soil and under unsaturated conditions in the sieved soil because of a greater bulk density of the compacted undisturbed soil compared to the sieved soil. The objective of this work was to determine transport characteristics of isoproturon relative to bromide tracer. Triplicate column experiments were performed with sieved (structure partially destroyed to simulate conventional tillage) and undisturbed (structure preserved) soils. Bromide experimental breakthrough curves were analyzed using convective-dispersive and dual-permeability (DP) models (HYDRUS-1D). Isoproturon breakthrough curves (BTCs) were analyzed using the DP model that considered either chemical equilibrium or non-equilibrium transport. The DP model described the bromide elution curves of the sieved soil columns well, whereas it overestimated the tailing of the bromide BTCs of the undisturbed soil columns. A higher degree of physical non-equilibrium was found in the undisturbed soil, where 56% of total water was contained in the slow-flow matrix, compared to 26% in the sieved soil. Isoproturon BTCs were best described in both sieved and undisturbed soil columns using the DP model combined with the chemical non-equilibrium. Higher degradation rates were obtained in the transport experiments than in batch studies, for both soils. This was likely caused by hysteresis in sorption of isoproturon. However, it cannot be ruled out that higher degradation rates were due, at least in part, to the adopted first-order model. Results showed that for similar rainfall intensity, physical and chemical non-equilibrium were greater in the saturated undisturbed soil than in the unsaturated sieved soil. Results also suggested faster transport of isoproturon in the undisturbed soil due to higher preferential flow and lower fraction of equilibrium sorption sites.     

Disinfection byproduct regulatory compliance surrogates and bromide-associated risk

Natural and anthropogenic factors can alter bromide concentrations in drinking water sources. Increasing source water bromide concentrations increases the formation and alters the speciation of disinfection byproducts (DBPs) formed during drinking water treatment. Brominated DBPs are more toxic than their chlorinated analogs, and thus have a greater impact on human health. However, DBPs are regulated based on the mass sum of DBPs within a given class (e.g., trihalomethanes and haloacetic acids), not based on species-specific risk or extent of bromine incorporation. The regulated surrogate measures are intended to protect against not only the species they directly represent, but also against unregulated DBPs that are not routinely measured. Surrogates that do not incorporate effects of increasing bromide may not adequately capture human health risk associated with drinking water when source water bromide is elevated. The present study analyzes trihalomethanes (THMs), measured as TTHM, with varying source water bromide concentrations, and assesses its correlation with brominated THM, TTHM risk and species-specific THM concentrations and associated risk. Alternative potential surrogates are evaluated to assess their ability to capture THM risk under different source water bromide concentration conditions. The results of the present study indicate that TTHM does not adequately capture risk of the regulated species when source water bromide concentrations are elevated, and thus would also likely be an inadequate surrogate for many unregulated brominated species. Alternative surrogate measures, including THM3 and the bromodichloromethane concentration, are more robust surrogates for species-specific THM risk at varying source water bromide concentrations.