Efficiency of ozonation and sulfate radical - AOP for removal of pharmaceuticals, corrosion inhibitors, x-ray contrast media and perfluorinated compounds from reverse osmosis concentrates.

This study investigated the elimination of pharmaceuticals, corrosion inhibitors, x-ray contrast media and perfluorinated compounds from reverse osmosis concentrates during ozonation and UV/persulfate processes. Second-order rate constants for the reactions of candesartan, irbesartan, methyl-benzotriazole, and chloro­benzotriazole with sulfate radical (SO4·-) were determined for the first time. Experiments were conducted in buffered pure water, in buffered water added with the matrix substituents chloride, carbonate, NOM, and reverse osmosis concentrate with spiked micropollutants (MP). UV/persulfate eliminated all MP to a higher extent than ozonation in RO concentrates due to the higher yield of oxidative species and photolytic degradation. Compounds with electron-rich moieties such as carbamazepine, diclofenac, metoprolol, and sulfamethoxazole were completely eliminated with small ozone doses (< 0.5 mg O3 / mg DOC) and with a small fluence (< 5000 J m-2) in UV/persulfate processes. Photosensitive compounds with high reactivity towards hydroxyl radicals (·OH) and SO4·- like the x-ray contrast media Iopamidol, Iohexol, and Amidotrizoic acid were successfully eliminated with a reasonable fluence in UV/persulfate, whereas these compounds persist in ozonation at common ozone dosages. However, much higher fluences and ozone dosages were required for the least reactive compounds like the class of benzotriazoles. Comparing the application of both oxidative processes to the RO concentrate, ozonation has the disadvantage of forming bromate. The energy input of both processes strongly depends on the target compounds to be eliminated. For the elimination of compounds such as sulfamethoxazole, ozonation is a feasible technique, whereas UV/persulfate is better suited for the elimination of recalcitrant compounds such as x-ray contrast media. In general, oxidative process treatment of RO concentrate could be applied to partly abate micropollutants before discharge.

Elucidating nicotine transfer into water environments via cigarette butt remaining parts.

Nicotine, the main alkaloid in tobacco, enters water environments through discarded cigarette butts (CBs), possibly causing detrimental effects. However, there is no comprehensive investigation on the long-term leaching of nicotine from the different CBs parts. Therefore, in the present study, the ecological risk and the leachate levels of nicotine from different CBs parts were investigated. Freshly smoked CBs, aged CBs collected from streets, remaining tobacco and ash of freshly smoked CBs, and filter plus paper of freshly smoked CBs were evaluated for the leachate experiments. The order of nicotine leachate from different types of CBs and parts investigated were as remaining tobacco plus ash of freshly smoked CBs > freshly smoked CBs > aged CBs > filter plus paper of freshly smoked CBs with the ranges of 5.73-17.34, 0.36-8.6, 0.31-4.12, and 0.17-2.79 mg of nicotine per g of CB or remaining parts (mg g-1), respectively. The ecological risk assessment revealed that nicotine leachates from all the CBs types or their remaining parts could be highly hazardous to fish, cladocerans, algae, and Daphnia magna. Based on the mean leachate levels of nicotine via freshly smoked CBs at exposure times of 1 min to 1 month and the estimated number of littered CBs every year on a worldwide scale, freshly smoked CBs may release 380-7065 tons of nicotine into water environments.

Oxidation of the N-containing phosphonate antiscalants NTMP and DTPMP in reverse osmosis concentrates: Reaction kinetics and degradation rate.

