Effects of Chlorine and Chlorine Monoxide on Stratospheric Ozone Depletion

This paper presents a system approach of mass balance calculations of ozone and other species under diffusion-convection-reaction processes to study the impacts of major ozone-depleting chemicals, chlorine (Cl) and chlorine monoxide (ClO), and the effect of photolysis on ozone concentrations, ozone depletion, total ozone abundance, and ozone layer along the altitude in the stratosphere. The calculated ozone concentrations and profile of the layer followed a similar trend and were generally in good agreement with the measurements above the tropical area. The calculated peak of the layer was at the same mid-stratosphere at Z = 30 km with a peak concentration and total ozone abundance about 20% higher than the measured peak concentration of 8.0 ppm and total abundance of 399 DU. In the presence of Cl and ClO, the calculated ozone concentrations and total abundance were substantially reduced. Cl generally depleted more uniformly of ozone across the altitude, while ClO reduced substantially the ozone in the upper stratosphere and thus shifted the peak of the layer to a much lower elevation at Z = 14 km. Although both ClO and Cl are active ozone-depleting chemicals, ClO was found to have a more pronounced impact on ozone depletion and distribution than Cl. The possible explanations of these interesting phenomena were discussed and elaborated. The approach and calculations in this paper were shown to be useful in providing an initial insight into the structure and behavior of the complex ozone layer.

Unveiling the geometric site dependent activity of spinel Co_(3)O_(4)for electrocatalytic chlorine evolution reaction

Spinel cobalt oxide(Co_(3)O_(4)),consisting of tetrahedral Co^(2+)(CoTd)and octahedral Co^(3+)(CoOh),is considered as promising earth-abundant electrocatalyst for chlorine evolution reaction(CER).Identifying the catalytic contribution of geometric Co site in the electrocatalytic CER plays a pivotal role to precisely modulate electronic configuration of active Co sites to boost CER.Herein,combining density functional theory calculations and experiment results assisted with operando analysis,we found that the Co_(Oh) site acts as the main active site for CER in spinel Co_(3)O_(4),which shows better Cl^(-)adsorption and more moderate intermediate adsorption toward CER than CoTd site,and does not undergo redox transition under CER condition at applied potentials.Guided by above findings,the oxygen vacancies were further introduced into the Co_(3)O_(4) to precisely manipulate the electronic configuration of Co_(Oh) to boost Cl^(-)adsorption and optimize the reaction path of CER and thus to enhance the intrinsic CER activity significantly.Our work figures out the importance of geometric configuration dependent CER activity,shedding light on the rational design of advanced electrocatalysts from geometric configuration optimization at the atomic level.

One-Step Scalable Fabrication of Nitrogen and Chlorine Co-doped Graphene by Electrochemical Exfoliation for High-Performance Supercapacitors

The stacking and aggregation of graphene nanosheets have been obstacles to their application as electrode materials for microelectronic devices.This study deploys a one-step,scalable,facile electrochemical exfoliation technique to fabricate nitrogen(N)and chlorine(Cl)co-doped graphene nanosheets(i.e.,N-Cl-G)via the application of constant voltage on graphite in a mixture of 0.1 mol/L H_(2)SO_(4)and 0.1 mol/L NH_(4)Cl without using dangerous and exhaustive operation.The introduction of Cl(with its large radius)and N,both with high electrical negativity,facilitates the modulation of the electronic structure of graphene and creation of rich structural defects in it.Consequently,in the as-constructed supercapacitors,N-Cl-G exhibits a high specific capacitance of 77 F/g at 0.2 A/g and remarkable cycling stability with 91.7%retention of initial capacitance after 20,000 cycles at 10 A/g.Furthermore,a symmetrical supercapacitor assembled with N-Cl-G as the positive and negative electrodes(denoted as N-Cl-G//N-Cl-G)exhibits an energy density of 3.38 Wh/kg at a power density of 600 W/kg and superior cycling stability with almost no capacitance loss after 5000 cycles at 5 A/g.This study provides a scalable protocol for the facile fabrication of high-performance co-doped graphene as an electrode material candidate for supercapacitors.

