Reactions of the amine-containing drugs fluoxetine and metoprolol during chlorination and dechlorination processes used in wastewater treatment

The reactivities of the amine-containing pharmaceuticals fluoxetine and metoprolol with hypochlorite were studied using conditions that simulate wastewater disinfection including neutral pH (7.0), a range of reaction times (2–60 min), and a molar excess of hypochlorite relative to the pharmaceutical concentration (5.7 times). The reactions were monitored using liquid chromatography (LC) with several detection modes including ultraviolet absorbance (UV), mass spectrometry (MS), and post-column reaction/reductive electrochemistry (EC) for determining active chlorine products. At levels of 10 μM, both compounds reacted rapidly (<2 min) to form principally N-chloramine products that were stable in aqueous solution for at least 1 h. The reaction was also studied in wastewater, and similar reactivity was noted. These results demonstrate that the cations fluoxetine and metoprolol are likely to be rapidly transformed into neutral N-chloramines during wastewater disinfection. The reactivity of the N-chloramines was also studied with sulfite to simulate dechlorination, which is often employed in wastewater treatment. Both N-chloramines reacted slowly with sulfite. In the pure water dechlorination experiments, it was estimated that 70% and 10% of the peak areas remained after 2 min reaction time for fluoxetine and metoprolol, respectively. At longer reaction times both N-chloramines had been completely reduced by sulfite, and the product of the sulfite reduction reaction was the parent pharmaceutical amine. Since typical dechlorination times in wastewater treatment are on the order of seconds, this suggests the chloramines formed from these two basic drugs might evade dechlorination and be released into the environment. The implications of chloramine release are discussed.     

Response of mussel Brachidontes variabilis to chlorination

Brachidontes variabilis is a common fouling mussel species in cooling water systems of tropical coastal power stations. However, there are hardly any data available on the response of B. variabilis to chlorine, a commonly used antifouling biocide. Therefore, lethal and sublethal responses of this mussel to chlorine are of considerable interest to the industry. The response of mussels in terms of mortality pattern (LT₅₀ and LT₁₀₀) and physiological activities (oxygen consumption, filtration rate, foot activity and byssus thread production) in different size groups (with shell lengths of 7–24 mm) of B. variabilis was studied in the laboratory under different chlorine concentrations (0.25, 0.50, 0.75 and 1.00 mg l^?1 for sublethal responses and 1, 2, 3 and 5 mg l^?1 for mortality). The results showed that the exposure time for 100% mortality of mussels decreased significantly with increasing chlorine concentration. However, mussel size was not a determinant of its chlorine tolerance: all size groups tested (with shell lengths of 7–24 mm) took comparable exposure times to reach 100% mortality at a given chlorine concentration (1–5 mg l^?1). All size groups of B. variabilis showed a progressive reduction in physiological activities such as oxygen consumption, filtration rate, foot activity and byssus thread production, when chlorine residuals were increased from 0 to 1 mg l^?1. The data generated in the present work are compared with similar data available for other tropical fouling mussel species to see how far relative chlorine toxicity could have influenced the relative distribution of the mussels inside the seawater intake tunnel of a power station at Kalpakkam in India. It is shown that in this insufficiently chlorinated system, the relative distribution of Brachidontes striatulus, B. variabilis and Modiolus philippinarum reflects the relative tolerance of the species to chlorine.     

Effect of ammonium sulfate and urea on PCDD/F formation from active carbon and possible mechanism of inhibition

The effect of ammonium sulfate （（NH4）2SO4） and urea （CO（NH2）2） on polychlorinated dibenzo-p-dioxin and dibenzofuran （PCDD/F） formation from active carbon was investigated in this study. Both additives could significantly inhibit PCDD/F formation, and PCDD/F （TEQ） generation was reduced to 98.5% （98%） or 64.5% （77.2%） after 5% （NH4）2S04 or CO（NH2）2 was added into model ash, respectively. The inhibition efficiency of PCDDs was higher than the value of PCDFs, however, the reduction of PCDD/F yield was mainly from PCDFs decreasing. In addition, the solid-phase products were reduced more than the gas-phase compounds by inhibitors. By the measurement of chlorine emission in the phase of ion （Cl[Cl^-]） and molecule gas （Cl[Cl2]）, it was observed that both Cl[Cl^-] and Cl[Cl2] were reduced after inhibitors were added into ash. Cl[Cl2] was reduced to 51.0% by urea addition, which was supposed as one possible mechanism of PCDD/F inhibition.     

Effect of CaO on retention of S, Cl, Br, As, Mn, V, Cr, Ni, Cu, Zn, W and Pb in bottom ashes from fluidized-bed coal combustion power station

This work was conducted to evaluate whether Ca-bearing additives used during coal combustion can also help with the retention of some other elements. This work was focused on the evaluation of bottom ashes collected during four full-scale combustion tests at an operating thermal fluidized-bed power station. Bottom ashes were preferred to fly ashes for the study to avoid interference from condensation processes usually occurring in the post-combustion zone. This work focused on the behaviors of S, Cl, Br, As, Mn, V, Cr, Ni, Cu,Zn, W, and Pb. Strong positive correlations with CaO content in bottom ashes were observed（for all four combustion tests） for S, As, Cl and Br（R = 0.917-0.999）. Strong inverse proportionality was calculated between the contents of Pb, Zn, Ni, Cr and Mn and CaO, so these elements showed association to materials other than Ca-bearing compounds（e.g., to aluminosilicates, organic matter, etc.）. Somewhat unclear behaviors were observed for W, Cu, and V. Their correlation coefficients were evaluated as statistically ＂not significant＂, i.e., these elements were not thought to be significantly associated with CaO. It was also discovered that major enrichment of CaO in the finest bottom ash fractions could be advantageously used for simple separation of elements strongly associated with these fractions, mainly S and As, but also Cl or Br. Removal of5% of the finest ash particles brings about a decrease in As concentration down to 77%-80% of its original bulk ash content, which can be conveniently used e.g., when high As content complicates further ash utilization.     