N-containing organophosphonate antiscalants such as Aminotris (methylene phosphonic acid) (NTMP/ATMP) and Diethylenetriamine penta(methylene phosphonic acid) (DTPMP) are commonly used in reverse osmosis (RO) to prevent scaling, as well as to increase permeate yields. However, the concentrate in RO still contains antiscalants which can cause adverse effects in the environment such as mobilization of heavy metals. The abatement of antiscalants from RO concentrate can promote the precipitation of oversaturated scale-forming substances and reduce the risk of adverse environmental effects. In the present study, the degradation of NTMP and DTPMP as representatives for N-containing organophosphonate by ozone, hydroxyl radicals (•OH), and sulfate radicals (SO4•-) are studied regarding reaction kinetics and degradation in different matrices. The results show that NTMP and DTPMP react fast with ozone and sulfate radicals (formed in UV/persulfate). Reaction rate constants of ozone showed a strong pH dependency due to the dissociation of the amine. The apparent reaction rates for pH 7 have been determined to be kapp(NTMP + ozone) = 1.44 × 105 M-1 s-1 and kapp(DTPMP + ozone) = 1.16 × 106 M-1 s-1. Reaction kinetics of •OH and SO4•- did not play a distinctive pH dependency (k(•OH) = 109-1010 M-1 s-1 and k(SO4•-) = 107-108 M-1 s-1). Furthermore, real water experiments have shown that ozonation and UV/persulfate are effective tools to abate organophosphonates in RO concentrates. The formation of carcinogenic bromate in ozonation is minimized by the presence of N-containing organophosphonates presumably due to enhanced ozone consumption and scavenging of free bromine.

Oxidation of the nitrogen-free phosphonate antiscalants HEDP and PBTC in reverse osmosis concentrates: Reaction kinetics and degradation rate.

Reverse osmosis (RO) is an advanced technology used to produce potable water from a variety of water sources, including surface water, seawater and wastewater. The yield of the product water from the RO systems is increased by the addition of antiscalants which prevent scaling from calcium and other ions. Removal of antiscalants from RO concentrate can induce the precipitation of oversaturated scale-forming substances, enable additional water recovery from RO concentrates, and reduce the risk of eutrophication after concentrate disposal into the receiving water (e.g., river water). This study aims to provide a better insight into oxidation reactions of the N-free phosphonate antiscalants 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) with ozone, hydroxyl radical (•OH) and sulfate radicals (SO4•-). Ozone barely reacts with HEDP and PBTC at pH 7 (k < 10 M-1s - 1), while second order reaction rates of SO4•- and •OH were determined to be in the range 107-108M - 1s - 1. Sulfate, silicate and chloride matrices increased HEDP ozone degradation rate possibly due to metal complexation effect. Whereas carbonate and chloride hindered PBTC ozone degradation, and natural organic matter (NOM) inhibited both HEDP and PBTC degradation through scavenging of •OH. The SO4•-- radical based oxidation process of HEDP and PBTC is mainly inhibited by carbonate and NOM, interestingly only HEDP degradation is inhibited by chloride whereby the PBTC could not be fully degraded (degradation < 60%). The oxidation of PBTC is in real RO concentrates in both processes limited to 10% degradation, whereas HEDP could be degraded up to 60% with ozone and UV/persulfate application.

Aromatic amines leachate from cigarette butts into aquatic environments: Is there risk for water organisms?

There are many toxics, such as aromatic amines (AAs), in cigarette butts (CBs). As CBs are the most abundant litter worldwide, these chemicals may leach into water bodies. In the present work, for the first time, the levels of AAs leachates from CBs in distilled water (DW) and river water (RW) samples were evaluated at different exposure times ranging from 15 min to 30 days. The mean leachate levels of AAs in DW and RW samples were in the range of 0.2-566 and 0.2-596 ng L-1, respectively, with overall mean values of 569 and 556 ng L-1. There was no significant difference (p > 0.05) between the total AAs levels as well as the level of each examined AA in DW and RW samples. Aniline (ANL) had the highest leaching rate from CBs into water. The mean leachates of AAs from CBs into water were ranked as: ANL> 1-naphthylamine (1-NA)> 2-naphthylamine (2-NA) > 2,6-dimethylaniline (2, 6-DMA)> ∑toluidine (∑TOL)> o-anisidine (o-ASD)> ∑aminobiphenyl (∑ABP). Ecological risk assessment showed that ∑7AAs, ANL, p-TOL, o-TOL, 2-NA, and ∑ABP had medium risks to sensitive crustaceans and fish. As AAs are not the only hazardous chemicals which may leach from CBs into aquatic environments, restrictions on littering CBs into the environment are required due to the release of different toxics ultimately causing adverse effects on aquatic organisms.

