Health Risk Assessment of Employees Exposed to Chlorination By-products of Recreational Water in Large Amusement Parks in Shanghai

Objective Chlorination is often used to disinfect recreational water in large amusement parks;however,the health hazards of chlorination disinfection by-products(DBPs)to occupational populations are unknown.This study aimed to assess the exposure status of chlorinated DBPs in recreational water and the health risks to employees of large amusement parks.Methods Exposure parameters of employees of three large amusement parks in Shanghai were investigated using a questionnaire.Seven typical chlorinated DBPs in recreational water and spray samples were quantified by gas chromatography,and the health risks to amusement park employees exposed to chlorinated DBPs were evaluated according to the WHO's risk assessment framework.Results Trichloroacetic acid,dibromochloromethane,bromodichloromethane,and dichloroacetic acid were detected predominantly in recreational water.The carcinogenic and non-carcinogenic risks of the five DBPs did not exceed the risk thresholds.In addition,the carcinogenic and non-carcinogenic risks of mixed exposure to DBPs were within the acceptable risk limits.Conclusion Typical DBPs were widely detected in recreational water collected from three large amusement parks in Shanghai;however,the health risks of DBPs and their mixtures were within acceptable limits.

Molecular packing tuning via chlorinated end group enables efficient binary organic solar cells over 18.5%

Designing novel nonfullerene acceptors(NFAs)is of vital importance for the development of organic solar cells(OSC).Modification on the side chain and end group are two powerful tools to construct efficient NFAs.Here,based on the high-performance L8BO,we selected 3-ethylheptyl to substitute the inner chain of 2-ethylhexyl,obtaining the backbone of BON3.Then we introduced different halogen atoms of fluorine and chlorine on 2-(3-oxo-2,3-dihydro-1Hinden-1-ylidene)malononitrile end group(EG)to construct efficient NFAs named BON3-F and BON3-Cl,respectively.Polymer donor D18 was chosen to combine with two novel NFAs to construct OSC devices.Impressively,D18:BON3-Cl-based device shows a remarkable power conversion efficiency(PCE)of 18.57%,with a high open-circuit voltage(V_(OC))of 0.907 V and an excellent fill factor(FF)of 80.44%,which is one of the highest binary PCE of devices based on D18 as the donor.However,BON3-F-based device shows a relatively lower PCE of 17.79%with a decreased FF of 79.05%.The better photovoltaic performance is mainly attributed to the red-shifted absorption,higher electron and hole mobilities,reduced charge recombination,and enhanced molecular packing in the D18:BON3-Cl films.Also,we performed stability tests on two binary systems;the D18:BON3-Cl and D18:BON3-F devices maintain 88.1%and 85.5%of their initial efficiencies after 169 h of storage at 85°C in an N2-filled glove box,respectively.Our work demonstrates the importance of selecting halogen atoms on EG and provides an efficient binary system of D18:BON3-Cl for further improvement of PCE.

Progress in Analytical Methods of Halogenated Disinfection By-Products

Ensuring the health and safety of drinking water is crucial for both nations and their citizens.Since the 20th century,the disinfection of drinking water,effectively controlling pathogens in water sources,has become one of the significant advances in public health.However,the disinfectants used in the process,such as chlorine and chlorine dioxide,react with natural organic matter in the water to produce disinfection by-products(DBPs).Most of these DBPs contain chlorine,and if the source water contains bromine or iodine,brominated or iodinated DBPs,collectively referred to as Halogenated disinfection byproducts(X-DBPs),are formed.Numerous studies have found that X-DBPs pose potential risks to human health and the environment,leading to widespread concern.Mass spectrometry has become an important means of discovering new types of X-DBPs.This paper focuses on the study of methods for analyzing X-DBPs in drinking water using mass spectrometry.

Prescreening teratogenic potential of chlorinated drinking water disinfection by-products by using Hydra regeneration assay

Practicability of method for the Hydra regeneration assay on the prescreening teratogenic potential of chlorinated drinking water disinfection by products was studied through both the assays of toxicity of adult Hydra (T) and inhibition of the growth of regeneration Hydra (I) by using chloroform, dichloromethane and chloroacetic acid. The results showed that T 50 / I 50 ratios of chloroform and chloroacetic acid were 2 77 and 6 16 respectively, with teratogenic potential. T 50 / I 50 ratio of dichloromethane was 1.69, with weaker teratogenic potential. These experimental results indicated preliminarily that the Hydra regeneration assay has certainly applied value as a prescreening assay for developmental toxicity.