浅析融雪剂对城市环境的影响

融雪剂是一把双刃剑,在快速除雪保障交通畅通的同时,也给城市带来了一系列的环境问题。对融雪剂对城市环境的影响进行了探讨分析,并提出了今后使用融雪剂的建议和策略。     

Characterization of halogenated DBPs and identification of new DBPs trihalomethanols in chlorine dioxide treated drinking water with multiple extractions

Chlorine dioxide(ClO_2) is a widely used alternative disinfectant due to its high biocidal efficiency and low-level formation of trihalomethanes and haloacetic acids. A major portion of total organic halogen(TOX), a collective parameter for all halogenated DBPs, formed in ClO_2-treated drinking water is still unknown. A commonly used pretreatment method for analyzing halogenated DBPs in drinking water is one-time liquid–liquid extraction(LLE), which may lead to a substantial loss of DBPs prior to analysis. In this study, characterization and identification of polar halogenated DBPs in a ClO_2-treated drinking water sample were conducted by pretreating the sample with multiple extractions. Compared to one-time LLE, the combined four-time LLEs improved the recovery of TOX by 2.3 times. The developmental toxicity of the drinking water sample pretreated with the combined four-time LLEs was 1.67 times higher than that pretreated with one-time LLE.With the aid of ultra-performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry, a new group of polar halogenated DBPs, trihalomethanols,were detected in the drinking water sample pretreated with multiple extractions; two of them,trichloromethanol and bromodichloromethanol, were identified with synthesized standard compounds. Moreover, these trihalomethanols were found to be the transformation products of trihalomethanes formed during ClO_2disinfection. The results indicate that multiple LLEs can significantly improve extraction efficiencies of polar halogenated DBPs and is a better pretreatment method for characterizing and identifying new polar halogenated DBPs in drinking water.     

Characteristics of typical dissolved black carbons and their influence on the formation of disinfection by-products in chlor(am)ination

● The physicochemical and structural properties of DBC were characterized. ● The effects of DBC on DBPs and DBPFP generation during disinfection were evaluated. ● The DBPs and DBPFP generation during chlor(am)ination were compared. Dissolved black carbon (DBC) released from biochar can be one of the potential disinfection by-products (DBPs) precursors in the dissolved organic matter pool. However, the physiochemical and structural properties of DBC and the effects on the development of DBPs and DBP formation potential (DBPFP) during the disinfection process remain unclear. In this study, the characteristics of two kinds of DBC, namely, animal-derived DBC (poultry litter DBC, PL-DBC) and plant-derived DBC (wheat straw DBC, WS-DBC), were investigated. The effects of different kinds of DBC on the evolution of DBPs and DBPFP in chlorine and chloramine disinfection processes were compared with natural organic matter (NOM). The results showed that the total DBPs concentrations derived from PL-DBC, WS-DBC and NOM were similar during chlorination (i.e., 61.23 μg/L, 64.59 μg/L and 64.66 μg/L, respectively) and chloramination (i.e., 44.63 μg/L, 44.42 μg/L and 45.58 μg/L, respectively). The lower total DBPs and DBPFP concentrations in chloramination could be attributed to the fact that the introduction of ammonia in chloramine inhibited the breaking of the bond between the disinfectant and the active group of the precursor. Additionally, DBC presented much lower total DBPFP concentrations than NOM in both chlorination and chloramination. However, both kinds of DBC tended to form more monochloroacetic acids and haloacetamides than NOM, which could result from the higher organic strength, higher protein matter, and nitrogen-rich soluble microbial products of DBC.     

The role of metal oxides on oxidant decay and disinfection byproduct formation in drinking waters: Relevance to distribution systems

Maintaining a residual disinfectant/oxidant (e.g., chlorine and chlorine dioxide), is a generally used strategy to control microbial contaminants and bacterial regrowth in distribution systems. Secondarily oxidant, such as hypobromous acid (HOBr), can be formed during chlorination of bromide-containing waters. The decay of oxidants and formation of disinfection byproducts (DBPs) due to the interaction between oxidants and selected metal oxides were studied. Selected metal oxides generally enhanced the decay of these halogen-containing oxidants via three pathways: (1) catalytic disproportionation to yield an oxidized form of halogen (i.e., halate) and reduced form (halide for chlorine and bromine or chlorite for chlorine dioxide), (2) oxygen formation, and (3) oxidation of a metal in a reduced form (e.g., cuprous oxide) to a higher oxidation state. Cupric oxide (CuO) and nickel oxide (NiO) showed significantly strong abilities for the first pathway, and oxygen formation was a side reaction. Cuprous oxide can react with oxidants via the third pathway, while goethite was not involved in these reactions. The ability of CuO on catalytic disproportionation of HOBr remained stable up to four cycles. In chlorination process, bromate formation tends to be important (exceeding 10 µg/L) when initial bromide concentration is above 400 µg/L in the presence of dissolved organic matter. Increasing initial bromide concentrations increased the formation of DBPs and calculated cytotoxicity, and the maximum was observed at pH 8.6 during chlorination process. Therefore, the possible disinfectant loss and DBP formation should be carefully considered in drinking water distribution systems.