Comparison of numerical calculations and ALOHA modeling in consequence assessment of chlorine gas emissions from ethylene dichloride reactors.

Incidents involving chemical storage tanks in the petrochemical industry are significant events with severe consequences. Within the petrochemical industry, EDC is a sector that produces ethylene dichloride through the reaction of chlorine and ethylene. The present research was conducted to evaluate the consequences of chlorine gas released from the EDC reactor in a petrochemical industry in southern Iran. Data regarding reactor specifications were obtained from the factory's technical office, while climatic data was acquired from the Meteorological Organization. The consequences of chlorine gas release from the reactor were assessed in four predefined scenarios using numerical calculation methods and modeling with the ALOHA software. The numerical calculation method involved thermodynamic fluid path analysis, discharge coefficient calculations, and wind speed impact analysis. The hazard radius was determined based on the ERPG1-2-3 index. Results showed that in the scenario of chlorine gas release from EDC reactors, according to the ALOHA model, an increase in wind speed from 3 to 7 m/h led to an expanded dispersion radius. At a radius of 700 m from the reactor, the maximum outdoor concentration reached 3.12 ppm, decreasing to 2.27 ppm at 800 m and further to 1.53 ppm at 1000 m. The comparison of numerical calculations and modeling using the ALOHA software indicates the desirable conformity of the results with each other. The R2 coefficient for evaluating the conformity of the results was 0.9964, indicating the desired efficiency of the model in evaluating the consequences of the release of toxic gasses from the EDC tank. The results of this research can be useful in designing the site and emergency response plan.

Transformation of 6PPDQ during disinfection: Kinetics, products, and eco-toxicity assessment.

N-phenyl-N'-(1,3-dimethyl butyl)-p-phenylenediamine-quinone (6PPDQ) currently arouses broad concerns because of its acute lethality to coho salmon and rainbow trout at environmentally relevant concentrations and the wide occurrence in runoff-impacted water. Investigation on the fate and transformation of 6PPDQ in various treatment processes is necessary for its risk assessment and control. Here, we explored the transformation of 6PPDQ during disinfection with its precursor 6PPD as a reference, focusing on kinetics, products, and toxicity variation. 6PPDQ readily reacted with hypochlorite and chlorine dioxide with second-order rate constants of 2580 ± 143 M-1 s-1 and 614 ± 52 M-1 s-1 (pH 7.0 and 25 °C), which are slightly lower than the reactions of 6PPD. We tentatively identified thirteen transformation products for 6PPDQ and eight for 6PPD in reaction with the two disinfectants. It seems that the quinone ring of 6PPDQ and the p-phenylenediamine moiety of 6PPD are reactive sites. The transformation of these compounds probably proceeds through Cl-substitution, ring cleavage, hydroxylation, and amine oxidation and hydrolysis. Tests with zebrafish embryos revealed that the transformation products of 6PPDQ could have higher eco-toxicity than the parent compound, while the toxicity of the 6PPD products remained nearly unchanged. The increased toxicity of 6PPDQ during disinfection highlights the necessity to substantially reduce its content before the disinfection of runoff-impacted water.

Chlorination of UV Filters with Antioxidant Shield in Swimming Pool Waters - Products Identification and Toxicity Assessment.

This work summarizes our research on synthesis, characterization and toxicity of selected UV-A filters and their antioxidant shield in commercial formulation - resveratrol. Benzophenone type of UV filters react under disinfection conditions with chlorine and form different mono- and dichlorinated products, while dibenzoylmethane derivatives, such as avobenzone, react with chlorine and form two main bridge chlorinated products followed by numerous chlorinated species at the advanced stages of the process. Resveratrol showed three main susceptible centers to chlorination, starting from the electrophilic addition to the double bond and continuing with the chlorination of the phenolic moieties. Several experiments conducted under different disinfection conditions (pool/sea water, addition of salts, irradiation) showed basically similar chlorination patters with some variations in terms of product formation. The results of toxicity assessment using different test organisms (Vibrio fischeri, microalgae, daphnids) have shown different sensitivity of testing organisms to the parent UV filters in comparison with chlorinated products as well as different toxicity for specific UV filter in comparison to the others. As the closing loop of all experiments in the laboratory, an up-scaling to the real human skin is presented.

