Formation Of Cl Research Articles

In-situ generation of highly-reactive FeIV=O and its contribution during CH4 conversion to CH3OH

Photocatalytic CH4 conversion to CH3OH under mild conditions is undoubtedly an efficient strategy to realize CH4 upgrading. In this work, in-situ formed highly reactive FeIV=O complex with a bound Cl axial ligand was detected at ambient temperature and its contribution to CH4 photoxidation to CH3OH was deeply investigated. Under optimized experimental condition, a high CH3OH yield of 3026.1 mmol molFe−1 (6.76 mmol gcat−1 h−1) with selectivity of 73.6 % was obtained during 8 h. Isotope labeling mass spectroscopy experiments manifested that O2 was the only source of oxygen in products. The formation of Cl-(H2O)4FeIVO complex was confirmed using low-temperature electron spin resonance spectroscopy and cryogenic Raman spectroscopy (ν(FeO) = 828 cm−1). Through density functional theory (DFT) calculation, we showed that the Cl axial ligand acts as an “electron reservoir” during CH4 conversion, i.e., electron acceptor during the process of CH4 oxidation to CH3OH, while electron donor in CH3OH desorption. This not only lowered C-H cleavage energy, but also facilitated CH3OH desoption and inhibited overoxidation. As far as we know, Cl-(H2O)4FeIVO is the first detected FeIVO complex generated directly from O2 and Fe3+ at ambient temperature.

Impact of Molecular Chlorine Production from Aerosol Iron Photochemistry on Atmospheric Oxidative Capacity in North China.

Elevated levels of atmospheric molecular chlorine (Cl2) have been observed during the daytime in recent field studies in China but could not be explained by the current chlorine chemistry mechanisms in models. Here, we propose a Cl2 formation mechanism initiated by aerosol iron photochemistry to explain daytime Cl2 formation. We implement this mechanism into the GEOS-Chem chemical transport model and investigate its impacts on the atmospheric composition in wintertime North China where high levels of Cl2 as well as aerosol chloride and iron were observed. The new mechanism accounts for more than 90% of surface air Cl2 production in North China and consequently increases the surface air Cl2 abundances by an order of magnitude, improving the model's agreement with observed Cl2. The presence of high Cl2 significantly alters the oxidative capacity of the atmosphere, with a factor of 20-40 increase in the chlorine radical concentration and a 20-40% increase in the hydroxyl radical concentration in regions with high aerosol chloride and iron loadings. This results in an increase in surface air ozone by about 10%. This new Cl2 formation mechanism will improve the model simulation capability for reactive chlorine abundances in the regions with high emissions of chlorine and iron.

In-situ oxidation of ammonia nitrogen to N2 in low temperature groundwater through Cl• − mediated peroxymonosulfate – Fe3O4 / chlorine process

The conventional ammonia in-situ treatment technology fails to achieve complete NH4+-N degradation, while the high concentration of native iron in groundwater further complicates its removal process, potentially leading to adverse environmental consequences. This study investigates the introduction of peroxymonosulfate (PMS) into groundwater containing high concentrations Fe2+ (Fe3O4 as a ferrous source), which can act as persistent catalysts, and Cl-, causing the degradation of ammonia through chlorine free radical-based advanced oxidation processes (PMS- Fe3O4/Cl-), and evaluates the advantages and limitations of employing the PMS- Fe3O4/Cl- system for ammonia treatment. The rapid reaction between SO4•- and Cl- resulted in the formation of Cl• as primary products. Cl• initiates a cascade of subsequent reactions with pH-dependent secondary active products. Under optimal conditions, the ammonia removal efficiency reached 97.44 % using the PMS- Fe3O4/Cl- system within 120 min of operation, which can be attributed to the selective oxidation of ammonia by chlorine reactive species. And this finding was substantiated by observations from experiments involving free radical quenching and EPR spectra coupled with DMPO. The HCO3– and humic acid (HA) in water can significantly affect the removal of ammonia, owing to their capability of quenching SO4•- and Cl•. Meanwhile, the levels of generated toxic chlorates in our system remain within acceptable limits. The PMS- Fe3O4/Cl- system exhibited outstanding transport capacity and stability in simulated columns, demonstrating excellent ammonia oxidation efficiency in natural groundwater, thereby confirming its promising practical potential. All experiments were executed at a temperature of 12 ℃, thereby verifying the remarkable efficacy of the PMS- Fe3O4/Cl- system in removing ammonia even under microtherm conditions.