Effects of surface chlorine atoms on charge distribution and reaction barriers for photocatalytic CO_(2)reduction

Photocatalytic CO_(2)reduction to produce high value-added carbon-based fuel has been proposed as a promising approach to mitigate global warming issues.However,the conversion efficiency and product selectivity are still low due to the sluggish dynamics of transfer processes involved in proton-assisted multi-electron reactions.Lowering the formation energy barriers of intermediate products is an effective method to enhance the selectivity and productivity of final products.In this study,we aim to regulate the surface electronic structure of Bi_(2)WO_(6)by doping surface chlorine atoms to achieve effective photocatalytic CO_(2)reduction.Surface Cl atoms can enhance the absorption ability of light,affect its energy band structure and promote charge separation.Combined with DFT calculations,it is revealed that surface Cl atoms can not only change the surface charge distribution which affects the competitive adsorption of H_(2)O and CO_(2),but also lower the formation energy barrier of intermediate products to generate more intermediate*COOH,thus facilitating CO production.Overall,this study demonstrates a promising surface halogenation strategy to enhance the photocatalytic CO_(2)reduction activity of a layered structure Bi-based catalyst.

Calculations and Sensitivity Analysis of Chlorine-,NO_(x)-,and Bromine-Depleting Cycles of Stratospheric Ozone

This paper presents an engineering system approach using a 2D model of conservation of mass to study the dynamics of ozone and concerned chemical species in the stratosphere.By considering all fourteen photolysis,ozone-generating,and-depleting chemical reactions,the model calculated the transient,spatial changes of ozone under different physical-chemical-radiative conditions.Validation against the measured data demonstrated good accuracy,close match of our model with the observed ozone concentrations at both 20°S and 90°N locations.The deviation in the average concentration was less than 1% and in ozone profiles less than 17%.The impacts of various chlorine-(Cl),nitrogen oxides-(NO_(x)),and bromine-(Br)depleting cycles on ozone concentrations and distribution were investigated.The chlorine catalytic depleting cycle was found to exhibit the most significant impact on ozone dynamics,confirming the key role of chlorine in the problem of ozone depletion.Sensitivity analysis was conducted with levels of 25%,50%,100%,200%,and 400% of the baseline value.The combined cycles(Cl+NO_(x)+Br)showed the most significant influence on ozone behavior.The total ozone abundance above the South Pole could decrease by a small 3%,from 281 DU(Dubson Units)to 273 DU for the 25% level,or by a huge thinning of 60%to 114 DU for the 400% concentration level.When the level of chlorine gases increased beyond 200%,it would cause ozone depletion to a level of ozone hole(below 220 DU).The 2D Ozone Model presented in this paper demonstrates robustness,convenience,efficiency,and executability for analyzing complex ozone phenomena in the stratosphere.

Detection of Oxidants Such as Hydroxyl Radicals and Chlorine Electrogenerated on a BDD Electrode by Simple Methods

The aim of this work is to detect electrogenerated hydroxyl radicals and chlorine by simple and less expensive methods. Preparative electrolyses of perchloric acid (HClO4) and sodium chloride (NaCl) were performed on a boron-doped diamond (BDD) electrode. The hydroxyl radicals were quantified indirectly by assaying the samples from the HClO4 (0.1 M) electrolysis with a 10−4 M potassium permanganate solution. The investigations showed that the amount of hydroxyl radicals depends on the concentration of HClO4 and the current density. As for chlorine, a qualitative determination was carried out. A mixture of the electrolyte solution of HClO4 (0.1 M) + NaI (0.2 M) + 2 mL of hexane, taken in this order, leads to a purplish-pink coloration attesting to the presence of Cl2. The same test was carried out with NaBr and NaI giving pale and very pale pink colourations, respectively, showing that the intensity of the colouration depends on the strength of the oxidant present. In addition, oxidants were detected during the electrooxidation of metronidazole (MNZ). The results showed the participation of electrogenerated hydroxyl radicals. The generation of chlorine has also been proven. Furthermore, the degradation leads to a chemical oxygen demand (COD) removal rate of 83.48% and the process is diffusion-controlled.