Bisphenol A degradation by chlorine dioxide (ClO2) and S(IV)/ClO2 process: Mechanism, degradation pathways and toxicity assessment.

Recently, it has been reported that chlorine dioxide (ClO2) and (bi)sulfite/ClO2 showed excellent performance in micropollutant removal from water; however, the degradation mechanisms and application boundaries of the two system have not been identified. In this study, bisphenol A (BPA) was chosen as the target contaminant to give multiple comparisons of ClO2 and S(IV)/ClO2 process regarding the degradation performance of contaminant, generation of reactive species, transformation of products and toxicity variation. Both ClO2 and S(IV)/ClO2 can degrade BPA within 3 min. The BPA degradation mechanism was mainly based on direct oxidation in ClO2 process while it was attributed to radicals (especially SO4·-) generation in S(IV)/ClO2 process. Meanwhile, the effect of pH and coexisting substances (Cl-, Br-, HCO3- and HA) were evaluated. It was found that ClO2 preferred the neutral and alkaline condition and S(IV)/ClO2 preferred the acidic condition for BPA degradation. An unexpected speed-up of BPA degradation was observed in ClO2 process in the presence of Br-, HCO3- and HA. In addition, the intermediate products in BPA degradation were identified. Three exclusive products were found in ClO2 process, in which p-benzoquinone was considered to be the reason of the acute toxicity increase in ClO2 process.

Formation characteristics and acute toxicity assessment of THMs and HAcAms from DOM and its different fractions in source water during chlorination and chloramination.

The formation characteristics of trihalomethanes (THMs) and haloacetamides (HAcAms) from dissolved organic matter and its fractions were investigated during chlorine-based disinfection processes. The relationships between water quality parameters, fluorescence parameters, and the formation levels of THMs and HAcAms were analyzed. The fractions contributing most to the acute toxicity were identified. The trichloromethane (TCM) generation level (72 h) generally followed the order of Cl2 > NH2Cl > NHCl2 process. The NHCl2 process was superior to the NH2Cl process in controlling TCM formation. Hydrophobic acidic substance (HOA), hydrophobic neutral substance (HON), and hydrophilic substance (HIS) were identified as primary precursors of 2,2-dichloroacetamide and trichloroacetamide during chlorination and chloramination. The formation of TCM mainly resulted from HOA, HON and HIS fractions relatively uniformly, while HOA and HIS fractions contributed more to the formation of bromodichloromethane and dibromomonochloromethane. UV254 could be used as an alternative indicator for the amount of ΣTHMs formed during chlorination and chloramination processes. Dissolved organic nitrogen was a potential precursor of 2,2-dichloroacetamide during chlorination process. The fractions with the highest potential acute toxicity after the chlorination were water-dependent.

Comparative Life Cycle Assessment of Water Disinfection Processes Applicable in Low-Income Settings.

Access to safe, sufficient water for health and sanitation is a human right, and the reliable disinfection of water plays a critical role in addressing this need. The environmental impact and sustainability of water disinfection methods will also play a role in overall public health. This study presents an investigation of the environmental life cycle impacts of four ultraviolet disinfection systems utilizing ambient solar radiation directly and indirectly for water disinfection in comparison to chlorination and water delivery for application in low-income settings. Product inspection and existing literature were used to define a life cycle functional unit of 1 m3 of water for each system, which allowed quantification of material use, infrastructure requirements, and life cycle of the original components of each system and those needed to keep them operational for the studied lifespans (1, 5, 10, and 20 years) and scales (30, 100, 500, and 1000 L per day). For all studied cases, chlorine had the lowest impact in all impact categories, but end-user acceptance of chlorine in some settings is low, driving interest in low-impact alternatives. Disinfection based on low-pressure mercury lamps had the next lowest normalized impact in most categories and may represent a viable alternative, particularly for long-term (10+ years), high production (500+ liters per day) scenarios.

Chlorination and bromination of 1,3-diphenylguanidine and 1,3-di-o-tolylguanidine: Kinetics, transformation products and toxicity assessment.

