Justine Criquet

Oxidative treatment of bromide-containing waters: Formation of bromine and its reactions with inorganic and organic compounds - A critical review

Bromide (Br(-)) is present in all water sources at concentrations ranging from ≈ 10 to >1000 μg L(-1) in fresh waters and about 67 mg L(-1) in seawater. During oxidative water treatment bromide is oxidized to hypobromous acid/hypobromite (HOBr/OBr(-)) and other bromine species. A systematic and critical literature review has been conducted on the reactivity of HOBr/OBr(-) and other bromine species with inorganic and organic compounds, including micropollutants. The speciation of bromine in the absence and presence of chloride and chlorine has been calculated and it could be shown that HOBr/OBr(-) are the dominant species in fresh waters. In ocean waters, other bromine species such as Br2, BrCl, and Br2O gain importance and may have to be considered under certain conditions. HOBr reacts fast with many inorganic compounds such as ammonia, iodide, sulfite, nitrite, cyanide and thiocyanide with apparent second-order rate constants in the order of 10(4)-10(9)M(-1)s(-1) at pH 7. No rate constants for the reactions with Fe(II) and As(III) are available. Mn(II) oxidation by bromine is controlled by a Mn(III,IV) oxide-catalyzed process involving Br2O and BrCl. Bromine shows a very high reactivity toward phenolic groups (apparent second-order rate constants kapp ≈ 10(3)-10(5)M(-1)s(-1) at pH 7), amines and sulfamides (kapp ≈ 10(5)-10(6)M(-1)s(-1) at pH 7) and S-containing compounds (kapp ≈ 10(5)-10(7)M(-1)s(-1) at pH 7). For phenolic moieties, it is possible to derive second-order rate constants with a Hammett-σ-based QSAR approach with [Formula in text]. A negative slope is typical for electrophilic substitution reactions. In general, kapp of bromine reactions at pH 7 are up to three orders of magnitude greater than for chlorine. In the case of amines, these rate constants are even higher than for ozone. Model calculations show that depending on the bromide concentration and the pH, the high reactivity of bromine may outweigh the reactions of chlorine during chlorination of bromide-containing waters.

Reaction of bromine and chlorine with phenolic compounds and natural organic matter extracts – Electrophilic aromatic substitution and oxidation

Phenolic compounds are known structural moieties of natural organic matter (NOM), and their reactivity is a key parameter for understanding the reactivity of NOM and the disinfection by-product formation during oxidative water treatment. In this study, species-specific and/or apparent second order rate constants and mechanisms for the reactions of bromine and chlorine have been determined for various phenolic compounds (phenol, resorcinol, catechol, hydroquinone, phloroglucinol, bisphenol A, p-hydroxybenzoic acid, gallic acid, hesperetin and tannic acid) and flavone. The reactivity of bromine with phenolic compounds is very high, with apparent second order rate constants at pH 7 in the range of 10(4) to 10(7) M(-1) s(-1). The highest value was recorded for the reaction between HOBr and the fully deprotonated resorcinol (k = 2.1 × 10(9) M(-1) s(-1)). The reactivity of phenolic compounds is enhanced by the activating character of the phenolic substituents, e.g. further hydroxyl groups. With the data set from this study, the ratio between the species-specific rate constants for the reactions of chlorine versus bromine with phenolic compounds was confirmed to be about 3000. Phenolic compounds react with bromine or chlorine either by oxidation (electron transfer, ET) or electrophilic aromatic substitution (EAS) processes. The dominant process mainly depends on the relative position of the hydroxyl substituents and the possibility of quinone formation. While phenol, p-hydroxybenzoic acid and bisphenol A undergo EAS, hydroquinone, catechol, gallic acid and tannic acid, with hydroxyl substituents in ortho or para positions, react with bromine by ET leading to quantitative formation of the corresponding quinones. Some compounds (e.g. phloroglucinol) show both partial oxidation and partial electrophilic aromatic substitution and the ratio observed for the pathways depends on the pH. For the reaction of six NOM extracts with bromine, electrophilic aromatic substitution accounted for only 20% of the reaction, and for one NOM extract (Pony Lake fulvic acid) it accounted for <10%. This shows that for natural organic matter samples, oxidation (ET) is far more important than bromine incorporation (EAS).

Iodate and Iodo-Trihalomethane Formation during Chlorination of Iodide-Containing Waters: Role of Bromide

The kinetics of iodate formation is a critical factor in mitigation of the formation of potentially toxic and off flavor causing iodoorganic compounds during chlorination. This study demonstrates that the formation of bromine through the oxidation of bromide by chlorine significantly enhances the oxidation of iodide to iodate in a bromide-catalyzed process. The pH-dependent kinetics revealed species specific rate constants of k(HOBr + IO(-)) = 1.9 × 10(6) M(-1) s(-1), k(BrO(-) + IO(-)) = 1.8 × 10(3) M(-1) s(-1), and k(HOBr + HOI) < 1 M(-1) s(-1). The kinetics and the yield of iodate formation in natural waters depend mainly on the naturally occurring bromide and the type and concentration of dissolved organic matter (DOM). The process of free chlorine exposure followed by ammonia addition revealed that the formation of iodo-trihalomethanes (I-THMs), especially iodoform, was greatly reduced by an increase of free chlorine exposure and an increase of the Br(-)/I(-) ratio. In water from the Great Southern River (with a bromide concentration of 200 μg/L), the relative I-incorporation in I-THMs decreased from 18 to 2% when the free chlorine contact time was increased from 2 to 20 min (chlorine dose of 1 mg Cl(2)/L). This observation is inversely correlated with the conversion of iodide to iodate, which increased from 10 to nearly 90%. Increasing bromide concentration also increased the conversion of iodide to iodate: from 45 to nearly 90% with a bromide concentration of 40 and 200 μg/L, respectively, and a prechlorination time of 20 min, while the I-incorporation in I-THMs decreased from 10 to 2%.