Chlorine-Substituent Regulation in Dopant-Free Small-Molecule Hole-Transport Materials Improves the Effi ciency and Stability of Inverted Perovskite Solar Cells

Although doped hole-transport materials(HTMs)off er an effi ciency benefi t for perovskite solar cells(PSCs),they inevi-tably diminish the stability.Here,we describe the use of various chlorinated small molecules,specifi cally fl uorenone-triphenylamine(FO-TPA)-x-Cl[x=para,meta,and ortho(p,m,and o)],with diff erent chlorine-substituent positions,as dopant-free HTMs for PSCs.These chlorinated molecules feature a symmetrical donor-acceptor-donor structure and ideal intramolecular charge transfer properties,allowing for self-doping and the establishment of built-in potentials for improving charge extraction.Highly effi cient hole-transfer interfaces are constructed between perovskites and these HTMs by strategi-cally modifying the chlorine substitution.Thus,the chlorinated HTM-derived inverted PSCs exhibited superior effi ciencies and air stabilities.Importantly,the dopant-free HTM FO-TPA-o-Cl not only attains a power conversion effi ciency of 20.82% but also demonstrates exceptional stability,retaining 93.8%of its initial effi ciency even after a 30-day aging test conducted under ambient air conditions in PSCs without encapsulation.These fi ndings underscore the critical role of chlorine-substituent regulation in HTMs in ensuring the formation and maintenance of effi cient and stable PSCs.

Study on metal corrosion caused by chlorine dioxide of various purities

Weight lost method was used to comparatively study the corrosion behavior of four different metals under the dosage of chlorine dioxide, chlorine and their mixture respectively. The experimental results indicated that chlorine causes the most serious corrosion of carbon steel, and the higher the concentration of chlorine, the more serious the corrosion. On the contrary, metals corrosion is the least serious in the case of chlorine dioxide. The results further revealed that chlorine dioxide is the most effective water treatment reagent, making it the best choice to use extensively in circulated cooling water disinfection and corrosion control.

Full-scale study of removal effect on Cyclops of zooplankton with chlorine dioxide

Cyclops of zooplankton propagated excessively in eutrophic water body and could not be effectively inactivated by the conventional disinfections process like chlorination due to its stronger resistance to oxidation. In this paper, a full-scale study of chlorine dioxide preoxidation cooperating with routine clarification process for Cyclops removal was conducted in a waterworks. The experimental results were compared with that of the existing prechlorination process in several aspects: including the Cyclops removal efficiencies of water samples taken from the outlets of sedimentation tank and sand filter and the security of drinking water and so on. The results showed that chlorine dioxide might be more effective to inactivate Cyclops than chlorine and Cyclops could be thoroughly removed from water by pre-dosing chlorine dioxide process. The GC-MS examination and Ames test further showed that the sort and amount of organic substance in the treated water by chlorine dioxide preoxidation were evidently less than that of prechlorination and the mutagenicity of drinking water treated by pre-dosing chlorine dioxide was substantially reduced compared with prechlorination.

Determination of Chlorine and Bromine in Plant Materials by Ion Chromatography

A method was developed for determination of chlorine and bromine in plant materials by ion chromatography using temperature programing-semi molten for sample preparation. Values of detection limits of the method found were 1.0×10^-5 for CI and 1.3×10^-6 for Br. The measuring range of the method found were 0.3-20.0 mg/L for CI and 4,0-120,0 μg/L for Br. The results obtained agreed quite well with those reference values.