This works investigates the chlorination and bromination of two rubber and polymer related chemicals, which have emerged as relevant water contaminants, i.e. 1,3-di-o-tolylguanidine (DTG) and 1,3-diphenylguanidine (DPG). Kinetic constants at different pH values were obtained and modelled, taking into account the pKa values of DTG/DPG and HClO, showing that the maximum reaction rate (kapp > 104 M-1 s-1) is obtained at pH values 8.8 for DPG and 9.1 for DTG. Bromination is also very fast, although unlike chlorination, deviation from the model was observed at neutral pH, which was attributed to formation of metastable transformation product (TP). A total of 35 TPs, corresponding to halogenation, hydroxylation, formation of monophenylguanidine derivatives and cyclization reactions, were tentatively identified. Furthermore it was found that chloroform can be formed up to a 25% molar yield, while dichloroacetonitrile was formed into less than a 3% yield. Several ecotoxicological endpoints were predicted by quantitative structure-activity relationship models (QSAR) for the TPs, some of which were predicted to be more toxic than DPG/DTG. Also a chlorinated solution investigated by a Vibrio Fisheri acute toxicity test, confirmed that toxicity increases with chlorination.

Oxidation of Microcystic-LR via the solar/chlorine process: Radical mechanism, pathways and toxicity assessment.

Microcystin-LR (MC-LR) is the most widely distributed and harmful variant toxins released by cyanobacteria, which poses potential threaten to people and aquatic animals when entering natural water. In our research, solar/chlorine process was comprehensively investigated to degrade and detoxify MC-LR. Under the chlorine concentration of 1.0 mg L-1, MC-LR (1.0 µM) was decreased by 96.7%, 26%, and 9% by solar/chlorine process, chlorination, and solar irradiation respectively. Quenching experiments confirmed that reactive chlorine species (RCS) and hydroxyl radical (HO) were the predominant reactive species in solar/chlorine process at neutral condition, and ozone was generated because of the participation of triplet-state oxygen (O(3P)). The respective contributions of each reactive species were calculated with the order as: RCS, HO, ozone, and solar irradiation. The presence of HCO3- and natural organic matter in water inhibited the degradation efficiency of MC-LR. Moreover, the transformation products of MC-LR generated during the solar/chlorine process were identified and a possible pathway was proposed. The hepatotoxicity of MC-LR and its transformation products was compared using protein phosphatase 2A. Our experimental results revealed that the concentration and hepatotoxicity of MC-LR both significantly decreased, and most products were not hepatoxic. Overall, the solar/chlorine process is a promising alternative technology to degrade MC-LR during eutrophication.

Mechanism insight of acetaminophen degradation by the UV/chlorine process: kinetics, intermediates, and toxicity assessment.

The removal of acetaminophen (AAP) in aqueous solution by the UV/chlorine process was evaluated. The effect of chlorine dose, the initial AAP concentration, pH value, and UV intensity on the reaction were also investigated. The degradation mechanism and the ecological risk were further discussed. The results indicated that AAP degradation fitted pseudo-first-order kinetics. Compared with UV alone or dark chlorination, the combination of UV and chlorine significantly accelerated the degradation process. The AAP degradation was positively affected by chlorine dose and UV intensity, while negatively affected by the initial AAP concentration and ammonia nitrogen concentration during the UV/chlorine process. The frontier orbital theory analysis shows that the C5 position in the benzene ring of AAP is likely to be the first site attacked by HO• and Cl• radical to form the products. Twelve intermediates were identified by Q-TOF and GC-MS. The possible degradation pathways were also proposed. Luminescent bacteria experiment and ECOSAR prediction both revealed that acute toxicity of AAP degradation could only be partially reduced. Ecological risks during the UV/chlorine process need to be further evaluated.

Free chlorine reactions of angiotensin II receptor antagonists: Kinetics study, transformation products elucidation and in-silico ecotoxicity assessment.