Simultaneous Control of Microorganisms and Disinfection By-products by Sequential Chlorination

Objective To introduce a new sequential chlorination disinfection process in which short-term free chlorine and chloramine are sequentially added. Methods Pilot tests of this sequential chlorination were carried out in a drinking water plant. Results The sequential chlorination disinfection process had the same or better efficiency on microbe （including virus） inactivation compared with the free chlorine disinfection process. There seemed to be some synergetic disinfection effect between free chlorine and monochloramine because they attacked different targets. The sequential chlorination disinfection process resulted in 35.7%-77.0% TTHM formation and 36.6%-54.8% THAA5 formation less than the free chlorination process. The poorer the water quality was, the more advantage the sequential chlorination disinfection had over the free chlorination. Conclusion This process takes advantages of free chlorine＇s quick inactivation of microorganisms and chloramine＇s low disinfection by-product （DBP） yield and long-term residual effect, allowing simultaneous control of microbes and DBPs in an effective and economic way.

Ordinary Toxicity of Chlorine Dioxide and By-products Chlorite and Chlorate in Water

Acute toxicity and accumulated toxicity of chlorine dioxide (ClO2) and by-products chlorite (ClO2-) and chlorate (ClO3-) in water acted on mice are studied by the method of Horn and accumulation coefficient. Subchronic toxicity of the mixture of ClO2 and ClO2-and ClO3- in water acted on rat is studied though feeding test for 90 days, including statistical analysis of variance on weight gaining, food utilization efficiency,index of blood and serum,liver (or kidney) to body weight ratio, and histopathological examination on liver and kidney. The results show that aqueous solution of ClO2, NaClO2 and NaClO3 ( with the concentration of 276.5 mg/L, 200 mg/L and 200 mg/L respectively) and the mixed aqueous solution of ClO2 with the concentration of 553 mg/L are actually non-poisonous , and non-cumulative aqueous solution as well.

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.

Reduction of Precursors of Chlorination By-products in Drinking Water Using Fluidized-bed Biofilm Reactor at Low Temperature

Objective To investigate the reduction of chlorination by-products （CBPs） precursors using the fluidized-bed biofdm reactor （FBBR）. Methods Reduction of total organic carbon （TOC）, ultraviolet absorbance （UV254）, tfihalomethane （THM） formation potential （THMFP）, haloacetic acid （HAA） formation potential （HAAFP）, and ammonia in FBBR were evaluated in detail. Results The reduction of TOC or UV254 was low, on average 12.6% and 4.7%, respectively, while the reduction of THMFP and HAAFP was significant. The reduction of ammonia was 30%-40% even below 3℃, however, it could quickly rise to over 50% above 3℃. Conclusions The FBBR effectively reduces CBPs and ammonia in drinking water even at low temperature and seems to be a very promising and competitive drinking water reactor for polluted surface source waters, especially in China.

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.

Low-temperature chlorination roasting technology for the simultaneous recovery of valuable metals from spent LiCoO_(2)cathode material

With the continuous increase in the disposal volume of spent lithium-ion batteries(LIBs),properly recycling spent LIBs has become essential for the advancement of the circular economy.This study presents a systematic analysis of the chlorination roasting kinetics and proposes a new two-step chlorination roasting process that integrates thermodynamics for the recycling of LIB cathode materials.The activation energy for the chloride reaction was 88.41 kJ/mol according to thermogravimetric analysis–derivative thermogravimetry data obtained by using model-free,model-fitting,and Z(α)function(αis conversion rate).Results indicated that the reaction was dominated by the first-order(F1)model when the conversion rate was less than or equal to 0.5 and shifted to the second-order(F2)model when the conversion rate exceeded 0.5.Optimal conditions were determined by thoroughly investigating the effects of roasting temperature,roasting time,and the mass ratio of NH_(4)Cl to LiCoO_(2).Under the optimal conditions,namely 400℃,20 min,and NH_(4)Cl/LiCoO_(2)mass ratio of 3:1,the leaching efficiency of Li and Co reached 99.43% and 99.05%,respectively.Analysis of the roasted products revealed that valuable metals in LiCoO_(2)transformed into CoCl_(2) and LiCl.Furthermore,the reaction mechanism was elucidated,providing insights for the establishment of a novel low-temperature chlorination roasting technology based on a crystal structure perspective.This technology can guide the development of LIB recycling processes with low energy consumption,low secondary pollution,high recovery efficiency,and high added value.

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.

The Toxic Effects of Strong Chlorin Disinfectant on Mangroves and Emission Thresholds

In this study, based on the simulated discharge results of chemical disinfectants, hypocotyl germination concentration gradient pre-test and concentration gradient determination experiment were set up respectively. Laboratory cultivation was conducted to compare and analyze the root germination and germination indexes, three mangrove hypocotyls of Kandelia candel (Linn.) Druce, Ceriopstagal C.B. Rob. and Bruguiera sexangula var. Rhynchopetalas’ efficiency of cumulative root germination, cumulative germination and the cumulative expansion of the second pair of leaves, one-way analysis of variance was used to obtain the tolerance threshold of three mangrove hypocotyls to strong chlorin disinfectant. The study determined that the by-products of strong chlorin disinfectant, the toxic threshold concentrations of Kandelia candel (Linn.) Druce, Ceriopstagal C.B. Rob. and Bruguiera sexangula var. rhynchopetala are close to 0.55 mg/L, 0.55 mg/L and 0.25 mg/L, respectively. This concentration range is lower than the average concentration of 1.183 mg/L of active chlorine emitted from strong chlorine concentrate during pond clearing in high-level shrimp ponds, indicating that transient emissions of strong chlorine concentrate during pond clearing can have a toxic effect on mangrove plants. The strength of tolerance of the embryonic axes of the three mangrove species to effective chlorine contamination was, Ceriopstagal C.B. Rob. stronger than Bruguiera sexangula var. rhynchopetala, and Kandelia candel (Linn.) Druce is the weakest.