Pilot-scale study of removal effect on Chironomid larvae with chlorine dioxide

Chironomid larvae propagated excessively in eutrophic water body and could not be effectively inactivated by the conventional disinfection process like chlorination due to its stronger resistance to oxidation. In this paper, a pilot-scale study of chlorine dioxide preoxidation cooperating with routine clarification process for Chironomid larvae removal was conducted in Shenzhen Waterworks in Guangdong Province, China. The experimental results were compared with that of the existing prechlorination process in several aspects, including the Chironomid larvae removal efficiencies of water samples taken from the outlets of sedimentation tank, sand filter, the security of drinking water and so on. The results showed that chlorine dioxide might be more effective to inactivate Chironomid larvae than chlorine and Chironomid larvae could be thoroughly removed from water by pre-dosing chlorine dioxide process. The GC-MS examination and Ames test further showed that the sort and amount of organic substance in the treated water by chlorine dioxide preoxidation were evidently less than that ofprechlorination and the mutagenicity of drinking water treated by pre-dosing chlorine dioxide was substantially reduced compared with prechlorination.

Inactivation of Resistant Mycobacteria mucogenicum in Water:Chlorine Resistance and Mechanism Analysis

Objective To better understand the mechanism of chlorine resistance of mycobacteria and evaluate the efficiency of various disinfection processes.Methods Inactivation experiments of one strain Mycobacteria mucogenicum,isolated from a drinking water distribution system in South China were conducted with various chlorine disinfectants.Inactivation efficiency and disinfectant residual,as well as the formation of organic chloramines,were measured during the experiments.Results This strain of M.mucogenicum showed high resistance to chlorine.The CT values of 99.9% inactivation by free chlorine,monochloramine and chlorine dioxide were detected as 29.6±1.46,170±6.16,and 10.9±1.55 min（mg/L） respectively,indicating that chlorine dioxide exhibited significantly higher efficiency than free chlorine and monochloramine.It was also found that M.mucogenicum reacted with chlorine disinfectants more slowly than S.aureus,but consumed more chlorine disinfectants during longer time of contact.Lipid analysis of the cell construction revealed that 95.7% of cell membrane lipid of M.mucogenicum was composed of saturated long chain fatty acids.Saturated fatty acids were regarded as more stable and more hydrophilic which enabled the cell membrane to prevent the diffusion of chlorine.Conclusion It was concluded that different compositions of cell membrane might endow M.mucogenicum with a higher chlorine resistance.

Study of Non-Ideal Effects for Extended Gate Field Effect Transistor Chlorine Ion Sensing Device

We use the extended gate field effect transistor (EGFET)as the structure of the chlorine ion sensor,and the chlorine ion ionophores (ETH9033 and TDDMAC1)are incorporated into solvent polymeric membrane (PVC/DOS),then the chlorine ion selective membrane is formed on the sensing window,and the fabrication of the EGFET chlorine ion sensing device is completed.The surface potential on the sensing membrane of the EGFET chlorine ion sensing device will be changed in the different chlorine ion concentration solutions,then changes further gate voltage and drain current to detect chlorine ion concentration.We will study non-ideal effects such as temperature,hysteresis and drift effects for the EGFET chlorine ion sensing device in this paper,these researches will help us to improve the sensing characteristics of the EGFET chlorine ion sensing device.

Closed Loop Recycling of Chlorine for Sustainable Development of Polyurethane Industry

Increasing demand is fueling the booming polyurethane industry worldwide. An impeding issue for poly- urethane industry is how to handle the large quantity of hydrogen chloride byproduct generated from the synthesis of intermediates, i.e., isocyanates. In the meantime, the traditional chloro-alkaline process sufibrs both from the high en- ergy intensity of electrolysis method and the disparity in the chlorine and caustic soda market. To solve these prob- lems, the state-of-the-art chlorine recycling technologies are reviewed and compared. Approaches for cost-effective utilization of chlorine in polyurethane industry are investigated. Chinese academies and enterprises＇ on-going effort on the development of a novel hydrogen chloride oxidation process for the synthesis of chlorine is presented. With this process, the closed loop recycling of chlorine can be realized. Tremendous economic, environmental and social bene- fits can be expected. A wide adoption of this technology will significantly advance the sustainable development of polyurethane industry.