Angiotensin II receptor antagonists (ARA II) are widely employed in the treatment of hypertension-related diseases. Because of their partial metabolization and limited biodegradability, these drugs have become ubiquitous pollutants in the aquatic environment, including surface water. This research evaluated the reactivity of the ARA II drugs: irbesartan (IRB), losartan (LOS) telmisartan (TEL) and valsartan (VAL) with free chlorine. Responses of parent compounds and their transformation products (TPs) were followed by liquid chromatography (LC) with quadrupole (Q) time-of-flight (TOF) mass spectrometry. Degradation experiments were carried out using ultrapure and river water samples, adjusted at different pHs and, in some cases, adding a small amount (ng mL-1 level) of bromide salts. Whilst TEL and VAL remained stable in presence of relatively high concentrations of free chlorine (10 mg L-1), IRB and LOS were removed according to a pseudo-first order kinetics model. Considering an initial chlorine concentration of 10 mg L-1, their half-lives varied between 6 and 734 min, depending mostly on the water pH. IRB reacted with free chlorine through hydroxylation processes, with and without molecular cleavage and re-arrangements in the imidazolone ring. Its TPs showed a lower in-silico predicted toxicity than the parent drug. In case of LOS, two major competitive degradation routes were identified. They involved replacement of the methanol group attached to the imidazole cycle by chlorine or bromine, and the cleavage of this cycle with removal of the chlorinated carbon and the nitrogen in alpha position. The TPs generated following the first route are predicted to be more toxic than LOS.

Quantitative Assessment of rPM6 for Fluorine- and Chlorine-Containing Metal Complexes: Comparison with Experimental, First-Principles, and Other Semiempirical Results.

We report a reparameterization of PM6 parameters for fluorine and chlorine using our training set containing transition metal complexes. Spin unrestricted calculations with the resulting rPM6 (UrPM6) were examined quantitatively using two test sets: (i) the description of magnetic interactions in 25 dinuclear metal complexes and (ii) the prediction of barrier heights and reaction energies for epoxidation and fluorination reactions catalyzed by high-valent manganese-oxo species. The conventional UPM6 and UPM7 methods were also evaluated for comparison on the basis of either experimental or computational (the UB3LYP/SVP level) outcomes. The merits of UrPM6 are highlighted by both the test sets. As regards magnetic exchange coupling constants, the UrPM6 method had the smallest mean absolute errors from the experimental data (19 cm-1), followed by UPM7 (119 cm-1) and UPM6 (373 cm-1). For the epoxidation and fluorination reactions, all of the transition state searches were successful using UrPM6, while the success rates obtained by UPM6 and UPM7 were only 50%. The UrPM6-optimized stationary points also agreed well with the reference UB3LYP-optimized geometries. The accuracy for estimating reaction energies was also greatly remedied.

Ozone and chlorine reactions with dissolved organic matter - Assessment of oxidant-reactive moieties by optical measurements and the electron donating capacities.

Oxidation processes are impacted by the type, concentration and reactivity of the dissolved organic matter (DOM). In this study, the reactions between various types of DOM (Suwannee River fulvic acid (SRFA), Nordic Reservoir NOM (NNOM) and Pony Lake fulvic acid (PLFA)) and two oxidants (ozone and chlorine) were studied in the pH range 2-9 by using a combination of optical measurements and electron donating capacities. The relationships between residual electron donating capacity (EDC) and residual absorbance showed a strong pH dependence for the ozone-DOM reactions with phenolic functional groups being the main reacting moieties. Relative EDC and absorbance abatements (UV254 or UV280) were similar at pH 2. At pH 7 or 9, the relative abatement of EDC was more pronounced than for absorbance, which could be explained by the formation of UV-absorbing products such as benzoquinone from the transformation of phenolic moieties. An increase in fluorescence abatement with increasing pH was also observed during ozonation. The increase in fluorescence quantum yields could not be attributed to formation of benzoquinone, but related to a faster abatement of phenolic moieties relative to fluorophores with low ozone reactivity. The overall •OH yields as a result of DOM-induced ozone consumption increased significantly with increasing pH, which could be related to the higher reactivity of phenolic moieties at higher pH. The •OH yields for SRFA and PLFA were proportional to the phenolic contents, whereas for NNOM, the •OH yield was about 30% higher. During chlorination of DOM at pH 7 an efficient relative EDC abatement was observed whereas the relative absorbance abatement was much less pronounced. This is due to the formation of chlorophenolic moieties, which exert a significant absorbance, and partly lose their electron donating capacity. Pre-ozonation of SRFA leads to a decrease of chloroform and haloacetic acid formation, however, only after a threshold of > ∼50% abatement of the EDC and under conditions which are not precursor limited. The decrease in chloroform and haloacetic acid formation after the threshold EDC abatement was proportional to the relative residual EDC.

[Chlorination of Naproxen: Removal, Transformation and Risk Assessment].

