Using fluorescence surrogates to track algogenic dissolved organic matter (AOM) during growth and coagulation/flocculation processes of green algae

Tracking the variation of the algogenic organic matter (AOM) released during the proliferation of green algae and subsequent treatment processes is crucial for constructing and optimizing control strategies. In this study, the potential of the spectroscopic tool was fully explored as a surrogate of AOM upon the cultivation of green algae and subsequent coagulation/flocculation (C/F) treatment processes using ZrCl₄ and Al₂(SO₄)₃. Fluorescence excitation emission matrix coupled with parallel factor analysis (EEM-PARAFAC) identified the presence of three independent fluorescent components in AOM, including protein-like (C1), fulvic-like (C2) and humic-like components (C3). Size exclusion chromatography (SEC) revealed that C1 in AOM was composed of large-sized proteins and aromatic amino acids. The individual components exhibited their unique characteristics with respect to the dynamic changes. C1 showed the highest correlation with AOM concentrations (R²?=?0.843) upon the C/F processes. C1 could also be suggested as an optical predictor for the formation of trihalomethanes upon the C/F processes. This study sheds a light for the potential application of the protein-like component (C1) as a practical surrogate to track the evolution of AOM in water treatment or wastewater reclamation systems involving Chlorella vulgaris green algae.     

Analysis,accumulation and central effects of trihalomethanes. I. bromoform†

The paper presents the results obtained in a study on the effects of organic micropollutants on the central nervous system of the rat, used herein as a suitable model for neurotoxicologic work. Bromoform, a member of the trihalomethane (THM) family, was the pollutant selected since it becomes a characteristic marker in the Barcelona potable water supply.

Analytical data on the GC‐ECD separation of THMs from other volatile halocarbons is presented. A mixed packed column 10% SE‐30/PEG 20M (94:6) at 70°C provides an adequate separation. The distribution of bromoform in rat plasma and tissues showed an accumulation in brain, kidney and fat, increasing in this order and a rapid elimination after 30 min. The effect on the central aminergic metabolism is studied by HPLC. The increased metabolic activity detected could be attributed either to an increased nervous activity, stimulating the metabolism of serotonin, or to its greater degradation.     

Monitoring the Trihalomethanes Present in Water After Treatment with Chlorine Under Laboratory Condition

In this work assays involving chlorinated water samples, which were previous spiked with humic substances or algae blue green and following the production of the THMs for 30 days is described. To implement the assays, five portions of 1,000 ml of water were stored in glass bottles. The water samples were treated with solutions containing 2, 3, 4 and 5 mg l⁻¹ chlorine. The samples aliquots (60 ml) were transferred into the glass vials, 10 ml were removed to have a headspace and 100 μl of the 10 mg l⁻¹ pentafluortoluene bromide solution was added to each vial. The extraction step was performed by adding 10 g of Na₂SO₄ followed by 5 ml of n-pentane. The vials were stopped with a TFE-faced septum and sealed with aluminum caps. The generated THMs were determined by gas chromatography with electron capture detector using reference solutions with concentration ranging from 8 to 120 μg l⁻¹ THMs. Three assays were monitored during 30 days and chloroform was the predominant compound found in the water samples, while other species of THMs were not detected. The results showed that when the chlorine concentration was increased in water samples containing algae the concentration of THM varied randomly. Nevertheless, in water samples containing humic substances the increase of the THM concentration presented a relationship with the chlorine concentration. It was also observed that chloroform concentration increased with the elapsed time up to one and six days to water samples spiked with humic substances and algae blue green, respectively and decreased along 30 days. By other hand, assays performed using water samples containing decanted algae material showed that THM was not generated by the chlorine addition.     

Trihalomethane concentrations in tap water as determinant of bottled water use in the city of Barcelona

Bottled water consumption is increasing worldwide, despite its huge economic and environmental cost. We aim to describe personal and tap water quality determinants of bottled water use in the city of Barcelona. This cross-sectional study used data from the Health Survey of Barcelona in 2006(N = 5417 adults). The use of bottled water to drink and to cook was evaluated in relation to age, gender, educational level, district and levels of trihalomethanes(THMs), free chlorine, conductivity, chloride, sodium, p H, nitrate and aluminium in municipal tap water using Robust Poisson Regression. The prevalence of bottled water use to drink and cook was 53.9% and 6.7%, respectively. Chemical parameters in water had a large variability(interquartile range of THMs concentrations: 83.2–200.8 μg/L)and were correlated between them, except aluminium. Drinking bottled water increased with educational level, while cooking with bottled water was higher among men than among women and decreased with age. After adjusting by these personal determinants, a dose–response relationship was found between concentrations of all chemicals except aluminium in tap water and bottled water use. The highest association was found for THMs,with a Prevalence Ratio of 2.00(95%CI = 1.86, 2.15) for drinking bottled water and 2.80(95%CI = 1.72, 4.58) for cooking with bottled water, among those with 150 μg/L vs. 100 μg/L THMs in tap water. Conclusion: More than half of Barcelona residents regularly drank bottled water, and the main determinant was the chemical composition of tap water,particularly THM level.     

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.     