Salinity-Induced Changes in Heavy Metal Behavior and Mobility in Semi-Arid Coastal Aquifers: A Comprehensive Review

Semi-arid coastal aquifers face critical challenges characterized by lower rainfall, higher evaporation rates, and looming risk of over-exploitation. These conditions, coupled with climate change, are conducive to seawater intrusion and promote mechanisms associated with it. The understanding of metal behavior in such environments is limited, and hence, an attempt is made through this review to bridge the knowledge gap. A study on the behavior of trace metals within a specific context of semi-arid coastal aquifers was carried out, and 11 aquifers from 6 different countries were included. The review observed that trace metals within semi-arid coastal aquifers exhibit distinctive behaviors influenced by their surrounding environment. The prevalence of evaporation and continuous seawater intrusion played a pivotal role in shaping trace metal dynamics by curtailing groundwater flux. The findings suggest that the formation of stable Cl and organic ligands under increased alkaline conditions (pH > 8) has higher control over Zn, Pb, and Cd toxicity in a highly ionic reactive condition. In addition, dominant control of Fe/Mn-hydroxide association with Pb and high organic affinity of Zn played a pivotal role in controlling its bioavailability in aquifers such as WFB, Saudi Arabia NW-C and India. On the contrary, under prevailing acidic conditions (pH < 6), carbonate and SO4-ligands become more dominant, controlling the bioavailability/desorption of Cu irrespective of its origin. The behavior of Ni is found to be controlled by stable organic ligands increasing salinity. An increase in salinity in the considered aquifers shows an increase in bioavailability of Ni, except UmC, South Africa, where organic ligands act as a sink for the metal, even at low pH conditions (pH < 5.5). This study indicates that factors such as mineral saturation, carbonate complexes, pH variations (pH > 8), and chloride complexes govern the distribution of trace metals further enhanced by prolonged water residence time. Nonetheless, specific conditions, such as a reducing and acidic environment, could potentially elevate the solubility of highly toxic Cr (VI) released from anthropogenic sources.

The impact of indole and mucin on sporulation, biofilm formation, and enterotoxin production in foodborne Clostridium perfringens.

Indole and mucin are compounds found in the host environment as they are produced by the host or by the host-associated microbiota. This study investigated whether indole and mucin impact Clostridium perfringens growth and sporulation, as well as enterotoxin production and biofilm formation. There was no impact on growth of Cl. perfringens for up to 400µM indole and 240mg/l mucin, and neither indole nor mucin affected sporulation. Reverse-transcriptase qPCR showed that mucin strongly upregulated the expression of Cl. perfringens enterotoxin (up to 121-fold increase), whereas indole had a much more modest effect (2-fold). This was also reflected in increased Cl. perfringens enterotoxin levels in mucin-treated Cl. perfringens (as assessed by a reversed passive latex agglutination assay). Finally, mucin and indole significantly increased biofilm formation of Cl. perfringens, although the effect size was relatively small (less than 1.5 fold). These results indicate that Cl. perfringens can sense its presence in a host environment by responding to mucin, and thereby markedly increased enterotoxin production.

Efficient Catalytic Elimination of Chlorobenzene Based on the Water Vapor-Promoting Effect within Mn-Based Catalysts: Activity Enhancement and Polychlorinated Byproduct Inhibition.