The by-products produced during chlorination of pharmaceutically active compounds (PhACs) have created widespread public concern. Chlorination of a typical PhAC, naproxen (NAP), was studied. NAP chlorination parameters, intermediates identification, chlorination mechanism, and risk assessment during chlorination process have also been discussed. The results showed that NAP chlorination could fit well with the fist-order kinetics. The rate of removal and rate constants of NAP chlorination decreased with increasing initial NAP concentration and ammonium dosage, while these values increased with increasing initial free chlorine concentration. Acidic condition of the solution could significantly promote NAP chlorination. Five intermediates were identified by HPLC-MS/MS, and the mechanism of NAP chlorination was also put forward. Vibrio fischeri toxicity analysis and ESCOAR prediction indicated that higher toxicity intermediates were produced during NAP chlorination, which pose a potential threat to drinking water safety.

Assessment of recommended approaches for containment and safe handling of human excreta in emergency settings.

Ebola and cholera treatment centres (ETC and CTC) generate considerable quantities of excreta that can further the transmission of disease amongst patients and health workers. Therefore, approaches for the safe handling, containment and removal of excreta within such settings are needed to minimise the likelihood of onward disease transmission. This study compared the performance and suitability of three chlorine-based approaches (0.5% HTH, NaDCC and NaOCl (domestic bleach)) and three lime-based approaches (10%, 20% and 30% Ca(OH)2). The experiments followed recent recommendations for Ebola Treatment Centres. Three excreta matrices containing either raw municipal wastewater, or raw municipal wastewater plus 10% or 20% (w/v) added faecal sludge, were treated in 14 litre buckets at a ratio of 1:10 (chlorine solutions or lime suspensions: excreta matrix). The effects of mixing versus non-mixing and increasing contact time (10 and 30 mins) were also investigated. Bacterial (faecal coliforms (FC) and intestinal enterococci (IE)) and viral (somatic coliphages (SOMPH), F+specific phages (F+PH) and Bacteroides fragilis phages (GB-124PH)) indicators were used to determine the efficacy of each approach. Lime-based approaches provided greater treatment efficacy than chlorine-based approaches, with lime (30% w/v) demonstrating the greatest efficacy (log reductions values, FC = 4.75, IE = 4.16, SOMPH = 2.85, F+PH = 5.13 and GB124PH = 5.41). There was no statistical difference in efficacy between any of the chlorine-based approaches, and the highest log reduction values were: FC = 2.90, IE = 2.36, SOMPH = 3.01, F+PH = 2.36 and GB124PH = 0.74. No statistical difference was observed with respect to contact time for any of the approaches, and no statistical differences were observed with respect to mixing for the chlorine-based approaches. However, statistically significant increases in the efficacy of some lime-based approaches were observed following mixing. These findings provide evidence and practical advice to inform safe handling and containment of excreta and ensure more effective health protection in future emergency settings.

Life cycle environmental and economic implications of small drinking water system upgrades to reduce disinfection byproducts.

Many of the small drinking water systems in the US that utilize simple filtration and chlorine disinfection or chlorine disinfection alone are facing disinfection byproduct (DBP) noncompliance issues, which need immediate upgrades. In this study, four potential upgrade scenarios, namely the GAC, ozone, UV30, and UV186 scenarios, were designed for a typical small drinking water systems and compared in terms of embodied energy, carbon footprint, and life cycle cost. These scenarios are designed to either reduce the amount of DBP precursors using granular activated carbon filtration (the GAC scenario) or ozonation (the ozone scenario), or replace the chlorine disinfection with the UV disinfection at different intensities followed by chloramination (the UV30 and UV186 scenarios). The UV30 scenario was found to have the lowest embodied energy (417 GJ/year) and life cycle cost ($0.25 million US dollars), while the GAC scenario has the lowest carbon footprint (21 Mg CO2e/year). The UV186 scenario consistently presents the highest environmental and economic impacts. The major contributors of the economic and environmental impacts of individual scenarios also differ. Energy and/or material consumptions during the operation phase dominate the environmental impacts of the four scenarios, while the infrastructure investments have a noticeable contribution to the economic costs. The results are sensitive to changes in water quality. An increase of raw water quality, i.e., an increase in organic precursor content, could potentially result in the ozone scenario being the least energy intensive scenario, while a decrease of water quality could greatly reduce the overall competitiveness of the GAC scenario.