Reaction of Chlorine Dioxide with Saturated Nitrogen-Containing Heterocycles and Comparison with the Micropollutant Behavior in a Real Water Matrix.

Chlorine dioxide (ClO2) is a very selective oxidant that reacts with electron-rich moieties such as activated amines and thus can degrade specific N-containing micropollutants. N-containing heterocycles (NCHs) are among the most frequent moieties of pharmaceuticals. In this study, the reactions of ClO2 with ritalinic acid and cetirizine, two abundant micropollutants, and model compounds representing their NCH moiety were investigated. The pH-dependent apparent reaction rates of all NCHs with ClO2 were measured and modeled. This model showed that neutral amines are the most important species having reaction rates between 800 and 3200 M-1 s-1, while cationic amines are not reactive. Ritalinic acid, cetirizine, and their representative model compounds showed a high stoichiometric ratio of ≈5 moles ClO2 consumption per degraded ritalinic acid and ≈4 moles ClO2 consumption per degraded cetirizine, respectively. Investigation of chlorine-containing byproducts of ClO2 showed that all investigated NCHs mostly react by electron transfer and form above 80% chlorite. The reactions of the model compounds were well comparable with cetirizine and ritalinic acid, indicating that the model compounds indeed represented the reaction centers of cetirizine and ritalinic acid. Using the calculated apparent reaction rate constants, micropollutant degradation during ClO2 treatment of surface water was predicted for ritalinic acid and cetirizine with -8 to -15% and 13 to -22% error, respectively. The results indicate that in ClO2-based treatment, piperidine-containing micropollutants such as ritalinic acid can be considered not degradable, while piperazine-containing compounds such as cetirizine can be moderately degraded. This shows that NCH model compounds could be used to predict micropollutant degradation.

Aromatic amines contents of cigarette butts: Fresh and aged cigarette butts vs unsmoked cigarette.

Cigarette butts (CBs) are some of the most abundant waste items in the environment and may contain high levels of different toxic chemicals, such as aromatic amines (AAs). However, to this date, there is no comprehensive study on the role of CBs in the emission of AAs into the environment. The present study investigated for the first time the concentration levels of 10 primary aromatic amines (PAAs), including ANL, p-TOL, m-TOL, o-TOL, 2,6-DMA, o-ASD, 2-NA, 1-NA, 3-ABP, and 4-ABP that were measured and compared in unsmoked cigarette, freshly smoked CBs, and CBs collected from urban streets (named here aged CBs). The mean levels of ∑PAAs in different sample categories were statistically significantly different and the mean level order was as freshly smoked CBs > aged CBs > unsmoked cigarette with the values of 3.43, 2.12 µg g-1, and 0.28 µg g-1, respectively. The levels of ∑PAAs, ANL, o-ASD, 2,6-DMA, 2-NA, and ∑TOL dramatically increased by 12.26, 4.05, 8.46, 10.41, 4.78, and 28.84 times, respectively, right after smoking comparing the freshly smoked CBs samples and unsmoked cigarette. The results also showed a substantial decrease in the levels of PAAs (except o-ASD) in the aged CBs samples compared to freshly smoked CBs. The levels of ∑PAAs, o-ASD, 2,6-DMA, ∑TOL, ANL, 2-NA, 1-NA, and ∑ABP decreased 1.62, 1.09, 1.91, 3.20, 3.42, 2.63, 2.00, and 1.88 times, respectively. Considering the average PAAS content and estimated CBs littered worldwide every year, freshly smoked CBs can theoretically emit 2.9 tons of ∑PAAs into the environment annually. Considering other chemicals that may also be released into the environment via CBs (beside PAAs), we can consider CBs as a critical source of toxic compounds into the environment and water bodies.