Comparison of POCIS passive samplers vs. composite water sampling: A case study

The relevance of Polar Organic Chemical Integrative Samplers (POCIS) was evaluated for the assessment of concentrations of 46 pesticides and 19 pharmaceuticals in a small, peri-urban river with multi-origin inputs. Throughout the period of POCIS deployment, 24h-average water samples were collected automatically, and showed the rapid temporal evolution of concentrations of several micropollutants, as well as permitting the calculation of average concentrations in the water phase for comparison with those estimated from POCIS passive samplers. In the daily water samples, cyproconazol, epoxyconazol and imidacloprid showed high temporal variations with concentrations ranging from under the limit of detection up to several hundreds of ngL-1. Erythromycin, cyprofloxacin and iopromide also increased rapidly up to tens of ngL-1 within a few days. Conversely, atrazine, caffeine, diclofenac, and to a lesser extent carbamazepine and sucralose, were systematically present in the water samples and showed limited variation in concentrations. For most of the substances studied here, the passive samplers gave reliable average concentrations between the minimal and maximal daily concentrations during the time of deployment. For pesticides, a relatively good correlation was clearly established (R2=0.89) between the concentrations obtained by POCIS and those gained from average water samples. A slight underestimation of the concentration by POCIS can be attributed to inappropriate sampling rates extracted from the literature and for our system, and new values are proposed. Considering the all data set, 75% of the results indicate a relatively good agreement between the POCIS and the average water samples concentration (values of the ratio ranging between 0,33 and 3). Note further that this agreement between these concentrations remains valid considering different sampling rates extracted from the literature.

A new application of passive samplers as indicators of in-situ biodegradation processes

In this paper, a method for evaluating the in-situ degradation of nitro polycyclic aromatic hydrocarbons (nitro-PAH) in sediments is presented. The methodology is adapted from the passive sampler technique, which commonly uses the dissipation rate of labeled compounds loaded in passive sampler devices to sense the environmental conditions of exposure. In the present study, polymeric passive samplers (made of polyethylene strips) loaded with a set of labeled polycyclic aromatic hydrocarbons (PAH) and nitro-PAH were immersed in sediments (in field and laboratory conditions) to track the degradation processes. This approach is theoretically based on the fact that a degradation process induces a steeper concentration gradient of the labeled compounds in the surrounding sediment, thereby increasing their compound dissipation rates compared with their dissipation in abiotic conditions. Postulating that the degradation magnitude is the same for the labeled compounds loaded in polyethylene strips and for their native homologs that are potentially present in the sediment, the field degradation of 3 nitro-PAH (2-nitro-fluorene, 1-nitro-pyrene, 6-nitro-chrysene) was semi-quantitatively analyzed using the developed method.

On the bioavailability of trace metals in surface sediments: a combined geochemical and biological approach

The bioavailability of metals was estimated in three river sediments (Sensée, Scarpe, and Deûle Rivers) impacted by different levels of Cu, Cd, Pb, and Zn (Northern France). For that, a combination of geochemistry and biological responses (bacteria and chironomids) was used. The results obtained illustrate the complexity of the notion of “bioavailability.” Indeed, geochemical indexes suggested a low toxicity, even in surface sediments with high concentrations of total metals and a predicted severe effect levels for the organisms. This was also suggested by the abundance of total bacteria as determined by DAPI counts, with high bacterial cell numbers even in contaminated areas. However, a fraction of metals may be bioavailable as it was shown for chironomid larvae which were able to accumulate an important quantity of metals in surface sediments within just a few days.We concluded that (1) the best approach to estimate bioavailability in the selected sediments is a combination of geochemical and biological approaches and that (2) the sediments in the Deûle and Scarpe Rivers are highly contaminated and may impact bacterial populations but also benthic invertebrates.

Assessing the transport of PAH in the surficial sediment layer by passive sampler approach

A new method based on passive samplers has been developed to assess the diffusive flux of fluorene, fluoranthene and pyrene in the sediment bed and across the sediment-water interface. The dissolved compound concentration gradient in the sediment in the vertical direction was measured at the outlet of a storm water pond by using polyethylene strips as passive samplers. Simultaneously, the dissipation of a set of tracer compounds preloaded in the passive samplers was measured to estimate the effective diffusion coefficients of the pollutants in the sediment. Both measurements were used to evaluate the diffusive flux of the compounds according to Ficks first law. The diffusive fluxes of the 3 studied compounds have been estimated with a centimetre-scale resolution in the upper 44cm of the sediment. According to the higher compound diffusion coefficient and the steeper concentration gradient in the surficial sediment layer, the results show that the net flux of compounds near the sediment interface (1cm depth) is on average 500 times higher than in the deep sediment, with average fluxes at 1cm depth on the order of 5, 0.1 and 0.1ng/m2/y for fluorene, fluoranthene and pyrene, respectively.