Achieving no or low polychlorinated byproduct selectivity is essential for the chlorinated volatile organic compounds (CVOCs) degradation, and the positive roles of water vapor may contribute to this goal. Herein, the oxidation behaviors of chlorobenzene over typical Mn-based catalysts (MnO2 and acid-modified MnO2) under dry and humid conditions were fully explored. The results showed that the presence of water vapor significantly facilitates the deep mineralization of chlorobenzene and restrains the formation of Cl2 and dichlorobenzene. This remarkable water vapor-promoting effect was conferred by the MnO2 substrate, which could suitably synergize with the postconstructed acidic sites, leading to good activity, stability, and desirable product distribution of acid-modified MnO2 catalysts under humid conditions. A series of experiments including isotope-traced (D2O and H218O) CB-TPO provided complete insights into the direct involvement of water molecules in chlorobenzene oxidation reaction and attributed the root cause of the water vapor-promoting effect to the proton-rich environment and highly reactive water-source oxygen species rather than to the commonly assumed cleaning effect or hydrogen proton transfer processes (generation of active OOH). This work demonstrates the application potential of Mn-based catalysts in CVOCs elimination under practical application conditions (containing water vapor) and provides the guidance for the development of superior industrial catalysts.

Formation of Chlorine in the Atmosphere by Reaction of Hypochlorous Acid with Seawater.

The highly reactive dihalogens play a significant role in the oxidative chemistry of the troposphere. One of the main reservoirs of these halogens is hypohalous acids, HOX, which produce dihalogens in the presence of halides (Y-), where X, Y = Cl, Br, I. These reactions occur in and on aerosol particles and seawater surfaces and have been studied experimentally and by field observations. However, the mechanisms of these atmospheric reactions are still unknown. Here, we establish the atomistic mechanism of HOCl + Cl- → Cl2 + OH- at the surface of the water slab by performing ab initio molecular dynamics (AIMD) simulations. Main findings are (1) This reaction proceeds by halogen-bonded complexes of (HOCl)···(Cl-)aq surrounded with the neighboring water molecules. (2) The halogen bonded (HOCl)···(Cl-)aq complexes undergo charge transfer from Cl- to OH- to form transient Cl2 at neutral pH. (3) The addition of a proton to one proximal water greatly facilitates the Cl2 formation, which explains the enhanced rate at low pH.

Dichlorine-pyridine N-oxide halogen-bonded complexes.

A new Cl-Cl···-O-N+ halogen-bonded paradigm has been demonstrated, using dichlorine as a halogen bond (XB) donor and N-oxide as an XB acceptor. Their crystalline complexes were formed during the warm-up process from -196 °C to -80 °C for X-ray diffraction analysis. They exhibit high instability in the crystalline state, even at these low temperatures, leading to rapid decomposition and the formation of Cl⋯H-O-N hydrogen-bonded complexes. The normalized XB interaction ratio (R XB) of Cl⋯O interactions in the solid-state demonstrates affinity comparable to traditional I⋯O interactions observed in I-I···-O-N+ halogen-bonded systems. The Cl-Cl⋯O XB angles vary from 172° to 177°, manifesting the structure-guiding influence of the electronegative chlorine atom's σ-hole on these XB interactions.

Acidic chloride electrolyte mediates the high conversion ratio of CO2-to-C2H4 and direct production of Cl2

We design an efficient catalytic system for C2 and Cl2 formation by coupling CO2R and CER in an acidic environment. It can support C2H4 and Cl2 with 63% and 89% FEs at 700 mA cm−2. This provides a valuable reference for the development of the CO2RR.

Comprehensive multiphase chlorine chemistry in the box model CAABA/MECCA: implications for atmospheric oxidative capacity