Degradation of 5,5-diphenylhydantoin by chlorination and UV/chlorination: kinetics, transformation by-products, and toxicity assessment.

This study investigated the reaction kinetics and mechanism of the degradation of 5,5-diphenylhydantoin (DPH) during conventional chlorination and UV/chlorination. DPH is one of the antiepileptic drugs, which has frequently been detected in the aquatic environment. For chlorination, the second-order rate constant for the reaction between DPH and free active chlorine (FAC) was determined at pH 5 to 8. At pH 6 to 8, the efficiency of chlorination in the removal of DPH was found to be dominated by the reaction involving hypochlorous acid (HOCl). The result also showed that anionic species of DPH was more reactive toward FAC as compared with neutral DPH. For UV/chlorination, the effect of FAC dosage and pH on the degradation of DPH was evaluated. UV/chlorination is a more effective method for removing DPH as compared with conventional chlorination and UV irradiation. The DPH degradation rate was found to increase with increasing FAC concentration. On the other hand, the degradation of DPH was found to be more favorable under the acidic condition. Based on the identified transformation by-products, DPH was found to be degraded through the reaction at imidazolidine-2,4-dione moiety of DPH for both chlorination and UV/chlorination. Toxicity study on the chlorination and UV/chlorination-treated DPH solutions suggested that UV/chlorination is a more efficient method for reducing the toxicity of DPH.

Reaction of diazepam and related benzodiazepines with chlorine. Kinetics, transformation products and in-silico toxicological assessment.

In this work, the reaction of four benzodiazepines (diazepam, oxazepam, nordazepam and temazepam) during water chlorination was studied by means of liquid chromatography-quadrupole-time of flight-mass spectrometry (LC-QTOF-MS). For those compounds that showed a significant degradation, i.e. diazepam, oxazepam and nordazepam, parameters affecting to the reaction kinetics (pH, chlorine and bromide level) were studied in detail and transformation products were tentatively identified. The oxidation reactions followed pseudofirst-order kinetics with rate constants in the range of 1.8-42.5 M-1 s-1, 0.13-1.16 M-1 s-1 and 0.04-20.4 M-1 s-1 corresponding to half-life values in the range of 1.9-146 min, 1.8-87 h and 2.5-637 h for oxazepam, nordazepam and diazepam, respectively, depending of the levels of studied parameters. Chlorine and pH affected significantly the reaction kinetics, where an increase of the pH resulted into a decrease of the reaction rate, whereas higher chlorine dosages led to faster kinetics, as expected in this case. The transformation of the studied benzodiazepines occurs mainly at the 1,4-diazepine 7-membered-ring, resulting in ring opening to form benzophenone derivatives or the formation of a 6-membered pyrimidine ring, leading to quinazoline derivatives. The formation of these by-products was also tested in real surface water samples observing kinetics of oxazepam degradation slower in river than in creek water, while the degradation of the two other benzodiazepines occurred only in the simpler sample (creek water). Finally, the acute and chronical toxicity and mutagenicity of precursors and transformation products were estimated using quantitative structure-activity relationship (QSAR) software tools: Ecological Structure Activity Relationships (ECOSAR) and Toxicity Estimation Software Tool (TEST), finding that some transformation products could be more toxic/mutagenic than the precursor drug, but additional test would be needed to confirm this fact.

A proposal for a test method for assessment of hazard property HP 12 ("Release of an acute toxic gas") in hazardous waste classification - Experience from 49 waste.