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.

High Resolution Mass Spectrometry Elucidation of Captopril’s Ozonation and Chlorination By-Products

The article evaluated the degradation of the captopril in aqueous solution after ozonation and chlorination. The process was continuously monitored focusing on the identification, mass spectrometry and elucidation of its by-products by applying direct infusion and high performance liquid chromatography, electrospray ionization high resolution mass spectrometry, in the negative ion mode. The cytotoxicity of its by-products solutions were evaluated with 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide (MTT) assay. It was observed through that after 30 min of ozonation and chlorination, there was complete oxidation of captopril, i.e., 100% removal efficiency. At these conditions, the rate of mineralization, by total organic carbon, was only 7.63% for ozonation and 6.40% for chlorination, evidencing the formation of degradation by-products. Ten captopril by-products were identified and their respective chemical structures elucidations are proposed. The treated samples and their by-products were nontoxic to HepG2 cells by MTT assay.

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.

Effects of molasses on the fermentation characteristics of mixed silage prepared with rice straw, local vegetable by-products and alfalfa in Southeast China

This experiment was conducted to study the effect of molasses on the fermentation characteristics of mixed silage ensiled rice straw and vegetable by-products with alfalfa.Mixture（202 g kg^-1 dry matter（DM））consisting of rice straw,broccoli residue and alfalfa at the ratio of 5：4：1 was ensiled with three experimental treatments：（1）no additives（control）;（2）molasses at 2.5%（M1）;（3）molasses at 5%（M2）on a fresh matter basis of mixture,respectively.All treatments were packed into laboratory-scale silos,and three silos per treatment were sampled on days 1,3,5,14 and 30.The result showed that the p H value of all mixed silages decreased gradually with the time of ensiling except for the control silage,in which a significant increase（P〈0.05）on day 30 occurred.The lactic acid content increased gradually with the time of ensiling and reached the highest value on day 14,and a marked decrease（P〈0.05）was found in the control silage on day 30.The changes of acetic acid content showed similar pattern with lactic acid content.A trace amount of propionic and butyric acid contents were found in the three mixed silages during the fermentation period.Comparing to the control,M1 and M2 treatments improved the fermentation quality of mixed silages as indicated by higher（P〈0.05）lactic acid contents and lower（P〈0.05）p H and ammonia-N contents.The Flieg points also showed that M1 and M2 silages were well preserved,whereas the control silage had a bad quality.Overall,the findings of this study suggested that adding molasses could improve fermentation quality of mixed silage,and M1 was more suitable for practical application.

Formation potentials of typical disinfection byproducts and changes of genotoxicity for chlorinated tertiary effluent pretreated by ozone

The effects of ozonation on the formation potential of typical disinfection byproducts （DBPs） and the changes of genotoxicity during post chlorination of tertiary effluent from a sewage treatment plant were investigated. Ozonation enhanced the yields of all detected chlorine DBPs except CHCI3. At a chlorine dose of 5 mg/L, the three brominated THMs and five HAAs increased, while chloroform decreased with the increase of ozone dose from 0 to 10 mg/L （ozone dose in consumption base）. At a chlorine dose of 10 mg/L, the two mixed bromochloro species THMs and two dominant HAAs （DCAA and TCAA） increased firstly and then decreased with the increase of ozone dose, with the turning point approximately occurring at an ozone dose of 5 mg/L. The genotoxicity detected using umu test, on the other hand, was removed from 7 Ixg 4-NQO/L to a negligible level by ozonation under an ozone dose of 5 mg/L. Chlorination could further remove the genotoxicity to some extent. It was found that SUVA （UV absorbance divided by DOC concentration） might be used as an indicative parameter for monitoring the removal of genotoxicity during the oxidation.

Residual Levels and New Inputs of Chlorinated POPs in Agricultural Soils from Taihu Lake Region

Selected persistent organochlorine pesticides (OCPs), including 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) and its principal metabolites 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (DDE) and 1,1-dichloro-2,2-bis(p-chlorophenyl)e- thane (DDD), hexachlorocyclohexane (HCH) and its isomers (α-,β-, γ-, and δ-HCH), hexachlorobenzene (HCB), endo- sulfan, dieldrin, and endrin were quantified to determine current levels of organochlorine pesticides, to assess the eco- toxicological potential, and to distin…