Date palm kernel-based GAC and its dynamic modeling of residual chlorine breakthrough curve in multimedia filter

First, the date palm kernel is used to produce granular activated carbon （GAC） by a physiochemical activation process. The process involves six steps： washing, drying, crushing, sieving, carbonization, and activation. Secondly, the ability of the produced GAC to remove pollutants is examined through batch experiments of residual chlorine adsorption whereas the equilibrium isotherm experimental data are tested for the Langmuir and Freundlich isotherms equations. Thirdly, the experimental and theoretical study of dynamic adsorption process and the effect of major operating parameters on dynamic adsorption are investigated. The results show that the Langmuir isotherm gives the best fitting to experimental data, which indicates that the residual chlorine adsorption can be characterized by mono layer adsorption behavior. The produced GAC has a great potential as an adsorbent for residual chlorine in water systems and it can compete favorably with the conventional adsorbents. The Thomas extended model with combined mass transfer resistances is used for verifying the experimental results and the results show that the proposed model coincides well with the experimental data of the dynamic adsorption process.

Investigation of heavy metal partitioning influenced by flue gas moisture and chlorine content during waste incineration

The impact of moisture on the partitioning of the heavy metals including Pb,Zn,Cu and Cd in municipal solid waste （MSW） was studied in a laboratory tubular furnace.A thermodynamic investigation using CHEMKIN software was performed to compare the experimental results.Simulated waste,representative of typical MSW with and without chlorine compounds,was burned at the background temperature of 700 and 950°C,respectively.In the absence of chlorine,the moisture content has no evident effect on the volatility of Pb,Zn and Cu at either 700 or 950°C,however,as flue gas moisture increasing the Cd distribution in the bottom ash increased at 700°C and reduced at 950°C,respectively.In the presence of chlorine,the flue gas moisture reduced the volatility of Pb,Zn and Cu due to the transformation of the more volatile metal chlorides into less volatile metal oxides,and the reduction became significant as chlorine content increase.For Cd,the chlorine promotes its volatility through the formation of more volatile CdCl 2.As a result,the increased moisture content increases the Pb,Zn,Cu and Cd concentrations in the bottom ash,which limits the utilization of the bottom ash as a construction material.Therefore,in order to accumulate heavy metals into the fly ash,MSW should be dried before incineration.

VARIATIONS IN ISOTOPIC COMPOSITIONS OF CHLORINE IN EVAPORATION-CONTROLLED SALT LAKE BRINES OF QAIDAM BASIN,CHINA

The variations in the isotopic compositions of chlorine in evaporation controlled saline lake brines were determined by using an improved procedure for precise measurement of chlorine isotopes based on Cs 2Cl + ion by thermal ionization mass spectrometry. The results showed that variation in δ 37 Cl values in these evaporation controlled brines are attributable to evaporation of brine accompanied by the deposition of saline minerals. The isotopic fractionation of chlorine between the deposited saline mineral and the co existing brine caused the variation of δ 37 Cl values in the brine. In general the isotopic fractionation of chlorine in nature indicates enrichment of 3 7Cl in the solid phase relative to 3 5Cl. The reverse isotopic fractionation of chlorine in which 3 5Cl is enriched in the solid phase, was observed to some extent during quick deposition under laboratory conditions as well as in nature. The mechanism of isotopic fractionation of chlorine during evaporation deposition was studied.