Abstract. Tropospheric chlorine chemistry can strongly impact the atmospheric oxidation capacity and composition, especially in urban environments. To account for these reactions, the gas- and aqueous-phase Cl chemistry of the community atmospheric chemistry box model Chemistry As A Boxmodel Application/Module Efficiently Calculating the Chemistry of the Atmosphere (CAABA/MECCA) has been extended. In particular, an explicit mechanism for ClNO2 formation following N2O5 uptake to aerosols has been developed. The updated model has been applied to two urban environments with different concentrations of NOx (NO + NO2): New Delhi (India) and Leicester (United Kingdom). The model shows a sharp build-up of Cl at sunrise through Cl2 photolysis in both the urban environments. Besides Cl2 photolysis, ClO+NO reaction and photolysis of ClNO2 and ClONO are also prominent sources of Cl in Leicester. High-NOx conditions in Delhi tend to suppress the nighttime build-up of N2O5 due to titration of O3 and thus lead to lower ClNO2, in contrast to Leicester. Major loss of ClNO2 is through its uptake on chloride, producing Cl2, which consequently leads to the formation of Cl through photolysis. The reactivities of Cl and OH are much higher in Delhi; however, the Cl/OH reactivity ratio is up to ≈ 9 times greater in Leicester. The contribution of Cl to the atmospheric oxidation capacity is significant and even exceeds (by ≈ 2.9 times) that of OH during the morning hours in Leicester. Sensitivity simulations suggest that the additional consumption of volatile organic compounds (VOCs) due to active gas- and aqueous-phase chlorine chemistry enhances OH, HO2, and RO2 near sunrise. The simulation results of the updated model have important implications for future studies on atmospheric chemistry and urban air quality.

Removal of kathon by UV-C activated hydrogen peroxide: Kinetics, mechanisms, and enhanced biodegradability assessment

Kathon (CMI-MI), a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one (CMI) and 2-methyl-4-isothiazolin-3-one (MI), was extensively used in industry as a nonoxidizing biocide or disinfectant. However, it would show adverse effects on aquatic life when it is discharged into surface water.In this study, the removal performance, parameter influence, degradation products and enhancement of subsequent biodegradation of CMI-MI in UV/H2O2 system were systematically investigated. The degradation rate of CMI-MI could reach 90% under UV irradiation for 20 min when the dosage of H2O2 was 0.3 mmol·L–1. The DOC (dissolved organic carbon) mineralization rate of CMI-MI could reach 35% under certain conditions ([H2O2] = 0.3 mmol·L–1, UV irradiation for 40 min). kobs was inversely proportional to the concentration of CMI-MI and proportional to the concentration of H2O2. The degradation rate of CMI-MI was almost unchanged in the pH range from 4 to 10. Except the presence of CO32- inhibited the removal rate of CMI-MI, SO42-, Cl−, NO3-, and NH4+ did not interfere with the degradation of CMI-MI in the system. It was found that UV/H2O2 system had lower energy consumption and more economic advantage compared with UV/PS system by comparing the EEO (electric energy per order) values under the same conditions. Two main organic products were identified, namely HCOOH and CH3NH2. There’s also the formation of Cl− and SO42-. After UV and UV/H2O2 photolysis, the biochemical properties of CMI-MI solution were obviously improved, especially the UV/H2O2 treatment effect was better, indicating that UV/H2O2 technology is expected to combine with biotechnology to remove CMI-MI effectively and environmentally friendly from wastewater.

Flow-through electrochemical organophosphorus degradation and phosphorus recovery: The essential role of chlorine radical

Phosphorus scarcity and the deleterious ecological impact of the release of organophosphorus pesticides have emerged as critical global issues. Previous research has shown the ability of electrochemistry to induce the precipitation of calcium phosphate from phosphorus-laden wastewater to recover the phosphorus. The current study presents a flow-through electrochemical system consisting of a column-shaped electrochemical reactor, a tubular stainless-steel (SS) cathode, and a titanium suboxides (TiSO) anode. This system simultaneously oxidizes tetrakis (hydroxymethyl) phosphonium sulfate (THPS) and recycles phosphates. The influence of current density, flow rate, and initial calcium ions concentration were examined under continuous flow operation. To enhance the electrochemical reactor's performance, we elevated the current density from 5 to 30 mA cm−2, which caused the phosphorus recovery efficiency to increase from 37% to 72% within 120 min, accompanied by an enhancement of the THPS mineralization efficiency from 57% to 90%. These improvements were likely due to the higher yield of reactive species chloride species (Cl•) formed at the TiSO anode and the higher local pH at the cathode. By investigating the formation of Cl• at the TiSO anode, we found that THPS mineralization exceeded 75% in the presence of NaCl at a current density of 20 mA cm−2. The demonstrated performance of the flow-through electrochemical system should enable the utilization of anodic oxidation-cathodic precipitation for the recovery of phosphorus from organophosphorus-contaminated wastewater.