Effect of bioflocculants on the coagulation activity of alum for removal of trihalomethane precursors from low turbid water

Reactivity of chlorine towards hydrophobic groups present in natural organic matter(NOM)provokes the formation of carcinogenic disinfection byproducts such as trihalomethanes in chlorinated water. The present study aimed to investigate the variations in coagulant activity of alum using two different bioflocculants(coagulant aid) namely, Moringa oleifera and Cyamopsis tetragonoloba for the removal of hydrophobic fractions of NOM and subsequent chlorine consumption by treated water. Effect of dual coagulants on trihalomethane surrogate parameters such as total organic carbon, dissolved organic carbon, UV absorbing materials and prominent hydrophobic species such as phenolic groups along with aromatic chromophores, polyhydroxy aromatic moiety have also been studied. The concept of differential spectroscopy and absorbance slope index has been employed to understand the combined effects of alum-bioflocculants on the reactivity of NOM with chlorine. Our result shows that the combination of alum and C. tetragonoloba is more efficient for reducing trihalomethane surrogates from chlorinated water as compared to M. oleifera. C. tetragonoloba elicited synchronized effects of sweep coagulation and particle bridging-adsorption which eventually facilitated efficient removal of hydrophobic fractions of NOM. The variation in the mechanistic approach of bioflocculants was due to the presence of cationic charge on M. oleifera and adhesive property of C. tetragonoloba.     

Unlocked disinfection by-product formation potential upon exposure of swimming pool water to additional stimulants

• Swimming pool water was studied for DBPs upon exposure to additional stimulants. • DBP formation could be induced by residual chlorine and extended incubation. • Urine led to a massive formation of chloroform with additional stimulants. • Reactions between chlorine and anthropogenic organics were slow and long-lasting. • Urine control and air ventilation should be on the priority list for pool management. Anthropogenic organics are known to be responsible for the formation of harmful disinfection by-products (DBPs) in swimming pool water (SPW). The research explored an important scenario of SPW with no additional anthropogenic organic input. With stimulations by residual chlorine or additional chlorine and extended incubation, the formation of DBPs, especially chloroform, was significantly induced. Similar observations were found by investigating synthetic SPW made with sweat and urine. The presence of urine led to a massive formation of chloroform, as noted by an approximate 19-fold increase after 165-day incubation with a shock chlorine dose. The research suggests that consistent residual chlorine and long water retention as two typical features of SPW could unlock the DBP formation potential of anthropogenic organics. Thus, limiting the introduction of anthropogenic organics may not have an immediate effect on reducing DBP levels, because their reactions with chlorine can be slow and long-lasting. Pool management should prioritize on control of urine and improving air ventilation. This work is useful to deepen understandings about DBP formation in SPW and provide implications for pool management and prospective legislation.     

Powdered activated carbon coupled with enhanced coagulation for natural organic matter removal and disinfection by-product control: application in a Western Australian water treatment plant

The removal of organic precursors of disinfection by-products (DBPs), i.e. natural organic matter (NOM), prior to disinfection and distribution is considered as the most effective approach to minimise the formation of DBPs. This study investigated the impact of the addition of powdered activated carbon (PAC) to an enhanced coagulation treatment process at an existing water treatment plant on the efficiency of NOM removal, the disinfection behaviour of the treated water, and the water quality in the distribution system. This is the first comprehensive assessment of the efficacy of plant-scale application of PAC combined with enhanced coagulation on an Australian source water. As a result of the PAC addition, the removal of NOM improved by 70%, which led to a significant reduction (80-95%) in the formation of DBPs. The water quality in the distribution system also improved, indicated by lower concentrations of DBPs in the distribution system and better maintenance of disinfectant residual at the extremities of the distribution system. The efficacy of the PAC treatment for NOM removal was shown to be a function of the characteristics of the NOM and the quality of the source water, as well as the PAC dose. PAC treatment did not have the capacity to remove bromide ion, resulting in the formation of more brominated DBPs. Since brominated DBPs have been found to be more toxic than their chlorinated analogues, their preferential formation upon PAC addition must be considered, especially in source waters containing high concentrations of bromide.     

水中溴离子对氯化消毒副产物的影响

根据我国某城市饮用水中三卤甲烷类物质的现状，对水中Ｂｒ＾－的存在，Ｂｒ＾－对ＴＨＭｓ，卤代乙酸类物质形成的影响以及ＴＨＭｓ，ＨＡＡｓ形成的机理等进行综述，且提出了控制饮用水氯化消毒副产物的相应对策。     

Monitoring and factors affecting levels of airborne and water bromoform in chlorinated seawater swimming pools

Water and air quality of eight seawater swimming pools using chlorine disinfection was measured during four sampling campaigns, spread on one full-year, and in four thalassotherapy centers located in Southeast of France. Concentrations of trihalomethanes(THMs) in air and in water as well as concentrations of parameters, including nonpurgeable organic carbon(NPOC), free residual chlorine(Cl_f), pH, Kjeldhal Nitrogen(KN), salinity,conductivity, bromide ions and, water and air temperature, were measured. Water and air samples were collected in triplicates morning — at the opening of the pools —, noon and night — at the closing of the pools —, in summer and winter. Data analysis was performed by Principal Component Analysis(PCA) and rotated component matrix, from both data quality and other parameters such as TOC, aromaticity(UV_(254)), pH, hygrometry, and free residual chlorine(Cl_f). This statistical analysis demonstrates a high correlation between TOC, Cl_fand UV_(254) and THM levels found in air and water, particularly for the major ones(CHBr_3in water:300.0 μg/L mean, 1029.0 μg/L maximum; CHBr_3 in air: 266.1 μg/m~3 mean,1600.0 μg/m~3 maximum, and CHClBr_2 in water: 18.9 μg/L mean, 81.0 μg/L maximum;CHClBr_2 in air: 13.6 μg/m~3 mean, 150.0 μg/m~3maximum). These high levels of bromoform(CHBr_3) are particularly worrisome in such health institutions, even these levels do not exceed the Permissible Exposure Limit(PEL) of 5 mg/m~3 as an 8 hour time-weighted average currently fixed by various administrations, such as Occupational Safety and Health Administration(OSHA).