Effects of Chlorine Dioxide Gas on Postharvest Physiology and Storage Quality of Green Bell Pepper (Capsicum frutescens L.var.Longrum)

The effects of treatment of chlorine dioxide （C1Oz） gas on postharvest physiology and preservation quality of green bell peppers were studied. Green bell peppers were collected in bags and treated with 0, 5, 10, 20, and 50 mg L^-1 ClO2 gas at 10±0.5℃ for over 40 d, and the changes in postharvest physiology and preservation quality of the peppers were evaluated during the storage. The inhibition of rot of the peppers was observed for all the tested ClO2 gas treatments. The rot rates of the treated samples were 50% lesser than those of the control after day 40 of storage. The highest inhibitory effect was obtained after 50 mg L^-1 ClO2 gas treatment, where the peppers did not decay until day 30 and showed only one-fourth of the rot rate of the control at day 40 of storage. The respiratory activity of the peppers was significantly （P〈0.05） inhibited by 20 and 50 mg L^-1 ClO2 treatments, whereas no significant effects on respiratory activity were observed with 5 and 10 mg L^-1 ClO2 treatments （P〉0.05）. Except for 50 mg L^-1 ClO2, malondialdenyde （MDA） contents in the peppers treated with 5, 10, or 20 mg L^-1 ClO2 were not significantly （P〉0.05） different from those in the control. Degradation of chlorophyll in the peppers was delayed by 5 mg L-1ClO2, but promoted by 10, 20, or 50 mg L^-1 ClO2. The vitamin C content, titratable acidity, and total soluble solids of the peppers treated by all the tested ClO2 gas did not significantly change during the storage. The results suggested that ClO2 gas treatment effectively delayed the postharvest physiological transformation of green peppers, inhibited decay and respiration, maintained some nutritional and sensory quality, and retarded MDA accumulation.

Studies on the Quantitative Structure-activity Relationship of Toxicity of Chlorophenol Serial Compounds in the ab initio Methods and Substitutive Position of Chlorine Atom (N_(PCS))

20 Quantum chemical parameters of chlorophenol compounds were fully optimized by using B3LYP method on both 6-31G^＊ and 6-311G^＊ basis sets. These structural parameters are taken as theoretical descriptors, and the experimental data of 20 compounds＇ aquatic photogen toxicity（-lgEC50） are used to perform stepwise regression in order to obtain two predicted -lgEC50 correlation models whose correlation coefficients R^2 are respectively 0.9186 and 0.9567. In addition, parameters of chlorine atom＇s substitutive positions and their correlations （NPCs） are taken as descriptors to obtain another predicted -lgEC50 model with the correlation coefficient R2 of 0.9444. Correlation degree of each independent variable in the three models is verified by using variance inflation factors （VIF） and t value. In the cross-validation method, cross-validation coefficients q^2 of 3 models are respectively 0.8748, 0.9119 and 0.8993, which indicates that the relativity and prediction ability of this model are superior to those of the model obtained by topological and BLYP methods.

Roasting and chlorine leaching of gold-bearing refractory concentrate:Experimental and process analysis

This paper deals with gold extraction from a refractory concentrate by chlorine leaching.The process considers a pre-treatment of refractory materials by low temperature oxidation carried out with low oxygen concentration.The oxidized material is treated by leaching with brine.After gold adsorption/reduction onto activated carbon,iron and base metals can be precipitated by NaOH.Roasting tests show the necessity to carry out a thermal pre-treatment at least at 550°C to obtain a reduction of sulfur and mercury in the material(50%and 90%,respectively).Highest gold extraction yield(around 93%)is obtained in the leaching test performed with material sample treated at 650°C.This result confrms the necessity to optimize the thermal pre-treatment to improve Au recovery and to reduce chlorine consumption.A comparison with conventional cyanidation confrms that chlorination could be an useful alternative:in fact,gold extraction yield is quite low:57%in non-pre-treated material and 25%in pre-treatment material.