The impact of chlorides on NMC leaching in hydrometallurgical battery recycling

The current paper studies the impact of chlorides on NMC111 (LiNi1/3Mn1/3Co1/3O2) leaching mechanism. Experiments were conducted in chloride (HCl) and mixed sulfate–chloride (H2SO4–NaCl) solutions as well as in sulfate solution (H2SO4, reference), in the absence of external reductants. The results suggest no major differences in the leaching performance between studied lixiviants at 30 °C (∼75% for Li, ∼35% for Co, Ni, Mn), and increasing the temperature to 80 °C mainly improved the dissolution of lithium (>90% in all lixiviants). However, the leaching behavior of manganese was found to be different – in sulfate solutions, Mn precipitated as MnO2 with only 6% Mn left in solution after 2 h (at 80 °C), whereas in chloride-containing solutions, dissolved Mn remained soluble (30–40% extraction). The presence of chlorides also supported cobalt and nickel extraction, the mixed H2SO4–NaCl system resulting in extractions of 55% for Co and 58% for Ni at 80 °C. The increase in the dissolutions is suggested to be explained by the experimentally verified reaction between Cl- ions and NMC111, resulting in Cl2 formation and simultaneous NMC dissolution. The results indicate that hydrometallurgical battery recycling processes may face challenges with manganese extraction to solution when operating at increased temperatures, and that the presence of chloride ions can help to mitigate such difficulties by inhibiting unwanted precipitation of manganese compounds, producing Cl2 gas as a result. Nevertheless, as the final extractions were low even in the most effective lixiviant (55% Co, 58% Ni, 39% Mn at 80 °C), the use of additional reductants is necessary to ensure high metal leaching efficiencies also in such chloride-containing systems.

Observation of nitrogen oxide-influenced chlorine chemistry and source analysis of Cl2 in the Yangtze River Delta, China

Atmospheric chlorine (Cl)- and nitrogen (N)-containing species such as Cl2, ClNO2, and N2O5 participate actively in atmospheric chemistry by triggering radical reactions that lead to the formation of secondary pollutants. Despite of their importance in atmospheric chemistry, the measurements of these species are scarce, due to analytical challenges. Herein, we report observation results of Cl2, ClNO2, and N2O5 from measurements using high-resolution time-of-flight chemical ionization mass spectrometry (HR-ToF-CIMS) in Shanghai and Changzhou in the highly industrialized and populated Yangtze River Delta (YRD) of East China. In Changzhou, the maximum concentrations of N2O5, ClNO2, and Cl2, were 0.4, 1.3, and 0.5 ppbv (1-min averages), respectively, while they were 0.5, 5.7, and 1.1 ppbv, respectively, in Shanghai. Much higher ClNO2 levels were found in Shanghai compared to Changzhou, although the concentrations of the precursor (N2O5) are similar, indicating different heterogenous N2O5 uptake and Cl activation efficiency at these two sites. The diurnal variation of Cl2 in Shanghai shows a strong daytime peak, which is contradictory to its fast lost by photolysis during daytime; the diurnal pattern of Cl2 in Changzhou shows a prominent night peak and a much smaller daytime peak than that in Shanghai. The heterogeneous uptake of ClNO2 and the photolysis of O3 on chloride-containing aerosols are believed to contribute to efficient Cl2 formation at night and day, respectively. The estimated heterogeneous uptake coefficient of O3 is 0.004 ± 0.007, with a maximum of 0.034. Further analysis on these heterogeneous reactions with the help of aerosol composition data (chloride, liquid water content, pH etc.) was also performed to ascertain the role of the secondary formation of Cl2 in daytime Shanghai. Through simple estimation methods, the maximum daytime production rate of Cl2 was estimated to be 0.95 ppbv h−1, while daytime photolysis of Cl2 contributed to 98% of Cl formation. Our results indicate that there is a large secondary source of Cl2 in the YRD region during the day, which can contribute substantially to Cl formation and requires more investigations.