A stepwise method for assessment of the HP 12 is proposed and tested with 49 waste samples. The hazard property HP 12 is defined as "Release of an acute toxic gas": waste which releases acute toxic gases (Acute Tox. 1, 2 or 3) in contact with water or an acid. When a waste contains a substance assigned to one of the following supplemental hazards EUH029, EUH031 and EUH032, it shall be classified as hazardous by HP 12 according to test methods or guidelines (EC, 2014a, 2014b). When the substances with the cited hazard statement codes react with water or an acid, they can release HCl, Cl2, HF, HCN, PH3, H2S, SO2 (and two other gases very unlikely to be emitted, hydrazoic acid HN3 and selenium oxide SeO2 - a solid with low vapor pressure). Hence, a method is proposed:For a set of 49 waste, water addition did not produce gas. Nearly all the solid waste produced a gas in contact with hydrochloric acid in 5 min in an automated calcimeter with a volume >0.1L of gas per kg of waste. Since a plateau of pressure is reached only for half of the samples in 5 min, 6 h trial with calorimetric bombs or glass flasks were done and confirmed the results. Identification of the gases by portable probes showed that most of the tested samples emit mainly CO2. Toxic gases are emitted by four waste: metallic dust from the aluminum industry (CO), two air pollution control residue of industrial waste incinerator (H2S) and a halogenated solvent (organic volatile(s) compound(s)). HF has not been measured in these trials started before the present definition of HP 12. According to the definition of HP 12, only the H2S emission of substances with hazard statement EUH031 is accounted for. In view of the calcium content of the two air pollution control residue, the presence of calcium sulphide (EUH031) can be assumed. These two waste are therefore classified potentially hazardous for HP 12, from a total of 49 waste. They are also classified as hazardous for other properties (HP 7, 10and14 for one of them, and HP 10and14 for the other one respectively). Given these results, it can be assumed that few common household and industrial waste will be classified hazardous only by HP 12.

Assessment of air and water contamination by disinfection by-products at 41 indoor swimming pools.

This study was aimed at assessing the profiles (occurrence and speciation) of disinfection by-product (DBP) contamination in air and water of a group of 41 public indoor swimming pools in Québec (Canada). The contaminants measured in the water included the traditional DBPs [i.e., four trihalomethanes (THMs), six haloacetic acids (HAAs)] but also several emergent DBPs [i.e., halonitriles, halonitromethanes, haloketones and nitrosodimethylamine (NDMA)]. Those measured in the air comprised THMs and chloramines (CAMs). Overall, extremely variable DBP levels were found from one pool to another (both quantitatively and in terms of speciation). For instance, in water, among the four THMs, chloroform was usually the most abundant compound (37.9±25.7µg/L). Nevertheless, the sum of the three other brominated THMs represented more than 25% of total THMs at almost half the facilities visited (19 cases). In 13 of them, the levels of brominated THMs (66±24.2µg/L) even greatly outweighed the levels of chloroform (15.2±6.31µg/L). Much higher levels of HAAs (294.8±157.6µg/L) were observed, with a consistent preponderance of brominated HAAs in the swimming pools with more brominated THMs. NDMA levels which were measured in a subset of 8 pools ranged between 2.8ng/L and 105ng/L. With respect to air, chloroform was still the most abundant THM globally (119.4±74.2µg/m(3)) but significant levels of brominated THMs were also observed in various cases, particularly in the previously evoked group of 13 swimming pools with preponderant levels of brominated THMs in water. CAM levels (0.23±0.15mg/m(3)) varied highly, ranging from not detected to 0.56mg/m(3). Overall, the levels were generally relatively high compared to current guidelines or reference values from several countries, and they point to a relatively atypical presence of brominated compounds, and to significant levels of emergent DBPs for which health risk is less documented.

Aqueous chlorination of mefenamic acid: kinetics, transformation by-products and ecotoxicity assessment.

Mefenamic acid (Mfe) is one of the most frequently detected nonsteroidal anti-inflammatory drugs in the environment. This study investigated the kinetics and the transformation by-products of Mfe during aqueous chlorination. The potential ecotoxicity of the transformation by-products was also evaluated. In the kinetic study, the second-order rate constant (kapp) for the reaction between Mfe and free available chlorine (FAC) was determined at 25 ± 0.1 °C. The result indicated that the degradation of Mfe by FAC is highly pH-dependent. When the pH was increased from 6 to 8, it was found that the kapp for the reaction between Mfe and FAC was decreased from 16.44 to 4.4 M(-1) s(-1). Characterization of the transformation by-products formed during the chlorination of Mfe was carried out using liquid chromatography-quadrupole time-of-flight accurate mass spectrometry. Four major transformation by-products were identified. These transformation by-products were mainly formed through hydroxylation, chlorination and oxidation reactions. Ecotoxicity assessment revealed that transformation by-products, particularly monohydroxylated Mfe which is more toxic than Mfe, can be formed during aqueous chlorination.