Synergistic oxidation of NH3 and Hg0 over Cu-ATP catalyst: Influence of SO2 and reaction mechanisms

NH3 and Hg0 could be synergistically oxidized by copper modified attapulgite (Cu3-ATP) catalyst at the gas hourly space velocity (GHSV) below 5 × 104 h−1 despite competition exist between these two reactions. Its Hg0 oxidation showed good sulfur resistance when HCl was present, but the NH3 oxidation was partially inhibited after SO2 was added. In order to explain this phenomenon, the composition and physical characteristics of Cu3-ATP before and after sulfurization were characterized by XRF, BET, XRD and FTIR. And H2-TPR, NH3-TPD, in situ DRIFT and XPS of the catalysts were adopted to reveal the influence of SO2 on NH3/Hg0 oxidation and the reaction mechanisms. The results showed that SO2 would adsorb and oxidize on the catalyst surface to form very small amount of sulfite and sulfate species, and partially change the composition and structure of Cu3-ATP. This reduced the reducibility of Cu3-ATP and increased the weak and moderate acid sites on its surface. The presence of SO2 was beneficial to NH3 adsorption, but inhibited NH2 → NOx conversion in iSCR mechanism for NH3 oxidation. Cl2 formation were also inhibited by SO2, while the generated surface active Cl and O species could ensure high Hg0 oxidation efficiency.

Nontoxic Artificial Chloride Channel Formation in Epithelial Cells by Isophthalic Acid-Based Small Molecules.

Artificial channels capable of facilitating the transport of Cl- ions across cell membranes while being nontoxic to the cells are rare. Such synthetic ion channels can mimic the functions of membrane transport proteins and, therefore, have the potential to treat channelopathies by replacing defective ion channels. Here we report isophthalic acid-based structurally simple molecules 1 a and 2 a, which self-assemble to render supramolecular nanochannels that allow selective transport of Cl- ions. As evident from the single-crystal X-ray diffraction analysis, the self-assembly is governed by intermolecular hydrogen bonding and π-π stacking interactions. The MD simulation studies for both 1 a and 2 a confirmed the formation of stable Cl- channel assembly in the lipid membrane and Cl- transport through them. The MQAE assay showed the efficacy of the compounds in delivering Cl- ions into cells, and the MTT assays proved that the compounds are nontoxic to cells even at a concentration of 100 μM.

Thiabendazole degradation by photo-NaOCl/Fe and photo-Fenton like processes, using copper slag as an iron catalyst, in spiked synthetic and real secondary wastewater treatment plant effluents.

Thiabendazole degradation (TBZD) in diferent types of water matrices was assessed by applying two Advanced Oxidation Processes, both using simulated solar light (SSL), copper slag (CS) as an iron based catalyst, and separately H2O2 or NaOCl as oxidants. First, optimum conditions for TBZD were evaluated in distilled water, TBZD = 90% at 60 min for CS-H2O2-SSL, and 92% of TBZD in a twelfth of the time by the system CS-NaOCl-SSL; minimum TBZ depletion variations were observed between the first and the fifth reuse test: 88 ± 2% for CS-H2O2-SSL (60 min) and 90 ± 1% for CS-NaOCl-SSL (5 min). Those conditions were tested using a synthetic (SE) and a real secondary effluent (RE) from a wastewater treatment plant. The CS-H2O2-SSL system achieved TBZD of 88 and 77% after 90 min for SE and RE, with kinetic constants of 0.024 and 0.016 min-1, respectively, whereas photo-NaOCl/Fe showed values of 0.365 and 0.385 min-1 for SE and RE, achieving a 94% TBZD removal in both types of water at 10 min. That might be related to the formation of Cl· and HO• during the photo-NaOCl/Fe process, highlighting that the CS-NaOCl-SSL is an attractive option that has great possibilities for scaling up by a better knowledge in real aqueous matrices.

Io’s Volcanic Activity and Atmosphere

Driven by tidal heating, Io’s extreme volcanism has created a young, impact crater–free surface dominated by hundreds of active volcanic centres. From these volcanoes erupt voluminous, low-viscosity, high-temperature silicate lavas. Volcanic plumes, from venting gas and mobilised surface ices (primarily SO2 and S), contribute to Io’s thin atmosphere. Away from volcanoes, SO2 ice on the surface alternately sublimes during the daytime and condenses during eclipses and at night, resulting in a strong day/night atmospheric dichotomy. Sunlight and radiation bombardment at high altitude breaks the gas molecules apart, leading to the formation of SO, O, O2, S, K, Na, and Cl. These atoms reside as both neutral and charged particles in clouds that are found along Io’s orbit around Jupiter.

Suppression on PCDD/Fs formation by a novel inhibition system consisting of phosphorous-based compounds coupled with a chlorine-deactivation material

The SN-containing inhibitors are effective for suppressing the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the post-combustion zone of municipal solid waste incineration systems, but the industrial application of the SN-containing inhibitors is restricted by the high cost and the generation of corrosive by-products (e.g., SOx). To develop cost-effective and environmentally friendly inhibitors, a new inhibition system consisting of P-based compounds (i.e., NH4H2PO4 (ADP) and KH2PO4 (PDP)) and a chlorine-deactivation material (CaO) was proposed in this study. Also, the performance of this inhibition system in terms of suppressing PCDD/Fs formation was evaluated in an experimental system which simulated PCDD/Fs generation in the post-combustion zone. Generally, the formation of PCDD/Fs was effectively suppressed by over 95 % by the mixed inhibitors (ADP/CaO and PDP/CaO) and the individual inhibitor of ADP. Based on the observation on PCDD/F-fingerprints and the chemical speciation of Cl and Cu, the mechanisms of inhibitors were identified as: (i) passivating metal catalyst by converting the speciation of Cu from chlorides and Cu2+ with high reactivities to phosphates, oxides, and Cu+ with low reactivities, and (ii) deactivating Cl by CaO to prevent the formation of organic Cl which was critical for PCDD/Fs formation. In addition, both mechanisms were supported by (i) the better performance of inhibitors on suppressing the PCDD/F-congeners formed via de novo pathway than congeners synthesized from chlorophenols and (ii) lower degrees of chlorination of PCDD/Fs for reaction systems with CaO involved than other systems.

Chloride Enhances DNA Reactivity with Chlorine under Conditions Relevant to Water Treatment.

Free available chlorine (FAC) is widely used to inactivate viruses by oxidizing viral components, including genomes. It is commonly assumed that hypochlorous acid (HOCl) is the chlorinating agent responsible for virus inactivation; however, recent studies have underscored that minor constituents of FAC existing in equilibrium with HOCl, such as molecular chlorine (Cl2), can influence FAC reactivity toward select organic compounds. This study measures the FAC reaction kinetics with dsDNA and ssDNA extracted from representative bacteriophages (T3 and ϕX174) in samples augmented with chloride. Herein, chloride enhances FAC reactivity toward dsDNA and, to a lesser extent, toward ssDNA, especially at pH < 7.5. The enhanced reactivity can be attributed to the formation of Cl2. Second-order rate constants were determined for reactions of ssDNA and dsDNA with HOCl and Cl2. DNA chlorination kinetics followed the reactivity-selectivity principle, where the more-reactive nucleophilic species (ssDNA, ∼100× more reactive than dsDNA) reacted less selectively with electrophilic FAC species. The addition of chloride was also shown to enhance the inactivation of bacteriophage T3 (dsDNA genome) by FAC but did not enhance the inactivation of bacteriophage ϕX174 (ssDNA genome). Overall, the results suggest that Cl2 is an important chlorinating agent of nucleic acids and viruses.